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Frontiers of Chemical Science and Engineering

Front. Chem. Sci. Eng.    2020, Vol. 14 Issue (5) : 689-748     https://doi.org/10.1007/s11705-019-1902-4
REVIEW ARTICLE
Mechanistic understanding of Cu-based bimetallic catalysts
You Han1,2, Yulian Wang1, Tengzhou Ma1, Wei Li1, Jinli Zhang1,3(), Minhua Zhang1,4()
1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
2. Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin University, Tianjin 300072, China
3. School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China
4. Key Laboratory for Green Chemical Technology of Ministry of Education, Research and Development Center for Petrochemical Technology, Tianjin University, Tianjin 300072, China
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Abstract

Copper has received extensive attention in the field of catalysis due to its rich natural reserves, low cost, and superior catalytic performance. Herein, we reviewed two modification mechanisms of co-catalyst on the coordination environment change of Cu-based catalysts: (1) change the electronic orbitals and geometric structure of Cu without any catalytic functions; (2) act as an additional active site with a certain catalytic function, as well as their catalytic mechanism in major reactions, including the hydrogenation to alcohols, dehydrogenation of alcohols, water gas shift reaction, reduction of nitrogenous compounds, electrocatalysis and others. The influencing mechanisms of different types of auxiliary metals on the structure-activity relationship of Cu-based catalysts in these reactions were especially summarized and discussed. The mechanistic understanding can provide significant guidance for the design and controllable synthesis of novel Cu-based catalysts used in many industrial reactions.

Keywords copper      bimetallic catalyst      coordination      modification mechanism      catalytic application     
Corresponding Author(s): Jinli Zhang,Minhua Zhang   
Just Accepted Date: 06 January 2020   Online First Date: 24 March 2020    Issue Date: 25 May 2020
 Cite this article:   
You Han,Yulian Wang,Tengzhou Ma, et al. Mechanistic understanding of Cu-based bimetallic catalysts[J]. Front. Chem. Sci. Eng., 2020, 14(5): 689-748.
 URL:  
http://journal.hep.com.cn/fcse/EN/10.1007/s11705-019-1902-4
http://journal.hep.com.cn/fcse/EN/Y2020/V14/I5/689
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You Han
Yulian Wang
Tengzhou Ma
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Minhua Zhang
Fig.1  Number of publications related to Cu-based bimetallic catalysts in last decades (data from Web of Science, searching by “copper” or “Cu” and “bimetallic catalyst”).
Fig.2  PDOS and d-band center for the 4d orbits of surface Cu and Co atoms of the four kinds of surface (reprinted from [48], copyright (2017), with permission from Elsevier).
Fig.3  The relative substitution energy for the replacement of one Cu atom by an Sn atom whether from the top or the layer below the surface (reprinted from [52], copyright (2016), with permission from American Chemical Society).
Fig.4  The selectivity (mol-%) of metals to (a) CH4, (b) methanol and (c) ethanol as a function of the ratio of monometallic Cu, Co and bimetallic CuCo surface sites according to DFT calculation and microkinetic modelling (reprinted from [55], copyright (2014), with permission from Wiley-VCH).
Fig.5  The interaction between Cu and Au, and the possible mechanism of selective hydrogenation of cinnamaldehyde over Cu–Au/SiO2 catalyst (reprinted from [64], copyright (2014), with permission from Wiley-VCH).
Fig.6  Major chemical reactions of the applications of Cu-based bimetallic catalysts.
Fig.7  Three reaction pathway for glycerol hydrogenolysis catalyzed by Ni/Cu/TiO2: (a) under external H2 pressure, in situ H2 produced by (b) CTH and (c) APR (reprinted from [88], copyright (2018), with permission from Elsevier).
Catalysts Composition of catalysts Preparation methods Reaction conditions Catalytic performance Comments Ref.
CuNi/Al2O3 20 wt-% CuO, 20 wt-% NiO, Cu/Ni molar ratio= 1.67:1 Wet impregnation method Aqueous glycerol solution (10 vol-%), N2 (4 MPa, 30 mL?min–1), WHSV= 2 h–1, catalyst (1.25 g), T = 523 K Glycerol conv.: 82%, 1,2-PDO yield: 24%, TOF= 1.7 h–1 Due to the Cu–Ni alloy interaction, Ni is important for glycerol reforming in inert atmosphere, generating in situ H2 that is used for acetol hydrogenation to propylene glycol [87]
CuNi/ZSM-5 20 wt-% CuO, 20 wt-% NiO, Cu/Ni molar ratio= 1.67:1 Wet impregnation method Aqueous glycerol solution (10 vol-%),
N2 (4 MPa, 30 mL?min–1), WHSVa) =2 h–1, catalyst (1.25 g), T = 523 K
Glycerol conv.: 87%, 1,2-PDO yield: 27%, TOF= 7.1 h–1 [87]
CuNi/Al2O3 20 wt-% CuO, 20 wt-% NiO, Cu/Ni molar ratio= 1.67:1 Wet impregnation method Aqueous glycerol solution (10 vol-%), H2 (4 MPa, 30 mL?min–1), WHSV= 2 h–1, catalyst (1.25 g), T = 523 K Glycerol conv.:>90%, 1,2-PDO yield: 50% (1) Ni site is not necessary when H2 is added.
(2) The high acidity of ZSM-5 favors the formation of acrolein when compared to the catalysts supported on Al2O3
[87]
CuNi/ZSM-5 20 wt-% CuO, 20 wt-% NiO, Cu/Ni molar ratio= 1.67:1 Wet impregnation method Aqueous glycerol solution (10 vol-%), H2 (4 MPa, 30 mL?min–1), WHSV= 2 h–1, catalyst (1.25 g), T = 523 K Glycerol conv.:>90%, 1,2-PDO yield: 25% [87]
Cu–Ni/γ-Al2O3 3.75 wt-% Cu, 1.25 wt-% Ni, Cu/Ni mass ratio= 3:1 Incipient wetness impregnation method Aqueous glycerol solution (40% v/v, 100 mL), H2 (3 MPa), catalyst (0.25 g), T = 523 K, stirring at 500 r?min–1 Glycerol conv.: 27%, 1,2-PDO select.: 97% The presence of Cu0.75Ni0.25Al2O4 mixed oxide phase contributes to the high PDO selectivity [81]
Cu–Ni/γ-Al2O3 10 wt-% Cu, Cu/Ni molar ratio= 1:1 Incipient wetness impregnation method Aqueous glycerol solution (20 wt-%, 100 mL), H2 (4.5 MPa), catalyst (2 g), T = 483 K, stirring at 700 r?min–1 Glycerol conv.: 59.3%, 1,2-PDO select.: 86.6%, 1,2-PDO yield: 51.3%, TOF= 53.4 h–1 Cu–Ni promotes the hydrogenolysis of C–O bonds and limits the cleavage of C–C bonds, and helps glycerol selectively convert to 1,2-PDO via a dehydration-hydrogenation pathway [82]
Cu–Ni/γ-Al2O3 20 wt-% Cu, Cu/Ni molar ratio= 1:1 Incipient wetness impregnation method Aqueous glycerol solution (20 wt-%), H2/glycerol molar ratio= 54.6, WHSV= 0.97 h–1, catalyst (4 g), T = 493 K, P = 0.75 MPa Glycerol conv.: 98.5%, 1,2-PDO yield: 88%, carbon deposition is almost negligible (0.3 mmol carbon gcat–1?h–1), the catalyst is very stable and lively Bimetallic Cu–Ni phase with bi-functional acid sites favors the selective hydrogenolysis of the C–O bonds and limits C–C bond scission [83]
Cu–Ni/MA 33 wt-% xCu-yNi, Cu/Ni molar ratio= 9:1 Sol-gel method Aqueous glycerol solution (80 wt-%, 50 g), H2 (4 MPa), catalyst (1 g), T = 493 K, t = 10 h, stirring at 500 r?min–1 Glycerol conv.: 76.6%, 1,2-PDO select.: about 52.8%, 1,2-PDO yield: 42.4% (1) The sol-gel method can effectively disperse active site.
(2) The addition of Ni contributes to the activation of H2 and the formation of Cu0
[84]
Ni/Cu/TiO2 17 wt-% Cu, 27.5 wt-% Ni, Cu/Ni molar ratio= 1:1.3 Incipient wetness impregnation method Glycerol solution in 2-propanol or water (5?wt-%, 27.8 mL·h–1), N2 (50?mL·min–1, 3.5 MPa), catalyst (6 g), T = 230 K, P = 3.5 MPa Glycerol conv.: 100%, 1,2-PDO select.: 82.2%, acetol select.: 5.3%, others select.: 12.5% The acidity of Ni/Cu/TiO2 is lower than Ni/Cu/γ-Al2O3, indicating that the acidity of catalyst has no significant effect on glycerol conversion rate [88]
CuZn Cu/Zn molar ratio= 2.5:1 Co-precipitation method Aqueous glycerol solution (80 wt-%, 50 g), H2 (2.4 MPa), catalyst (1 wt-%), stirring at 500 r?min–1 Glycerol conv.: 25.9%, 1,2-PDO select.: 38.8% Leaching of ZnO causes the sintering of Cu particles [86]
CuZn/MgO 50 wt-% Cu, Cu/Zn molar ratio= 8:2 Precipitation-deposition method Under mild reaction conditions Glycerol conv.: 98.7%, 1,2-PDO select.: 94.6% The presence of Zn facilitates the H2 overflow [85]
Cu–Zn/γ-Al2O3 15 wt-% Cu, Cu/Zn molar ratio= 4:1 Wet impregnation method Aqueous glycerol solution (20 wt-%), flow rates of glycerol are 0.12–1.33 h–1, H2/glycerol molar ratio= 0.813–16.50, T = 453 K–473 K, P = 4 MPa Glycerol conv.: ~90%, 1,2-PDO select.: 83%–97% Zn is recognized as an active agent in hydrogenation processes [89]
Cu–Al Cu/Al molar ratio= 1:1 Co-precipitation method Glycerol concentration (20 wt-%), N2 (2 MPa), GHSV= 513 h–1, LHSV= 1.53 h–1, catalyst (1.0 g), T = 493 K Glycerol conv.: 90%, 1,2-PDO select.: 23% The majority of Cu2+ is in the form of CuAl2O4, and the formation of acid site contributes to the reaction [90]
CuPd-Graphene 2 wt-% Cu, 0.05 wt-% Pd, Cu/Pd mass ratio= 20:1 In situ reduction method Aqueous glycerol solution (100.0 kg·m–3), NaOH/glycerol molar ratio= 1.1, N2 (1.4 MPa), catalyst (6.7 kg?m–3), T = 473 K Glycerol conv.: 96%, 1,2-PDO select.: 10%, TOF= 114 (mol·g–1·atom Cu)·h–1 The introduction of Pd facilitates spillover of in situ formed H2 on carbon materials, which is resulted in the unique cluster-in-cluster alignment of the CuPd nanostructures [73]
CuPd/TiO2-Na 5 wt-% Cu, Cu/Pd molar ratio= 1.67:1 Wet impregnation method Aqueous glycerol solution (20 wt-%, 50 mL), H2 (0.7 MPa), Na (0.5 wt-%) catalyst (0.3 g), T = 493 K, stirring at 480 r?min–1 Glycerol conv.: 65%, 1,2-PDO select.: 85% TOF= 0.14 s–1 The formation of CuPd alloys and the rich Cu on the surface as well as the activation of H2 by Pd contribute to the high catalytic activity [70]
PdCu-KF/γ-Al2O3 4.8 wt-% Cu, 0.4 wt-% Pd, 2.2 wt-% KF, Cu/Pd/KF molar ratio= 1:0.05:0.5 Impregnation method Glycerol solution in methanol (40 wt-%), H2 (2.5 MPa), catalyst (9%, based on glycerol), T = 473 K Glycerol conv.: 94.1%, 1,2-PDO select.: 98.3%, the catalyst can be reused The presence of Pd contributes to the transform of Cu2+ to Cu+/Cu [72]
Pd0.04Cu0.4/Mg5.56Al2O8.56 7.23 wt-% Cu, Cu/Pd molar ratio= 10:1 Co-precipitation method Aqueous glycerol solution (75 wt-%, 8 g), H2 (2 MPa), catalyst (1 g), T = 453 K, t = 10 h Glycerol conv.: 76.9%, 1,2-PDO select.: 97.2%, the catalyst can be reused for 5 times (1) The presence of Pd facilitates the H2 overflow from Pd to Cu. (2) The catalytic activity is better when using methanol and ethanol as solvents, because the adsorption of water on the catalyst surface is stronger than methanol and ethanol, which hinders the availability of glycerol [71]
Pd0.04Cu0.4/Mg5.56Al2O8.56 7.23 wt-% Cu, Cu/Pd molar ratio= 10:1 Co-precipitation method Glycerol solution in alcohol (75 wt-%, 8 g), H2 (2 MPa), catalyst (1 g), T = 453 K, t = 10 h In methanol solvent: glycerol conv.: 89.5%, 1,2-PDO select.: 98.2%, in ethanol solvent: glycerol conv.: 88%, 1,2-PDO select.: 99.6% [71]
Cu–Pt/SiO2 10 wt-% Cu, Cu/Pt molar ratio= 1:0.2 Wet impregnation method Glycerol solution in methanol (40 wt-%, 20 g), H2 (4 MPa), catalyst (1.5 g), T = 473 K, stirring at 600 r?min–1 Glycerol conv.: 100%, 1,2-PDO select.: 96% The strong reduction of Pt promotes the reduction of Cu2+ [74]
Ru–Cu/SiO2 5 wt-% Cu, Cu/Ru molar ratio= 1:3 Wet impregnation method Glycerol (120 mL), H2 (8 MPa), catalyst (0.9 g), catalyst/glycerol mass ratio= 0.006, T = 513 K, t = 5 h, stirring at 1000 r?min–1 Glycerol conv.: 39.2%, 1,2-PDO select.: 85.9% The incorporation of Ru increases the glycerol conversion, while reduces the 1,2-PDO selectivity as Ru contributes to the cleavage of C–C bond [77]
Cu-Ru/CNT 10 mol-% Cu Chemical substitution method Aqueous glycerol solution (80 wt-%, 4 mL), H2 (4 MPa), catalyst (0.8 g), T = 473 K, stirring at 800 r?min–1 Glycerol conv.: 99.8%, 1,2-PDO select.: 86.5 mol-% Ru can not only promote the hydrogenolysis of glycerol but also promote hydrogen spillover [78]
Ru0.02Cu0.4/Mg5.6Al1.98O8.57 7.26 wt-% Cu, Cu/Ru molar ratio= 20:1 Co-precipitation method Solution of glycerol (75 wt-%, 8.0 g), H2 (2.0 MPa), catalyst (1.0 g), T = 453 K, t = 10 h Glycerol conv.: 70.6%, 1,2-PDO select.: 96.1 mol-% (1) The improvement of these two catalysts is ascribed to the interaction between Ru and Re on the Cu sites instead of additional M sites. (2) Glycerol solution in alcohol is better than aqueous glycerol solution, because the adsorption of water on the catalyst surface is stronger than methanol, ethanol and other alcohols, which hinders the accessibility of glycerol. (3) The addition of external hydrogen helps increase the glycerol conversion and 1,2-PDO selectivity [75]
Re0.02Cu0.4/Mg5.6Al1.98O8.57 7.23 wt-% Cu, Cu/Re molar ratio= 20:1 Co-precipitation method Solution of glycerol (75 wt-%, 8.0 g), H2 (2.0 MPa), catalyst (1.0 g), T = 453 K, t = 10 h Glycerol conv.: 71.6%, 1,2-PDO select.: 96.7 mol-% [75]
Ru0.02Cu0.4/Mg5.6Al1.98O8.57 7.26 wt-% Cu, Cu/Ru molar ratio= 20:1 Co-precipitation method Glycerol solution in alcohol (75 wt-%, 8.0 g), H2 (2.0 MPa), catalyst (1.0 g), T = 453 K, t = 10 h In methanol solvent: glycerol conv.: 91.2%, 1,2-PDO select.: 98.6%, in ethanol solvent: glycerol conv.: 90.2%, 1,2-PDO select.: 98.5%, in 1-propanol solvent: glycerol conv.: 89.4%, 1,2-PDO select.: 98.3% [75]
Re0.02Cu0.4/Mg5.6Al1.98O8.57 7.23 wt-% Cu, Cu/Re molar ratio= 20:1 Co-precipitation method Glycerol solution in alcohol (75 wt-%, 8.0 g), H2 (2.0 MPa), catalyst (1.0 g), T = 453 K, t = 10 h In methanol solvent: glycerol conv.: 91.5%, 1,2-PDO select.: 98.5%, in ethanol solvent: glycerol conv.: 91.0%, 1,2-PDO select.: 98.7%, in 1-propanol solvent: glycerol conv.: 90.5%, 1,2-PDO select.: 98.6% [75]
Cu-Re-ZnO 30 wt-% Cu, 1 wt-% Re, Wet impregnation method Aqueous glycerol solution (60 wt-%, 30 mL), GHSV= 1860 h–1, LHSV=10 h–1, hydrogen/glycerol molar ratio= 1:1, T = 523 K, P = 6 MPa Glycerol conv.: 63%, 1,2-PDO select.: 45%, no change in catalyst structure after 24 h The presence of Re increases the acidity and promotes the cleavage of C–C bonds [76]
CuAg/γ-Al2O3 Cu+Ag/γ-Al2O3 = 2.7 mmol, Cu/Ag molar ratio= 7:3 Incipient wetness impregnation method Aqueous glycerol solution (50 wt-%), H2 (1.5 MPa, initial pressure), (Cu+Ag)/glycerol molar ratio= 3:100, T = 473 K, t = 10 h, stirring at 400 r?min–1 Glycerol conv.: 27%, 1,2-PDO select.: 100% Ag contributes to the H2 spillover to CuO and helps reduce CuO to active Cu sites [79]
Cu–Ag/Al2O3 1 wt-% Ag Incipient wetness impregnation method Aqueous glycerol solution (15 wt-%, 1.32 cm3·h–1), H2 (360 cm3?min–1), hydrogen/glycerol mass ratio= 700:1, catalyst (8.7 g), at ambient hydrogen pressure and a low gradient temperature from 443 K to 378 K 1,2-PDO yield: 98.3% (1) Ag reduces the hydrogenation capacity, so double-layer catalysts are used.
(2) The presence of Ag changes the surface chemical and electronic properties, reducing the cracking capacity of Cu
[80]
CuAg/Al2O3 6 mmol Cu Wet impregnation method Aqueous glycerol solution (50% v/v, 30 mL), H2 (4 MPa), catalyst (2 g), T = 473 K, stirring at 400 r?min–1 Glycerol conv.: 38%, 1,2-PDO select.: 71% (1) The addition of Ag leads to sintering of the support or clogging of the supporting pores. (2) The Al2O3-supported catalyst is much more selective for 1,2-PDO [91]
CuAg/TiO2 2 mmol Cu Wet impregnation method Glycerol conv.: 44%, 1,2-PDO select.: 62% [91]
Tab.1  Reported catalysts for the glycerol hydrogenolysis reaction
Fig.8  Brief catalytic mechanism diagram of CuCo/Al2O3 in the hydrogenation of EL to 1,4-PeD (reprinted from [99], copyright (2017), with permission from American Chemical Society).
Catalysts Composition of catalysts Preparation methods Reaction conditions Catalytic performance Comments Ref.
Cu–Zn/SiO2 Cu/Zn molar ratio= 1:1 Coprecipitation method H2 flow= 60 mL·min–1, WHSV= 2 h–1, catalyst (1.35 g), T = 523 K, P = 2 MPa ethyl acetate conv.: 81.6%, EtOH select.: 93.8% When Cu/Zn molar ratio= 1:1, Cu particles are the smallest, resulting in higher dispersion and catalytic activity [96]
CuZn-SiO2 27.96 wt-% Cu, 4.56 wt-% Zn, Cu/Zn molar ratio= 9:1 Hydrolysis precipitation method H2/methyl acetate molar ratio= 20, catalyst (0.55 g), T = 493 K, P = 2.0 MPa Methyl acetate conv.: 92%, EtOH select.: 90%, EtOH STY: 1.024 gEtOH·gcat–1·h–1 The larger ratio of Cu/Zn is, the more favorable to form Cu–ZnOx species, which is beneficial to the formation of Cu+ active sites [97]
CuCo/TiO2 1.2 wt-% Cu, Cu/Co molar ratio= 1:9 (Co) impregnation method GBL in 1,4-dioxane solution (20 g, 10 wt-%), catalyst (0.4 g), T = 413 K, P = 3.4 MPa H2, t = 24 h, stirring at 750 r?min–1 GBL select.: 11.5%, 1,4-butanediol yield: 100% The formation of Co-rich core and CuCo alloy near-surface shell nanoparticles results in higher activity and selectivity [93]
CuCo/Al2O3 36.9 wt-% Cu, 16.7 wt-% Co, Cu/Co molar ratio= 2:1 Incipient wetness impregnation method EL (5 mmol), 1,4-dioxane (20 mL), catalyst (80 mg), T = 435 K, P = 3.4 MPa H2, stirring at 800 r?min–1 EL conv.: 100%, 1,4-PeD select.: 93%, TOF= 11.1 h–1, initial reaction rate= 311.4 μmol·gcat–1·min–1 Cu0 is mainly responsible for the activation of H2. Cu+ is beneficial for adsorbing C=O group and activating GVL intermediate due to the presence of electron lone pair of oxygen. The electron-deficient CoOx formed can further activate the C=O of EL and GVL [99]
Cu–Ni/Al2O3 10 wt-% Cu, 5 wt-% Ni Incipient impregnation method EL (1.0 mmol), solvent 2-butanol (3 mL), catalyst (100 mg), T = 423 K, t = 12 h, stirring at 600 r?min–1 EL conv.: 100%, GVL yield: 97% Cu2+ species are prone to be reduced to Cu0/Cu+ and Ni2+ are inclined to be reduced to Ni0 at the same time, which provides more hydrogenating sites and results in higher activity [98]
Tab.2  Reported catalysts for the hydrogenation of esters
Fig.9  Schematic representation of alcohol formation at the Cu–FeCx double site. Left side: The interaction between Cu and FeCx leads to higher alcohol formation prior to phase separation. Right side: After phase separation, the weakened interaction hinders the formation of alcohol (reprinted from [119], copyright (2013), with permission from Elsevier).
Fig.10  Functional diagram of each site on the catalyst surface during CO2 hydrogenation (reprinted from [143], copyright (2008), with permission from Elsevier).
Fig.11  Potential energy profiles for the CO2 hydrogenation to methanol on Cu (111) and PdCu (111) surfaces (reprinted from [150], copyright (2017), with permission from American Chemical Society).
Catalysts Composition of catalysts Preparation methods Reaction conditions Catalytic performance Comments Ref.
CuNi/SiO2 20 wt-% Cu+Ni, Cu/Ni molar ratio= 1:1 Wet co-impregnation method H2/CO= 1:1, GHSV= 2000 h–1, T = 548 K, P = 10 MPa CO conv.: 12.1%, ROH select. based on carbon: (MeOH: 99%, C2+OH: 0.4%), MeOH STY: 167 g·kgcat–1·h–1 The CO adsorbed on Ni is basically an observation molecule that determines the surface structure, and methanol synthesis occurs on the Cu step [61]
Cu–Ni/SiO2 20 wt-% Cu+Ni, Cu/Ni molar ratio= 2:1 Impregnation method H2/CO volume ratio= 2:1, GHSV= 4000 h–1, T = 548 K, P = 10 MPa CO conv.: 8.5%, ROH select. based on carbon: (MeOH: 99.7%, EtOH: 0.2%), MeOH STY: 0.19 kg·kgcat–1·h–1 (1) Coprecipitation and deposition-coprecipitation are more effective for preparing small and uniform Cu–Ni alloy NPs. (2) The uniform Cu–Ni alloy NPs are beneficial to the reaction. (3) Due to the formation of nickel carbonyl, the loss of Ni may emerge as a serious problem [122]
Cu–Ni/SiO2 20 wt-% Cu+Ni, Cu/Ni molar ratio= 2:1 Co-precipitation method H2/CO volume ratio= 2:1, GHSV= 4000 h–1, T = 548 K, P = 10 MPa CO conv.: 14.3%, ROH select. based on carbon: (MeOH: 99.1%, EtOH: 0.2%), MeOH STY: 0.52 kg·kgcat–1·h–1 [122]
Cu–Ni/SiO2 20 wt-% Cu+Ni, Cu/Ni molar ratio= 2:1 Deposition-coprecipitation method H2/CO volume ratio= 2:1, GHSV= 4000 h–1, T = 548 K, P = 10 MPa CO conv.: 16.6%, ROH select. based on carbon: (MeOH: 99.2%, EtOH: 0.3%), MeOH STY: 0.66 kg·kgcat–1·h–1 [122]
CuFe 25 wt-% Cu, Cu/Fe molar ratio= 1:3 Wet-chemical method H2/CO/N2 molar ratio= 65/32/3, GHSV= 6000 h–1, T = 493 K, P = 6 MPa, T = 24 h CO conv.: 17.1%, ROH select.: 21.9% (MeOH: 9.5%, EtOH: 8.9%, PrOH isopropanol: 8.5%, Butanol: 9.1%, PEOH: 8.2%, C6+OH: 55.8%) The dual sites of Cu–FeCx facilitate the synthesis of higher alcohols. Cu acts as a site for the activation and insertion of CO, while FeCx is the site of CO dissociative activation and chain growth [119]
Cu–Fe/N-CNT Cu/Fe molar ratio= 15:1 Co-impregnation method H2/CO= 2:1, GHSV= 6000 mL·g–1·h–1, quartz sand (1 mL), catalyst (200 mg), T = 493 K, P = 2 MPa CO conv.: 20.9%, ROH select.: 27.2% (MeOH:31.2%, C2+OH: 68.8%) The dispersion of Cu–Fe and the interaction between Cu, Fe and N-CNT are improved when doping N in CNT, and many surface basic sites are introduced [156]
Cu–Fe/SiO2 10 mol-% Cu–Fe, Cu/Fe molar ratio= 0.13:1 Co-impregnation method H2/CO mixture: 30 mL·min–1, VH2/VCO = 2:1, SV= 6000 mL·gcat–1·h–1, catalyst (0.3 g), T = 523 K, P = 3 MPa CO conv.: 13.9%, ROH select.: 23.5% (MeOH: 67.8%, C2+OH: 32.2%), ROHSTY: 90 g·kgcat–1·h–1 (1) A higher Cu/Fe ratio will favor the formation of alcohol, while a higher Fe/Cu ratio will favor the formation of hydrocarbon. (2) The surface content of Cu of the catalysts follows the order of Fe/Cu/SiO2>Cu/Fe/SiO2>Cu–Fe/SiO2. (3) The method of impregnating Fe first and then immersing Cu facilitates the higher ROH selectivity and STY, probably due to the lowest surface content of Cu and the formation of relatively smallest Fe3O4 particles on this catalyst [121]
Fe/Cu/SiO2 10 mol-% Cu–Fe, Cu/Fe molar ratio= 0.12:1 Sequential Impregnation method H2/CO mixture: 30 mL·min–1, VH2/VCO = 2:1, SV= 6000 mL·gcat–1·h–1, catalyst (0.3 g), T = 523 K, P = 3 MPa CO conv.: 17.6%, ROH select.: 26.1% (MeOH: 56.3%, C2+OH: 43.7%), ROH STY: 126.6 g·kgcat–1·h–1 [121]
Cu/Fe/SiO2 10 mol-% Cu–Fe, Cu/Fe molar ratio= 0.18:1 Sequential Impregnation method H2/CO mixture: 30 mL·min–1, VH2/VCO = 2:1, SV= 6000 mL·gcat–1·h–1, catalyst (0.3 g), T = 523 K, P =3 MPa CO conv.: 15.4%, ROH select.: 36.1% (MeOH: 62.5%, C2+OH: 37.5%), ROH STY: 153.3 g·kgcat–1·h–1 [121]
CuFe@SiO2 50 wt-% CuFe, Cu/Fe molar ratio= 8.8:2.8 Combining a facile thermal decomposition and the reverse microemulsion method H2/CO= 2:1, GHSV= 2000 h–1, T = 573 K, P = 5 MPa CO conv.: 71.35%, ROH select.: 8.56% (MeOH: 41.02%, C2−4OH: 56.67%, C5+OH: 2.31%), CHn select.: 35.86%, CO2 select.: 55.58%, TOF= 27.41×10–3 s–1, no sintering and phase separation CuFe@SiO2 catalyst has more active sites than CuFe catalyst, and the active sites are more dispersed [120]
CuFeMg-LDHs/CFs 0.33 mol-% Cu, Cu/Fe/Mg molar ratio= 1:1:1 Co-precipitation method H2/CO/N2 = 8/4/1, GHSV= 3900 mL·gcat–1·h–1, catalysts/quartz sand mass ratio= 1:4, T = 553 K, P = 3 MPa, t = 20 h CO conv.: 35.4%, ROH select.: 41.1% (MeOH: 31.3%, EtOH: 34.5%, C3H7OH: 20.7%, C4+OH: 13.5%) Cu is the active site for CO activation and insertion, and Fe2C is the active site for CO dissociation and carbon chain growth. The interaction between them promotes the formation of higher alcohols [117]
MnCuFe/ZnO Co-precipitation method Add cetyl trimethyl ammonium bromide SC24OH/Salc=63%, low-carbon alcohols yield: 0.151 g·mLcat–1·h–1 The addition of Mn and cetyl trimethyl ammonium bromide facilitates the reduction of Cu2+ to Cu0 and the generation of Cu–Fe3C double active sites on ZnO supports [116]
CuZnAl Cu/Zn/Al molar ratio= 2:1:0.8 A complete liquid-phase method Flow rate: 150 mL·min–1 (H2/CO= 2, v/v), T = 523 K, P = 4.5 MPa CO conv.: 23%, ROH select.: 20% (MeOH: 55%, C2+OH: 45%) Increasing the pH can reduce the size of Cu0 and increase the amount of reducible Cu+, and the probable amount of acid sites enhance the catalytic performance [128]
Cu–Co/CNTs Cu/Co molar ratio= 5:10 Co-impregnation method H2/CO= 2:1, GHSV= 10000 mL·gcat–1·h–1, TOS= 7 h, T = 573 K, P = 4.5 MPa CO conv.: 38.9%, CH4 select.: 48.5 C mol-%, C2–C4 select.: 14.0 C mol-%, CO2 select.: 1.7 C mol-%, ROH select.: 35.8 C mol-% (MeOH: 52.7 C mol-%, EtOH: 57.7 C mol-%, PrOH: 12.5 C mol-%, BuOH: 7.3 C mol-%), EtOH STY: 372.9 mg·gcat–1·h–1 Besides Cu0–Co0, the Co0–Co2+ also has two active sites for the synthesis of higher alcohols, because Co could stop carbon chain growth [112]
Cu–Co/Al2O3 [Cu2+]+[Co2+]+[Al3+]=1.0 mol?L–1, [Cu2+]+[Co2+]/[Al3+] = 2 mol?L–1, Cu/Co molar ratio= 1:2 Co-precipitation method H2/CO/N2 = 8:4:1, GHSV= 720 mL·gcat–1·h–1, T = 513 K, P = 3 MPa, t = 24 h, stirring at 1000 r?min–1 CO conv.: 61.3%, ROH select.: 56.8% (MeOH: 5.5%, EtOH: 80.2%, C3OH: 12.0%, C4+OH: 2.3%) More Co transfers into Co2C later in the reaction, which protects Cu@Co@Co2C from Co loss and the Cu sintering, resulting in higher ethanol selectivity [109]
Cu/Co Cu:Co molar ratio= 1:1.3 Use lysine as a surfactant template H2/CO/N2 molar ratio= 65:32:3, GHSV= 10000 mL·h–1·g–1, catalyst (2 g), T = 573 K, P = 6 MPa CO conv.: 35.6%, ROH select.: 14.1% (MeOH: 43.8%, EtOH: 30.7%, isopropanol: 9%, butanol: 5.3%, C5+OH: 11.2%) The interaction between Co (100) and Cu (111) surfaces as well as the interfacial electron transfer cause the higher selectivity of higher alcohols [111]
Cu–Co/graphene-LaFeO3 10 wt-% Cu–Co, 5% graphene-LaFeO3, Cu/Co molar ratio= 1:2 Wet co-impregnation method H2/CO/N2 = 8:4:1, GHSV= 3900 mL·h–1·g–1, catalyst (800 mg), T = 573 K, P = 3 MPa CO conv.: 59.7%, ROH select.: 56.9% (MeOH: 9.7%, EtOH: 26.7%, C3OH: 13.1%, C4+OH: 7.4%) The mesopores of graphene-LaFeO3 promote the transfer of reactive molecules, and the formation of CuCo alloys results in high selectivity of higher alcohols [105]
CuCo/MoOx Cu/(Cu+Co) molar ratio= 0.3:1 Co-precipitation method H2/CO= 1:1, T = 543 K, P = 4 MPa EtOH select.: 48% (C2+OH: 58%), C2+OH yield: 27 mmol·gCu+Co–1·h–1 The formation of CuCo alloys contributes to the generation of long-chain alcohol [55]
Cu@Mn3O4 Cu/Mn molar ratio= 2.2:1 Wet-chemical method H2/CO= 2:1, space velocity= 18000 scc·h–1·gcat–1, catalyst (0.2 g), T = 543 K, P = 1 MPa MeOH select.: 16%, EtOH select.: 7.8%, C2+OH select.: 4.9% The dissociation and association for the formation of CO adsorption on Cu@Co3O4 contributes to the higher selectivity of the alcohol [103]
Cu@Co3O4 Cu/Co molar ratio= 8.7:1 MeOH select.: 26.6%, EtOH select.: 15.1%, C2+OH select.: 5.3%
Au–Cu/CrAl3O6 1% Au to 5% Cu/CrAl3O6, Cr/Al molar ratio= 1:3 Wet aqueous impregnation method H2/CO/CO2 molar ratio= 4:2:1, catalysts (about 0.5 g), T = 713 K, t>12 h MeOH yield: 2.5×10–6 mol·gcat–1·h–1 Au has no promotion on the catalyst [123]
Ag–Cu/CrAl3O6 1% Ag to 5% Cu/CrAl3O6, Cr/Al molar ratio= 1:3 Wet aqueous impregnation method MeOH yield: 2.5×10–7 mol·gcat–1·h–1 The formation of Ag2CrO4 and extra active sites enhance the activity [123]
Tab.3  Reported catalysts for the hydrogenation of CO to alcohol
Catalysts Composition of catalysts Preparation methods Reaction conditions Catalytic performance Comments Ref.
NiCu/γ-Al2O3 9.6 wt-% Cu, 1.2 wt-% Ni, Cu/Ni molar ratio= 8:1 Atomic layer deposition method H2/CO2 volume ratio= 3:1, total flow rate= 30?mL·min–1, catalyst (0.5 g), T = 523 K, P = 2.0?MPa CO2 conv.: 6.4%, MeOH select.: 58.8%, MeOH yield: 1.5?mmol·g–1·h–1 This method provides higher alloy dispersion than impregnation method, promoting the synthesis of methanol [157]
Cu–Ni/CeO2-nanotube Cu/Ni molar ratio= 1:2 Impregnation method CO2/H2/N2 molar ratio= 1:3:1, GHSV= 6000 h–1, catalyst (0.1 g), T = 533 K,
P = 3.0 MPa
CO2 conv.: 17.8%, MeOH select.: 76%, MeOH STY: 18.1 mmol·gcat–1·h–1 The formation of CuNi alloy advances the reduction of CeO2, which produces numerous oxygen vacancies to adsorb and activate CO2 [154]
Cu/ZnO 0.4 mL ZnO Deposition method T = 540 K, PH2= 0.45 MPa, PCO2= 0.05 MPa MeOH yield: 0.16×1015 molecules·cm–2·s–1 Zn is converted to ZnO in ZnCu during the reaction, which makes ZnCu reach the activity of ZnO/Cu, suggesting the interaction between Cu and ZnO [137]
Cu–Zn/reduced graphene oxide 10 wt-% Cu–Zn Incipient wetness impregnation method CO2/H2 = 1:3, GHSV= 2400 h–1, STY= 424 mgMeOH·gcat–1·h–1, T = 523 K, P = 1.5 MPa CO2 conv.: 26%, MeOH select.: 5.1%, MeOH STY: 424 mg·gcat–1·h–1 Pyridine-N is a favorable site for hydrogen bond interaction and it can attract hydrogen donors to increase MeOH STY, resulting from the rGO reduced by hydrazine [135]
CuO·ZnO·Al2O3 Cu:Zn molar ratio= 2:1 Co-precipitation method CO2/H2 molar ratio= 1:3, GHSV= 40000 mLC O2·gCat–1·h–1, T = 523 K, P = 5 MPa CO2 conv.: 12.9%, MeOH select.: 93.8%, MeOH yield: 1641.6 mL·gcat–1·h–1, the intrinsic activity: 531.3 mLC H3OH·m2Cu–1·h–1 (1) Intermetallic compounds bimetallic oxides and copper-f block element oxides show higher catalytic activity in producing methanol. (2) The close interaction facilitates electronic sharing between them and subsequent increase in catalytic activity [155]
CuO·ZnO·Al2O3 Cu:Zn molar ratio= 2:1 Co-precipitation method CO2/H2/CH4 molar ratio= 1:3:1, GHSV= 40000 mLC O2· g Ca t 1·h–1, T = 523 K, P = 5 MPa CO2 conv.: 15.3%, MeOH select.: 95.3%, MeOH yield: 585.3 mL·gcat–1·h–1, the intrinsic activity: 189.4 mLC H3OH·m2Cu–1·h–1 [155]
Cu–Zn/γ-Al2O3 Cu/Zn molar ratio= 1:1 Incipient wetness impregnation method H2/CO2 molar ratio= 3:1, GHSV= 500 h–1, catalyst (5 g), T = 543 K, P = 4 MPa CO2 conv.: 0.192%, MeOH select.: 22.54%, MeOH STY= 16.36 g·kgCat–1·h–1 The high calcination temperature has a negative effect on the microstructure and Cu dispersion, which is not conducive to the methanol production [134]
CuZn-BTC Cu/Zn/BTC molar ratio= 1:1:0.56 “Acidic etching-self assembly” method H2/CO2/N2 73:24:3, WHSV= 1500 mL·gcat–1·h–1, catalyst (0.5 g), T = 523 K, P = 4 MPa CO2 conv.: 20.9%, MeOH select.: 58.2%, MeOH yield: 62 g·kgcat–1·h–1, TOF= 0.0365 s–1 This new method can inhibit the aggregation of Cu and ZnO, and generate the more stable Cu–ZnO interface [138]
Cu–ZnO/ZrO2 41.2 wt-% CuO, 14.8 wt-% ZnO, 43 wt-% ZrO2 Co-precipitation method GHSV= 8800 NLh–1·kgcat–1, catalyst (0.5 g), P = 1.0 MPa The Cu-oxide interface is the surface region of the formate that is further hydrogenated to methanol [143]
Cu/ZrO2/CNFs-O 15 wt-% Cu, 10 wt-% ZrO2, Cu/Zr atom ratio= 1.2:1 Deposition precipitation method CO2/H2 feed volume ratio= 1:3, catalyst (0.5 g), T = 453 K,
P = 3 MPa
CO2 conv. :11%, MeOH TOF= 5.4×10–4 s–1, MeOH activity: 20 g·kg–1·h–1 The increase of SCu provides more atomic H, resulting in more H2 being supplied to the ZrO2 site for reduction of CO2 adsorption [147]
Cu·ZrO2/CNFs-O 15 wt-% Cu, 10 wt-% ZrO2 Deposition precipitation method CO2/H2 feed volume ratio= 1:3, T = 453 K, P = 3 MPa CO2 conv.: 14%, MeOH TOF= 1.52×10–3 s–1, MeOH yield: 34 g·kgcat–1·h–1 There is a linear relationship between the activity of CO2 conversion and the SCu of catalyst [146]
Pd–Cu–Zn/SiC 12.5 mol-% Cu, Pd/Cu/Zn molar ratio= 37.5:12.5:50 Impregnation method CO2/H2 = 1:9 v/v, total flow rate: 100 Ncm3·min–1, catalyst (0.8 g), T = 473 K MeOH activity: 1.84 μmol·g–1·min–1, MeOH select.: 80.9% The interaction between Pd, Cu and Zn contributes to the better performance and the formation of PdZn and PdCu alloys are selective for methanol and CO, respectively [136]
Pd–Cu/SiO2 10 wt-% Cu, 5.7 wt-% Pd Co-impregnation method CO2/H2/Ar volume ratio= 24%:72%:4%, GHSV= 3600 mL (STP)·gcat–1·h–1, W/F = 6.2 gcat·h·mol–1, catalyst (0.2 g), T = 523 K, P = 4.1 MPa CO2 conv.: 6.6%, MeOH select.: 34 mol-%, MeOH yield: 0.31 μmol·gcat–1·s–1 The Pd–Cu alloy formation is the key factor for the promotion of catalytic activity [148]
Tab.4  Reported catalysts for the hydrogenation of CO2 to alcohol.
Fig.12  Methanol adsorption mechanism on different catalyst (mono- and bimetallic) surface (reprinted from [161], copyright (2015), with permission from Elsevier).
Catalysts Composition of catalysts Preparation methods Reaction conditions Catalytic performance Comments Ref.
Cu–NiO 10% Cu Space-confinement method H2O/EtOH (S/E) molar ratio= 6:1, GHSV= ∼180 h–1, WHSV= 2 gEtOH·gcat–1·h–1, T = 573 K EtOH conv.: ∼100%, H2 yield: ∼5 mol/per mol of EtOH, SCO2/CH4: ∼13 mol/per mol of CH4 formed The interaction of Cu–NiO surface enhances the catalytic activity and their close contact enlarges this effect [168]
Cu–Ni/γ-Al2O3 6.6 wt-% Cu, 2 wt-% Ni Incipient wetness impregnation method DBO (2 mmol), styrene (4 mmol), mesitylene (2 mL), under N2, catalyst (0.40 g), T = 403 K, t = 24 h DBO conv.: 52%, DBA select.:>99% (1) The presence of styrene (H2 acceptor) contributes to the transformation of primary aliphatic alcohol to the corresponding aldehyde with high conversion. (2) The introduction of Ni decreases the size of Cu particles [164]
Cu–Ni/γ-Al2O3 6.6 wt-% Cu, 2 wt-% Ni Incipient wetness impregnation method DBO (2 mmol), catalyst (0.40 g), styrene (8 mmol), mesitylene (2 mL), T = 423 K, t = 24 h DBO conv.: 93%, DBA select.:>99%, after four cycles:
DBO conv.: 73%, DBA select.:99%
[164]
Cu–Ni/γ-Al2O3 6.6 wt-% Cu, 2 wt-% Ni Incipient wetness impregnation method DBO (2 mmol), styrene (4 mmol), mesitylene (2 mL), N2 atmosphere, catalyst (0.4 g), T = 423 K, t = 24 h DBO conv.: 93%, DBA select.:>99% The addition of Ni greatly improves the hydrogenation of C=C bonds instead of C=O bonds, improving the styrene hydrogenation and obstructing the DBA rehydrogenation [165]
Cu–Ni/Al2O3 10 wt-% Cu, 10 wt-% Ni Impregnation method Water/methanol mole ratio= 1.7:1, flow rate= 0.06 mL·min–1, T = 598 K MeOH conv.: 96.1%, H2 yield: 2.08 mol·molMeOH–1, CO2 yield: 0.71 mol·molMeOH–1, CO yield: 0.13 mol·molMeOH–1, CH4 yield: 0.11 mol·molMeOH–1 The alloyed Cu inhibits the CO and CO2 hydrogenation during the methanol decomposition [169]
Cu–Ni/ZrO2 1.5 wt-% Cu, 1.5 wt-% Ni Deposition-precipitation method total flow rate of O2 (5%)/He= 50 mL·min–1, GHSV= 30000 h–1, MeOH= 75 Torr, H2O= 12.75 Torr, O2 = 25.2 Torr, catalyst (0.1 g), T = 623 K MeOH conv.: ∼100%, H2 select.: ∼60 mol-%, CO2 select.: ∼20 mol-%, CO, CH4 select.: ∼20 mol-%, the catalyst can be reused for 4 times The reaction intermediates are mainly located in ZrO2 Cu and Ni are functioning in facilitating H2 overflow and released to raw materials [160]
Ni–Cu/ZrO2 Ni/Cu molar ratio= 1:4 Precipitation method MeOH/H2O molar ratio= 1:1, catalyst (0.3 g), T = 573 K, annealed at 623 K MeOH conv.: 100%, H2 yield: 1.5 mol·molMeOH–1, CO yield: ∼0, CO2 yield: 0.5 mol· mo l CH3OHr–1 (1) Annealed at lower temperature can achieve the maximum hydrogen production. (2) Rich Cu results in lower Fermi level and enhances the adsorption of alcohol, further accelerating the convert into CO2 [161]
Ni–Cu/Y0.1Zr0.9O1.95 20 wt-% Ni+Cu, Ni/Cu molar ratio= 1:4 Coprecipitation method MeOH/H2O molar ratio= 1:1, mixture rate= 1 cm3·h–1, GHSV=172 h–1, catalyst (0.3 g), T = 573 K MeOH conv.: ∼28%, H2 select.: 99.8% The catalyst doped Ce is the most active and the reduction of Ce4+ to Ce3+ becomes easier when solid solution of ZrO and CeO2 is formed [163]
Ni–Cu/La0.1Zr0.9O1.95 MeOH conv.: ∼44%, H2 select.: 99.8%
Ni–Cu/Ce0.1Zr0.9O1.95 MeOH conv.: ∼60%, H2 select.: 100%
Cu–Zr Cu/Zr molar ratio= 2:1 PMeOH = 0.0012 MPa, PH2O= 0.0024 MPa, Par = 0.0008 MPa, PHe = 0.0956 MPa, T = 550 K MeOH conv.: ~100%, CO2 select.:>99.9% The Cu-tetragonal ZrO2 interface is greatly beneficial to catalysis [162]
Cu–Co/CNFs/ACF 5 wt-% Cu–Co, Cu/Co molar ratio= 1:1 Incipient wetness impregnation method EtOH in water: 93 wt-%, GHSV= 32 h–1, T = 573 K Activity: 410 gEtOH·gM–1·h–1, acetaldehyde yield: 9.3% Co is partly covered by carbon and Cu is located in the edge without carbon. The redistribution of active sites affects a lot on the catalytic activation [170]
Au–Cu/MWCNT 20 wt-% Cu, 0.5 wt-% Au Deposition-precipitation method H2O/MeOH/O2 molar ratio= 1:1:0.4, mixture rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.1 g), T = 573 K MeOH conv.: ~100%, H2 yield: ~3.1 mLH2·molMeOH–1 (1) Defects on CNTs facilitate the electrons transfer, thereby promoting the reduction of CuO to Cu. (2) The presence of acid sites facilitates the stabilization of reactant intermediates [173]
Cu–Ag/hydrotalcite 95 wt-% Cu, 10 wt-% Cu+Ag, Mg2+/Al3+ molar ratio= 2:1 Co-impregnation method Benzyl alcohol (1.0 mmol), 1-phenylethanol (1.0 mmol), o-xylene (3 mL), at a relative pressure of 0.995, 0.1 MPa N2, catalyst (0.1 g), T = 423 K, T = 0.5 h benzyl alcohol conv.: ~99%, β-phenylpropiophenone yield: ~99%, the catalyst can stable for five cycles without any loss of activity (1) Alkaline support promotes dehydrogenation cross-coupling of primary and secondary benzyl alcohols, and acidic support promotes etherification of primary and secondary benzyl alcohols. (2) Ag activates Cu sites and obstructs their oxidation [174]
Ru–Cu/ZnO–Al2O3 20 wt-% Cu, 1 wt-% Ru Incipient wetness impregnation method H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa MeOH conv.: 28%, H2 select.: 20%, CO select.: 0%, CO2 select.: 100% (1) The adsorption and dissociation of H2 are easier to occur on precious metals, subsequently H2 spills over to accelerate the reduction of CuO to Cu2O. (2) Precious metal can enhance the adsorption of CH3OH during the dehydrogenation process. (3) Appropriate acidity favors the conversion of CH3OH. (4) The catalyst supported on ZrO2–Al2O3 shows lower CH3OH conversion than that of ZnO–Al2O3 [172]
Rh–Cu/ZnO–Al2O3 20 wt-% Cu, 1 wt-% Rh Incipient wetness impregnation method H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa MeOH conv.: 99%, H2 select.: 70.5%, CO select.: 0%, CO2 select.: 99.6% [172]
Ag–Cu/ZnO–Al2O3 20 wt-% Cu, 1 wt-% Ag Incipient wetness impregnation method H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa MeOH conv.: 87%, H2 select.: 62.2%, CO select.: 0%, CO2 select.: 100% [172]
Ir–Cu/ZnO–Al2O3 20 wt-% Cu, 1 wt-% Ir Incipient wetness impregnation method H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa MeOH conv.: 86%, H2 select.: 53%, CO select.: 0%, CO2 select.: 88% [172]
Ru–Cu/ZrO2–Al2O3 20 wt-% Cu, 1 wt-% Ru Incipient wetness impregnation method H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa MeOH conv.: 31%, H2 select.: 24%, CO select.: 0%, CO2 select.: 100% [172]
Rh–Cu/ZrO2–Al2O3 20 wt-% Cu, 1 wt-% Rh Incipient wetness impregnation method H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa MeOH conv.: 74%, H2 select.: 71%, CO select.: 15%, CO2 select. : 85% [172]
Ag–Cu/ZrO2–Al2O3 20 wt-% Cu, 1 wt-% Ag Incipient wetness impregnation method H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa MeOH conv.: 48%, H2 select.: 64%, CO select.: 0%, CO2 select.: 97.3% [172]
Ir–Cu/ZrO2–Al2O3 20 wt-% Cu, 1 wt-% Ir Incipient wetness impregnation method H2O/MeOH/O2 molar ratio= 1:1:0.4, total flow rate= 31.5 mL·min–1, GHSV= 26700 h–1, catalyst (0.2 g), T = 473 K, P = 0.1 MPa MeOH conv.: 41%, H2 select.: 33%, CO select.: 0%, CO2 select.: 82.3% [172]
Tab.5  Reported catalysts for the dehydrogenation of alcohols
Fig.13  The trend of Cu surface area (blue) and WGS rate (red) with the variation of Cu/(Cu+Fe) ratio, and microscopic map of Cu on the surface of the catalyst (reprinted from [190], copyright (2018), with permission from Elsevier).
Catalysts Composition of catalysts Preparation methods Reaction conditions Catalytic performance Comments Ref.
Cu–Ni/Ac 20 wt-% CuO+NiO, Cu/Ni molar ratio= 2:1 Wetness impregnation method CO/H2O/N2 molar ratio= 4.5%:30.5%:65%, catalyst (0.25 g), T = 623 K CO conv.: 95% The size of the catalyst plays a more important role rather than Cu/Ni content [185]
Cu–Ni/AC 62.7 wt-% Cu, Cu/Ni molar ratio= 1.56:1 Wetness impregnation method CO/H2O molar ratio= 4.5%:30.6%, N2 balance, GHSV= 4000 h–1, catalyst (0.25 g), T = 623 K CO conv.: 82.5% Cu remains in Cu0 during the reaction and the CuNi alloy formation inhibits methane production [188]
Ni–Cu/SiO2 10 wt-% Ni–Cu, Ni/Cu molar ratio= 5:5 In situ self-assembled core-shell precursor method CO/H2O molar ratio= 5%:25%, He balance, the total flow rate= 50 mL·min–1, GHSV= 68000 h–1, catalyst (0.05 g), T = 673 K CO conv.: 78.9%, H2 yield: 45%, TOF= 0.002 s–1 The highly dispersed NiCu alloy can promote the CO adsorption and activate hydroxyl on the SiO2 surface [187]
Ni–Cu/SiO2 (OA) 10 wt-% Ni–Cu, Ni/Cu molar ratio= 5:5,
OA/metal molar ratio=0.25:1
In situ self-assembled core-shell precursor method CO conv.: 96.8%, H2 yield: 53%, TOF= 0.004 s–1 OA can promote metal dispersion and enhance the interaction between metal and support [187]
Cu–Ni/SiO2 Thermal decomposition precursor H2O/CO= 4:1, GHSV= 3600 h–1, catalyst (1.0 g), T = 573 K, P = 0.1 MPa CO conv.: 97.83%, CO2 select.: 98.64% This preparation method contributes to the high dispersion of CuO and NiO [194]
Cu–Ni/γ-Al2O3 10 wt-% Cu, 10 wt-% Ni Co-precipitation method H2 (60 vol-%), CO (1 vol-%), O2 (1 vol-%), He balance, GHSV= 60000 h–1, T = 473 K Without H2O and CO2, CO conv.: 2.91 mmolCO·s–1·kgcat–1, with 10 vol-% H2O: 3.58 mmolCO·s–1·kgcat–1, with 10 vol-% CO2: 2.42 mmolCO·s-1·kgcat–1, with 10 vol-% H2O and 10 vol-% CO2: 2.51 mmolCO·s–1·kgcat–1 (1) The addition of H2O has a positive effect on CO conversion while the addition of CO2 has a negative effect. (2) CO conversion is in the order of Cu–Mn/Al2O3>Cu–Ni/Al2O3>Cu/Al2O3>Ni/Al2O3>Mn/Al2O3>Al2O3. (3) The formation of CuMn2O4 contributes to the high dispersion of Cu and Mn, resulting in high CO conversion [193]
Cu–Mn/γ-Al2O3 10 wt-% Cu, 10 wt-% Mn Co-precipitation method H2 (60 vol-%), CO (1 vol-%), O2 (1 vol-%), He balance, GHSV= 60000 h–1, T = 473 K Without H2O and CO2, CO conv.: 3.32 mmolCO·s–1·kgcat–1, with 10 vol-% H2O: 3.85 mmolCO·s–1·kgcat–1, with 10 vol-% CO2: 2.66 mmolCO·s–1·kgcat–1, with 10 vol-% H2O and 10 vol-% CO2: 3.11 mmolCO·s–1·kgcat–1 [193]
Ce0.7Cu0.1Fe0.2O2−δ Ce/Cu/Fe molar ratio= 0.7:0.1:0.2 Sonochemical method CO (2 vol-%), N2 balance, total gas flow rate= 100 mL·min–1, The flow rate of water vapor= 55 mL·min–1, GHSV= 48000 h–1, P = 0.1 MPa CO conv.: 100%,
H2 select.: 100%
Compared to Cu–Ni/CeO2, the activity of Cu–Fe/CeO2 is lower because Fe is more easily to be oxidized under reaction conditions [191]
Ce0.75Cu0.1Ni0.15O2−δ Ce/Cu/Ni molar ratio= 0.75:0.1:0.15
Cu0.3Fe0.7Ox Cu/Fe molar ratio= 3:7 Aerosol-spray self-assembly method 2.2% CO/N2 stream (56 cm3·min–1), CO/H2O feed ratio= 1:7, GHSV= 42000 cm3·g–1·h–1, catalyst (20 mg), T = 523 K, P = 0.1 MPa, t = 140 h Rate= 1.46×10–6 mol·m–2·s–1, TOF= 0.047 s–1, CO conv.: 50% (1) The addition of Fe can promote the dispersion of Cu0 and enhance the adsorption of CO and CO2. (2) The addition of Al enhances the durability of the catalyst [190]
Cu0.3Fe0.6Al0.1Ox Cu/Fe/Al molar ratio= 3:6:1 Aerosol-spray self-assembly method Rate= 3.98×10–6 mol·m–2·s–1, TOF= 0.136 s–1, CO conv.: 85% [190]
CuPd/CeO2 30 wt-% Cu, 1 wt-% Pd Incipient wetness impregnation method CO (4 vol-%), CO2 (10 vol-%), air (2 vol-%), Ar (26 vol-%), H2 balance, H2O/CO molar ratio= 10:1 CO conv.: 77% H2 prefers to be adsorbed and dissociated on Pd site, and H2 spillovers to CuO site, resulting in the congregation of reduced Cu accompanied with water desorption [183]
Pd–Cu/CeO2 5 wt-% Cu, 1 wt-% Pd Incipient wetness impregnation method CO/H2O/CO2/H2/Air= 9.7%:22.8%:6.3%:37.9%:6.9% (1.4% O2), argon balance, a total flow rate of 132.5 mL·min–1, GHSV= 64400 h–1 (dry), catalyst (0.15 g), T = 533 K H2 production rates: 122 μmol·g–1·s–1 Compared with Pt in Pt-Cu/CeO2, the Pd in Pd–Cu/CeO2 is more surrounded by Cu and the interaction between Cu and Pd is stronger [184]
Pt–Cu/CeO2 5 wt-% Cu, 1 wt-% Pt Incipient wetness impregnation method H2 production rates: 160 μmol·g–1·s–1 [184]
Pt–Cu/ZnO/Al2O3 Cu/Zn molar ratio= 1:1, 0.05 wt-% Pt, 10 mol-% Al Co-precipitation methods CO/H2O/H2/CO2/N2 = 0.77:2.2:4.46:0.57:30, GHSV= 4800 mL·h–1·gcat–1, catalyst (0.05 g), T = 523 K CO conv.: 78%,
TOF=1.95×10–2 s–1
Pt promotes the H2 spillover from Pt to Cu to prohibit Cu from sintering and accelerates the reduction-oxidation cycle of Cu0 and Cu+ [182]
Au–Cu/CeO2 7 wt-% Cu, 1 wt-% Au Incipient wetness impregnation method A total flow rate of 200 mL·min–1, balanced to He, GHSV= 12000 h–1, WSV= 1.83 NL min–1·g–1, catalyst (0.1 g), T = 483 K, in WGS.
CO/H2O/H2/CO2 = 4:9.4:37.9:3, in CO-PROX:
CO/O2/H2 = 4:0.56:37.9, in OWGS: CO/H2O/H2/CO2/O2 = 4:9.4:37.9:3:0.56
In CO-PROX: CO conv.: 36%, in WGS: CO conv.: 1%, in OWGS: CO conv.: 35%, in CO-PROX: CO conv.: 37%, in WGS: CO conv.: 3.8%, in OWGS: CO conv.: 40% The catalyst prepared by deposition-precipitation shows higher Au dispersion and oxygen storage capacity than the catalyst prepared by incipient wetness impregnation [181]
Au–Cu/CeO2 7 wt-% Cu, 1 wt-% Au Deposition-precipitation method [181]
Au–CuO/CeO2 7 wt-% CuO, 1 wt-% Au Incipient wetness impregnation method A total flow rate of 200 mL·min–1, He to balance, GHSV= 12000 h–1, WSV= 1.83 NL min–1·g–1, catalyst (0.1 g), in CO-PROX: CO/H2/O2 = 0.5:30:0.5 (in % by vol.), T = 372 K, in WGS: CO/H2O/H2/CO2 = 0.5:20:30:4, T = 623 K, in OWGS: CO/H2/H2O/O2 = 0.5:30:20:0.5, T = 493 K In CO-PROX: CO conv.: 100%, in WGS:
CO conv.: 31%, in OWGS: CO conv.: 95%
(1) The addition of O2 greatly promotes the CO conversion.
For WGS, the addition of Au in CuO/CeO2 has no promotion on catalytic activation. (2) The presence of Au influences the reduction of CeO2 surface
[180]
ReCu/gadolinium doped ceria 4% Cu, 1% Re Impregnation method CO (5%), H2O (10%), N2 balance, a total flow rate= 100 mL·min–1, catalyst (0.15 g), T = 673 K CO conv.: 93%, the rate of WGS reaction= 61.6 μmol·g–1·s–1 (1) The transfer of electron density between Re, Cu, Ce and Gd contributes to the decrease of catalyst surface. (2) Re helps Cu reduce Ce4+ and produce more Ce3+ on the ceria surface, and leads the catalyst to be more resistant to deactivation [192]
Tab.6  Reported catalysts for the water gas shift reaction
Fig.14  The mechanism of SCR reaction catalyzed by CuxMny-OMC catalysts and the interaction between Cu and Mn ions (reprinted from [208], copyright (2015), with permission from Royal Society of Chemistry).
Catalysts Composition of catalysts Preparation methods Reaction conditions Catalytic performance Comments Ref.
Cu5Mn5-OMC 5 wt-% Cu, 5 wt-% Mn Solvent evaporation-induced self-assembly method [NO] = [NH3] = 500 ppm, [O2] = 5 vol-%, Ar balance, a total flow rate= 60 cm3·min–1, GHSV= 36000 h–1, catalyst (0.2 g), T = 523 K NO conv.: 85%, N2 select.: 90%, N2O concentrations:<50 ppm (1) Some Cu ions are replaced by Mn ions, causing lattice shrinkage by forming solid solutions. (2) Mn can improve acidity which is good for NH3 adsorption. (3) Mn can provide more adsorption sites for NO, and may be responsible for the adsorption of NH3 and NO [208]
CexCuy-OMC 5 wt-% Cu, 5 wt-% Ce “One-pot” self-assembly method [NO] = [NH3] = 500 ppm, [O2] = 5 vol-%, N2 balance, GHSV= 36000 h–1, catalyst (0.2 g), T = 523 K NO conv.: 88%, N2 select.: 95% The addition of Ce increases the relative concentration of Cu2+ as well as the Lewis-acid site, which is active for NH3 activation [209]
Cu–Fe/MWCNT 25 wt-% Cu, 25 wt-% Fe Facile impregnation method [NO] = 5 vol-%, [CO] = 10 vol-%, Ar balance, GHSV= 60000 h–1, catalyst (0.05 g), T = 723 K NO conv.: ~100%, CO conv.: ~50%, Activity: 4.82 kmolNO·s–1·kgcat–1, TOF= 16.3×10–3 s–1 (1) The introduction of Cu–Fe into CNT channels enhances the NO adsorption. (2) Acidic and alkaline sites accelerate NO reduction [206]
Cu–Fe-ZSM-5 1.48 wt-% Cu, 1.24 wt-% Fe Solid-state ion exchange method [NO] = [NH3] = 1000 ppm, He balance, GHSV= 250000 h–1, a total flow rate= 6 L·h–1, catalyst (0.024 g) 50% of NO conv. at 502 K, 100% of NO conv. starting from 569 K (1) The metal exchange sequence influences the catalytic activation. (2) The addition of Fe to Cu reduces the gathering of Cu particles through the formation Fe–Cu nano compounds. (3) The influence of catalyst acidity is not obvious [207]
Fe–Cu-ZSM-5 1.36 wt-% Cu, 1.16 wt-% Fe Solid-state ion exchange method 50% of NO conv. at 507 K, 100% of NO conv. starting from 608 K [207]
Cr–Cu/ZSM-5 5 wt-% Cu, 3 wt-% Cr Excess-solution impregnation method [NO] = 1000 ppm, [NH3] = 1000 ppm, [O2] = 5 vol-%, Ar balance, a total flow Rate= 200 mL·min–1, GHSV= 12000 h–1, catalyst (0.2 g), T = 573 K NO conv.: 82% (1) Adding too much Fe has a negative effect because of metal agglomeration and formation of bulk metal particles, resulting in the decrease of active sites. (2) Highly dispersed Lewis-acid sites are produced due to the Lewis nature of Fe ions caused by pyridine adsorption, thus enhancing the adsorption of NH3 [204]
Mn–Cu/ZSM-5 5 wt-% Cu, 3 wt-% Mn Excess-solution impregnation method NO conv.: 86% [204]
Co–Cu/ZSM-5 5 wt-% Cu, 3 wt-% Co Excess-solution impregnation method NO conv.: 89% [204]
Fe–Cu/ZSM-5 5 wt-% Cu, 3 wt-% Fe Excess-solution impregnation method NO conv.: 93% [204]
Fe4–Cu4/ZSM-5 4 wt-% Cu, 4 wt-% Fe Improved incipient-wetness-impregnation method [NO] = 1000 ppm, [NH3] = 1000 ppm, [O2] = 3%, N2 balance, a total flow rate= 500 mL·min–1, GHSV= 45000 h–1, catalyst (0.4 g), T = 473 K–648 K NO conv.: 100%, N2 select.:>95% (1) Fe can enhance the dispersion of Cu species, produce acidic sites and enhance the adsorption of NH3. (2) Electronic properties of Fe3O4 structures can be changed and accelerates the formation of oxygen vacancies, resulting in high Fe2+/Fe3+ ratio and good activity [205]
Cu0.54Co2.43/Al2O3 0.54 wt-% Cu, 2.43 wt-% Co, Cu/Co molar ratio= 0.21:1 Polyol process method [Toluene] = 250 ppm, [NO] = 500 ppm, [O2] = 7 vol-%, N2 balance, total flow= 0.4 l min–1·STP, catalyst (2.5 g), T = 573 K, P = 0.1 MPa, retention time= 4.48×10–5 h–1 NO conv.: 83%, Toluene conv.: 98% (1) The change of pore structure in Cu–Co/Al2O3 enhances the activity in the reduction of NO with toluene. (2) Toluene conversion is reduced in the presence of NO due to the competitive reaction of O2-toluene-NO [211]
CuCo/DFS 12.4 wt-% Cu, 8.3 wt-% Co Wet impregnation method [NO] = 1200 ppm, [CO] = 1200 ppm, Ar balance, T = 423 K NO conv.: ~100%, CO conv.: ~100% The interaction of metal and support is beneficial to the formation of CuCo2O4, Cu1.5Mn1.5O4 and CuO which are responsible for increasing activity [210]
CuMn/DFS 13.5 wt-% Cu, 10.2 wt-% Mn Wet impregnation method NO conv.: ~90%, CO conv.: ~96% [210]
Cu–Zn/γ-Al2O3 3 wt-% Cu, Cu/Zn molar ratio= 2:1 Chemical reduction method by a liquid polyol solution [NO] = 400 ppm, [CO] = 200 ppm, [O2] = 6 vol-%, He balance, the total flow rate= 650 mL·min–1, GHSV= 2.4×104 h–1, T = 473 K, P = 0.1 MPa NO conv.: 100%, CO conv.: 100% (reduction temperature: 413 K, reduction time: 313 K) The presence of Zn promotes the dispersion of Cu particles, and enhances the redox properties of CuO [212]
Cu–Ag/mordenite 1.5 wt-% Cu, 1.5 wt-% Ag Conventional ion exchange method [NO] = 650 ppm, [C3H6] = 550 ppm, [O2] = 2 vol-%, [CO] = 0.4 vol-%, N2 balance, a total gas flow of 100 mL·min–1, catalyst (0.03 g) NO conv.: 67% (1) The CuO formed by the migration of Cu on the surface causes catalyst deactivation. (2) Cu+ and Cu2+ can both adsorb NO, and Ag can promote Cu+/Cu2+ redox cycle [213]
Tab.7  Reported catalysts for the reduction of nitric oxide
Fig.15  Reaction mechanism of the nitrate reduction catalyzed by maghemite/Cu/Pd (reprinted from [231], copyright (2012), with permission from Elsevier).
Catalysts Composition of catalysts Preparation methods Reaction conditions Catalytic performance Comments Ref.
Cu–Ni/Ac 20 wt-% CuO+NiO, Cu/Ni molar ratio= 2:1 Wetness impregnation method CO/H2O/N2 molar ratio= 4.5%:30.5%:65%, catalyst (0.25 g), T = 623 K CO conv.: 95% The size of the catalyst plays a more important role rather than Cu/Ni content [185]
Cu–Ni/AC 62.7 wt-% Cu, Cu/Ni molar ratio= 1.56:1 Wetness impregnation method CO/H2O molar ratio= 4.5%:30.6%, N2 balance, GHSV= 4000 h–1, catalyst (0.25 g), T = 623 K CO conv.: 82.5% Cu remains in Cu0 during the reaction and the CuNi alloy formation inhibits methane production [188]
Ni–Cu/SiO2 10 wt-% Ni–Cu, Ni/Cu molar ratio= 5:5 In situ self-assembled core-shell precursor method CO/H2O molar ratio= 5%:25%, He balance, the total flow rate= 50 mL·min–1, GHSV= 68000 h–1, catalyst (0.05 g), T = 673 K CO conv.: 78.9%, H2 yield: 45%, TOF= 0.002 s–1 The highly dispersed NiCu alloy can promote the CO adsorption and activate hydroxyl on the SiO2 surface [187]
Ni–Cu/SiO2 (OA) 10 wt-% Ni–Cu, Ni/Cu molar ratio= 5:5,
OA/metal molar ratio=0.25:1
In situ self-assembled core-shell precursor method CO conv.: 96.8%, H2 yield: 53%, TOF= 0.004 s–1 OA can promote metal dispersion and enhance the interaction between metal and support [187]
Cu–Ni/SiO2 Thermal decomposition precursor H2O/CO= 4:1, GHSV= 3600 h–1, catalyst (1.0 g), T = 573 K, P = 0.1 MPa CO conv.: 97.83%, CO2 select.: 98.64% This preparation method contributes to the high dispersion of CuO and NiO [194]
Cu–Ni/γ-Al2O3 10 wt-% Cu, 10 wt-% Ni Co-precipitation method H2 (60 vol-%), CO (1 vol-%), O2 (1 vol-%), He balance, GHSV= 60000 h–1, T = 473 K Without H2O and CO2, CO conv.: 2.91 mmolCO·s–1·kgcat–1, with 10 vol-% H2O: 3.58 mmolCO·s–1·kgcat–1, with 10 vol-% CO2:2.42 mmolCO·s–1·kgcat–1, with 10 vol-% H2O and 10 vol-% CO2: 2.51 mmolCO·s–1·kgcat–1 (1) The addition of H2O has a positive effect on CO conversion while the addition of CO2 has a negative effect. (2) CO conversion is in the order of Cu–Mn/Al2O3>Cu–Ni/Al2O3>Cu/Al2O3>Ni/Al2O3>Mn/Al2O3>Al2O3. (3) The formation of CuMn2O4 contributes to the high dispersion of Cu and Mn, resulting in high CO conversion [193]
Cu–Mn/γ-Al2O3 10 wt-% Cu, 10 wt-% Mn Co-precipitation method H2 (60 vol-%), CO (1 vol-%), O2 (1 vol-%), He balance, GHSV= 60000 h–1, T = 473 K Without H2O and CO2, CO conv.: 3.32 mmolCO·s–1·kgcat–1, with 10 vol-% H2O: 3.85 mmolCO·s–1·kgcat–1, with 10 vol-% CO2: 2.66 mmolCO·s–1·kgcat–1, with 10 vol-% H2O and 10 vol-% CO2: 3.11 mmolCO·s–1·kgcat–1 [193]
Ce0.7Cu0.1Fe0.2O2−δ Ce/Cu/Fe molar ratio= 0.7:0.1:0.2 Sonochemical method CO (2 vol-%), N2 balance, total gas flow rate= 100 mL·min–1, The flow rate of water vapor= 55 mL·min–1, GHSV= 48000 h–1, P = 0.1 MPa CO conv.: 100%,
H2 select.: 100%
Compared to Cu–Ni/CeO2, the activity of Cu–Fe/CeO2 is lower because Fe is more easily to be oxidized under reaction conditions [191]
Ce0.75Cu0.1Ni0.15O2−δ Ce/Cu/Ni molar ratio= 0.75:0.1:0.15
Cu0.3Fe0.7Ox Cu/Fe molar ratio= 3:7 Aerosol-spray self-assembly method 2.2% CO/N2 stream (56 cm3·min–1), CO/H2O feed ratio= 1:7, GHSV= 42000 cm3·g–1·h–1, catalyst (20 mg), T = 523 K, P = 0.1 MPa, t = 140 h Rate= 1.46×10–6 mol·m–2·s–1, TOF= 0.047 s-1, CO conv.: 50% (1) The addition of Fe can promote the dispersion of Cu0 and enhance the adsorption of CO and CO2. (2) The addition of Al enhances the durability of the catalyst [190]
Cu0.3Fe0.6Al0.1Ox Cu/Fe/Al molar ratio= 3:6:1 Aerosol-spray self-assembly method Rate= 3.98×10–6 mol·m–2·s–1, TOF= 0.136 s–1, CO conv.: 85% [190]
CuPd/CeO2 30 wt-% Cu, 1 wt-% Pd Incipient wetness impregnation method CO (4 vol-%), CO2 (10 vol-%), air (2 vol-%), Ar (26 vol-%), H2 balance, H2O/CO molar ratio= 10:1 CO conv.: 77% H2 prefers to be adsorbed and dissociated on Pd site, and H2 spillovers to CuO site, resulting in the congregation of reduced Cu accompanied with water desorption [183]
Pd–Cu/CeO2 5 wt-% Cu, 1 wt-% Pd Incipient wetness impregnation method CO/H2O/CO2/H2/Air= 9.7%:22.8%:6.3%:37.9%:6.9% (1.4% O2), argon balance, a total flow rate of 132.5 mL·min–1, GHSV= 64400 h–1 (dry), catalyst (0.15 g), T = 533 K H2 production rates: 122 μmol·g–1·s–1 Compared with Pt in Pt-Cu/CeO2, the Pd in Pd–Cu/CeO2 is more surrounded by Cu and the interaction between Cu and Pd is stronger [184]
Pt–Cu/CeO2 5 wt-% Cu, 1 wt-% Pt Incipient wetness impregnation method H2 production rates: 160 μmol·g–1·s–1 [184]
Pt–Cu/ZnO/Al2O3 Cu/Zn molar ratio= 1:1, 0.05 wt-% Pt, 10 mol-% Al Co-precipitation methods CO/H2O/H2/CO2/N2 = 0.77:2.2:4.46:0.57:30, GHSV= 4800 mL·h–1·gcat–1, catalyst (0.05 g), T = 523 K CO conv.: 78%,
TOF=1.95×10–2 s–1
Pt promotes the H2 spillover from Pt to Cu to prohibit Cu from sintering and accelerates the reduction-oxidation cycle of Cu0 and Cu+ [182]
Au–Cu/ CeO2 7 wt-% Cu, 1 wt-% Au Incipient wetness impregnation method A total flow rate of 200 mL·min–1, balanced to He, GHSV= 12000 h–1, WSV= 1.83 NL min–1·g–1, catalyst (0.1 g), T = 483 K, in WGS.
CO/H2O/H2/CO2 = 4:9.4:37.9:3, in CO-PROX:
CO/O2/H2 = 4:0.56:37.9, in OWGS: CO/H2O/H2/CO2/O2 = 4:9.4:37.9:3:0.56
In CO-PROX: CO conv.: 36%, in WGS: CO conv.: 1%, in OWGS: CO conv.: 35%, The catalyst prepared by deposition-precipitation shows higher Au dispersion and oxygen storage capacity than the catalyst prepared by incipient wetness impregnation [181]
Au–Cu/ CeO2 7 wt-% Cu, 1 wt-% Au Deposition-precipitation method in CO-PROX: CO conv.: 37%, in WGS: CO conv.: 3.8%, in OWGS: CO conv.: 40% [181]
Au–CuO/CeO2 7 wt-% CuO, 1 wt-% Au Incipient wetness impregnation method A total flow rate of 200 mL·min–1, He to balance, GHSV= 12000 h–1, WSV= 1.83 NL min–1·g–1, catalyst (0.1 g), in CO-PROX: CO/H2/O2 = 0.5:30:0.5 (in % by vol.), T = 372 K, in WGS: CO/H2O/H2/CO2 = 0.5:20:30:4, T = 623 K, in OWGS: CO/H2/H2O/O2 = 0.5:30:20:0.5, T = 493 K In CO-PROX: CO conv.: 100%, in WGS:
CO conv.: 31%, in OWGS: CO conv.: 95%
(1) The addition of O2 greatly promotes the CO conversion.
For WGS, the addition of Au in CuO/CeO2 has no promotion on catalytic activation. (2) The presence of Au influences the reduction of CeO2 surface
[180]
ReCu/gadolinium doped ceria 4% Cu, 1% Re Impregnation method CO (5%), H2O (10%), N2 balance, a total flow rate= 100 mL·min–1, catalyst (0.15 g), T = 673 K CO conv.: 93%, the rate of WGS reaction= 61.6 μmol·g–1·s–1 (1) The transfer of electron density between Re, Cu, Ce and Gd contributes to the decrease of catalyst surface. (2) Re helps Cu reduce Ce4+ and produce more Ce3+ on the ceria surface, and leads the catalyst to be more resistant to deactivation [192]
Tab.8  Reported catalysts for the water gas shift reaction
Fig.16  Possible reaction mechanism of reducing 4-NP to 4-AP with NaBH4 on the CuNiOS-0.6 catalyst (reprinted from [257], copyright (2017), with permission from Royal Society of Chemistry).
Catalysts Composition of catalysts Preparation methods Reaction conditions Catalytic performance Comments Ref.
Ni/Cu nanowires Cu/Ni molar ratio= 1:2 Liquid phase reduction of Ni and transmetalation reaction of Cu assisted by a magnetic field Reactant: 4-NP (1×10–4 mol·L–1, 30 mL), reducing agent: NaBH4 (0.05 mol·L–1, 10 mL), at room temperature K = 0.9118 min–1, 4-NP conv.: 98.65%, the catalyst can be reused for 10 times Ni has no catalytic activity. The high ratio of corners and edges, and interaction between them enhance the activity [251]
Cu(0)-Ni(0)-AAPTMS@GO 5 wt-% Cu, Cu/Ni molar ratio= 1:1 Incipient wetness impregnation method Reactant: 4-NP (5.0 mol·L–1, 30 mL), reducing agent: NaBH4 (60 mg), at room temperature 4-NP conv.: 100%, 4-AP select.: 100%, (in 20 min), the catalyst can be reused for 6 times Ni is more easily coordinated with the electron-donated N atom of the organic group due to the higher binding capacity than Cu [258]
CuxNiy Cu/Ni molar ratio= 7:3 Wet chemical reduction method Reactant: NMA methanol solution (0.2 mol·L–1, 150 mL), reducing agent: H2 (0.8 MPa), T = 413 K, stirring at 400 r?min–1 NMA conv.: 95.7%, 3-amino-4-methoxy-acetylaniline select.: 99.4%, the catalyst can be reused for 4 times The formation of CuNi alloy contributes to the reduction of NMA to AMA [256]
CuNiOS-0.6 Cu/Ni molar ratio= 1:0.6 Solution-based method Reactant: 4-NP solution (20 ppm, 100 mL), reducing agent: NaBH4 solution (0.1 mol·L–1, 3 mL) K = 7.0×10–3 s–1·mg–1, better than the catalysts reported before The presence of Ni can enhance the electron transfer in the reduction reaction [257]
Cu54Ni46@SiO2 2.3 wt-% Cu, Cu/Ni molar ratio= 54:46 Co-reduction method Reactant: 4-NP (4 mmol, 25 mL), reducing agent: NaBH4 (175 mg), catalyst (5.0 mg) Kapp= 5.10×10–3 s–1, stably cycle 10 times. The catalyst can be reused for 10 times The presence of Ni changes the surface electronic structure and the binding energy to the adsorbate is between Cu and Ni [255]
Fe–Cu/SiO2 3 wt-% Cu, 7 wt-% Fe, Cu/Fe molar ratio= 3:8 Impregnation method Reactant: P-DB (0.08 mol·L–1, 30 mL), T = 418–453 K, P = 1.3 MPa H2 p-Phenylenediamine select.: 89% The method of synthesis and the conditions of thermal treatment affect a lot on the catalytic properties of the supported bimetallic Fe–Cu catalysts [253]
Au/Cu/MgO 0.05 wt-% Cu, Cu/Au molar ratio= 1:1.16 Deposition method of preformed nanocluster beams Reactant: 4-NP solution (0.06×10–3 mol·L–1), reducing agent: NaBH4 solution 2.5×10–3 mol·L–1), at room temperature K = 3.49×104 min−1·mol−1, 8.9 (6.6) times higher than the Au-rich (Cu-rich) clusters, 25 times higher than that produced by traditional impregnation method The Au/Cu alloy NPs shows higher catalytic activity either than rich Au or rich Cu clusters maybe because Au and Cu atoms are randomly located in clusters without chemical ordering, which could be interpreted that there are more Cu/Au sites on the surface to adsorb 4-NPA [250]
Cu–Au Cu/Au volume ratio= 99.5:0.5 Co-electrodeposition method Reactant: 4-NP (1 mmol·L–1), reducing agent: NaBH4 (0.1 mol·L–1), a total volume of 30 mL, T = (293±2) K k = 27.3 s−1·g−1 The incorporation of Au increases the crystallite size of Cu2O, decreases the size of Cu, and prevents Cu2O from further oxidation [249]
Cu/Ru/MWCNT 10 wt-% Cu, Cu/Ru molar ratio= 15.78:1 In situ reduction method Reactant: 4-BTN (1 mmol), reducing agent: NaBH4, anhydrous CoCl2 (0.5 mmol), at room temperature 4-BTN conv.: 100%, 4-bromoaniline select.: 100%, the catalyst can be reused for 5 times (1) Ru sites are responsible for the dissociative activation of H2 and Cu+ sites contribute on adsorption-activation of C=O bond. (2) NaBH4 is a valid hydrogen source compared to H2, hydrated hydrazine, formic acid and acetic acid [246]
Cu nanowires-Ag heterostructures Cu/Ag molar ratio= 22:1 Unique hydrothermal synthesis method Reactant: 4-NP solution (1 mmol·L–1, 1 mL), reducing agent: NaBH4 (0.025 mol·L–1, 2 mL), at room temperature, stirring at 4000 r?min–1 k = 0.0067 s–1, the catalyst can be reused for 3 times The small variation in local electronic structure at the interface between Cu and Ag can contribute to the enhancement of the catalytic activity [241]
Cu/Ag NPs Cu/Ag molar ratio= 1:1 A one-pot method Reactant: 4-NP (0.1 mmol·L–1, 4 mL), reducing agent: NaBH4 (0.3 mol·L–1, 150 μL), at room temperature k = 3.95×10−3 s−1, activity is about 5 times higher than that of single-metal Ag NPs, the catalyst can be reused for 4 times Electron transfer from Cu to Ag increases the surface electron density. The formation of Cu/Ag alloy will produce strong binding energy [242]
C–CuAg NPs Cu/Ag molar ratio= 9.65:9.10 A facile one-pot method Reactant: 4-NP solution (0.1 mmol·L–1, 2.0 mL), reducing agent: NaBH4 (10 mmol·L–1, 1.0 mL), C–CuAg NPs (0.05 mg) k = 0.442 min−1, the catalyst can be reused at least ten times The formation of carbon shell and electron transfer from Cu to Ag increases the surface electron density [243]
Cu/CuO–Ag 1.28 wt-% Ag In situ reduction method Rreactant: 4-NP solution, reducing agent: NaBH4 k = 4.60×10–2 s–1, no significant activity loss in the consecutive five reaction runs CuO NPs can help Cu/CuO–Ag capture the electron/hydrogen anion and accelerate the 4-NP reduction [245]
Cu0–Ag0/CA–CuO In situ reduction method Reactant: 4-NP (0.15 mmol, 100.0 mL), reducing agent: NaBH4 (15.0 mmol, 100.0 mL) k = 0.20 min–1, the catalyst can be reused for 4 times The higher catalytic activity may be due to higher metal uptake [244]
Cu–Ag Cu/Ag molar ratio= 35:65 Electrochemical displacement method Reactant: 4-NP solution (1 mmol·L–1, 10 mL), reducing agent: NaBH4 solution (25 mmol·L–1, 1 mL), at room temperature k = 28.2×10–3 mmol·L–1·g–1·s–1 (1) Phase separated mixtures were formed for higher Cu2+ concentration. (2) Sponge/dendrites are effective in the reduction of 4-NP [237]
Ag–Cu Cu/Ag molar ratio= 1:1 Nanocasting method Reactant: 4-NP solution (0.01 mol·L–1, 30 μL), reducing agent: NaBH4 solution (0.1 mol·L–1, 200 μL), deionized water (2 mL), at room temperature k = 5.5×10–2 s–1, about 96% reduction efficacy, the catalyst can be reused for 8 times The bimetallic composites have high electron density on the surface by means of electron transfer from one metallic state to other [247]
Cu/Pd Cu/Pd molar ratio= 53:32 A mild hydrothermal one-pot method Reactant: 4-NP (10 mmol·L–1, 50 μL), reducing agent: NaBH4 (10 mmol·L–1, 3 mL), bimetallic solution (1 mg·mL–1, 50 μL), treated with lactic acid Two times better than Cu/Pd without lactic acid treatment The lattice constant decreases arising from the smaller diameter of Cu/Pd atoms relative to Cu atoms [240]
CuPd Cu/Pd molar ratio= 9:1 Surfactant-free hydrothermal method Reactant: 4-NP solution (0.10 mmol·L–1, 20 mL), reducing agent: NaBH4 solution (20 mmol·L–1, 5 mL) k = 35×10–2 min–1 Presence of Pd increases the surface area of CuPd alloy NPs [239]
Reactant: 4-NA (0.10 mmol·L–1, 20 mL), reducing agent: NaBH4 solution k = 33.046×10–2 min–1
Pt–Cu@3DG 5 wt-% Cu, Cu/Pt molar ratio= 5.08:1 Mild chemical reduction method Reactant: 4-NP (0.033 mmol?L–1, 6 mL), reducing agent: NaBH4 (0.4 mmol?L–1, 14 mL), at room temperature k = 0.430 min−1, 4-NP conv.: 98.6%, the catalyst can be recycled for 5 times Macroporous structure and large specific surface
area result in high catalytic activity
[259]
TiO2 NWs/polymer brush/Cu–Pt Regenerative counterion exchange-reduction method Reactant: 4-NP, reducing agent: NaBH4 (excessive) Nearly two times the photocatalytic rate as TiO2 NWs /polymer brush/Cu The coexistence of Cu and Pt on TiO2 results in the smaller particle size and higher surface area [20]
Cu–Ag/GP 20.44 wt-% Cu, 23.92 wt-% Ag, 25.38 wt-% C, 30.26 wt-% O Simple adsorption method Reactant: 4-NP (1 mmol?L–1, 3 mL), 2-NP (1 mmol?L–1, 3 mL), reducing agent: NaBH4 (0.5 mol?L–1, 0.5 mL), catalyst (10 mg) For 4-NP: k = 4.05×10–3 s–1, TOF= 81.34 h–1 (1) The catalyst supported on ginger rhizome powder exhibits excellent reusability and stability. (2) The catalysts own excellent absorbance of metal ions, surface distribution of nanoparticles, outstanding reusability and stability [248]
For 2-NP: k = 1.21×10–3 s–1, TOF= 45.86 h–1
Cu–Ni/GP 19.2 wt-% Cu, 13.32 wt-% Ni, 35.15 wt-% C, 32.33 wt-% O Simple adsorption method Reactant: 4-NP (1 mmol?L–1, 3 mL), 2-NP (1 mmol?L–1, 3 mL), reducing agent: NaBH4 (0.5 mol?L–1, 0.5 mL), catalyst (10 mg) For 4-NP: k = 6.08×10–3 s–1, TOF= 85.83 h–1 [248]
For 2-NP: k = 1.11×10–3 s–1, TOF= 27.16 h–1
Cu/Ag Cu/Ag molar ratio= 61:39 Electrodeposition method Reactant: 4-NP, reducing agent: NaBH4, a total volume of 30 mL, stirring at 800 r?min–1 k(Cu/Pd) = 2.4×10–4 s–1, k(Cu/Au) = 1.4×10–3?s–1, k(Cu/Ag) = 1.6×10–2 s–1, the performance is greatly enhanced with the small amount of CuSO4, and k(Cu/Ag) = 8.5×10–2 s–1 (5.1 min–1) (1) The presence of Ag forms a network of bulk microcrystals and narrow nanowires, causing many hot pots, while the presence of Au forms large dendrites, reducing hot spots. (2) The localised change in the electronic structure of Cu/Ag contributes to the electron transfer from Cu to Ag and increases the electron density of Ag, and further enhances the adsorption of nitro group [238]
Cu/Au Cu/Au molar ratio= 35:65 Electrodeposition method Reactant: 4-NP, reducing agent: NaBH4, a total volume of 30 mL, stirring at 800 r?min–1 [238]
Cu/Pd Cu/Pd molar ratio= 56:44 Electrodeposition method Reactant: 4-NP, reducing agent: NaBH4, a total volume of 30 mL, stirring at 800 r?min–1 [238]
AgCu Two simultaneous replacement method to prepare dendrites in one step Reactant: 4-NP solution (7×10–5 mol?L–1, 50 mL), reducing agent: NaBH4 solution (0.2 mol?L–1, 3.6 mL), at room temperature CuPd catalyst has been proved to be the most active catalyst, and the order of activity is as follows: CuPd (k = 193×10–3 mmol·g–1·s–1)>CuPt>CuAu>Cu>Ag1Cu1 >Ag3Cu1 >AuPd>Ag1Cu3 >AgPd>Ag (k = 1.75×10–3 mmol·g–1·s–1) (1) AgCu exhibited normal dendrites, CuAu dendrites were short with symmetric branches, the CuPd dendrites had longer trunks but irregular branches, and the CuPt dendrites consisted of randomly aggregated nanoparticles. (2) The formation of different dendritic structures results in the various Cu loading and distinct performance [236]
CuAu Two simultaneous replacement method to prepare dendrites in one step [236]
CuPt Two simultaneous replacement method to prepare dendrites in one step [236]
CuPd Two simultaneous replacement method to prepare dendrites in one step [236]
Tab.9  Reported catalysts for the reduction of aromatic nitro compounds
NPs Nanoparticles
CSNPs Core-shell nanoparticles
WGS Water gas shift
DFT Density functional theory
CNFs Carbon nanofibers
PROX Preferential oxidation reaction
GHR Glycerol hydrogenolysis reaction
1,2-PDO 1,2-Propanediol
H2-TPR H2-temperature programmed reduction
IWI Incipient wetness impregnation
NH3-TPD NH3-temperature programmed desorption
CTH Catalytic transfer hydrogenation
APR Aqueous phase reforming
HR-TEM High resolution-transmission electron microscope
XPS X-ray photoelectron spectroscopy
EL Ethyl levulinate
WHSV Weight hourly space velocity
TOF Turnover frequency
MA Mesoporous alumina
GHSV Gas hourly space velocity
LHSV Liquid hour space velocity
CNT Carbon nanotube
GVL γ-Valerolactone
1,4-PeD 1,4-pentanediol
GBL γ-Butyrolactone
STY Space time yield
DRIFTS Diffused reflectance infrared fourier transform spectroscopy
FTs Fischer-Tropsch synthesis
STM Scanning tunneling microscope
LDHs Layered double hydroxides
CFs Carbon fibers
BTC 1,3,5-Benzenetricarboxylic acid
DBA 3,3-Dimethyl-1-butanal
ACF Activated carbon fibrous
XRD X-ray diffraction
DBO 3,3-Dimethyl-1-butanol
MWCNT Multi-walled carbon nanotube
OWGS Oxygen-assisted-water gas shift
DP Deposition-precipitation
WSV Water space velocity
SCR Selective catalytic reduction
OMC Ordered mesoporous carbons
DFS Depleted fullerene soot
TNTs Titanate nanotubes
SS Stainless steel
4-NP 4-Nitrophenol
NZVI Nanoscale zerovalent iron
AC Activated carbon
AC1 Oxidation of AC in liquid phase with HNO3
AC2 Heat treatment of AC1 during 1 h at 700°C under N2
AC3 Heat treatment of AC1 during 1 h at 700°C under H2 flow
CNT1 Carbon nanotubes sample Nanocyl-3100
CNT2 Carbon nanotubes treated in an acid bath of H2SO4 (50 vol.%)
CXG Carbon xerogel
P-DB p-Dinitrobenzene
4-AP 4-Aminophenol
4-NA 4-Nitroaniline
4-BTN 4-Bromonitrobenzene
2-NP 2-Nitrophenol
GP Ginger rhizome powder
NMA 3-Nitro-4-methoxy-acetylaniline
AAPTMS N-(2 amino ethyl)-3-amino propyl trimethoxy silane
GO Graphene oxide
CA Cellulose acetate
3DG Three-dimensional graphene
ORR Oxygen reduction reaction
EXAFS Extended x-ray absorption fine structure
NPCC Nanoporous carbon composite
CB Conduction band
  
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