Single-atom catalysts for (photo)electrocatalytic biomass valorization to high-value-added chemicals

Abstract

As a crucial renewable energy resource, biomass can be converted into high-value-added chemicals via unique catalytic routes, which facilitate the reduction of excessive dependency on fossil resources. However, the complex functional groups inherent in biomass and biomass-derived compounds enable considerable difficulties for their selective functionalization. The precise cleavage of special chemical bonds in biomass highly depended on the structure design of catalysts. Single-atom catalysts (SACs) have garnered significant attention in biomass valorization through the electrocatalytic and photoelectrocatalytic processes due to their maximal atom utilization efficiency, unique electronic structure, and tunable coordination environments. The present review outlines the latest research progress in this emerging field, focusing on the (photo)electrocatalytic application of SACs in biomass valorization, including cellulose-derived and hemicellulose-derived compounds and lignin. We also emphasize the innovative design and precise modulation of atomically dispersed metal active sites at the atomic level. Through state-of-the-art catalytic systems, we elaborately discuss the structure-activity relationship and elucidate the mechanisms of the (photo)electrocatalytic processes over SACs. Finally, we provide the prospects of SACs in (photo)electrocatalytic biomass valorization.

Keywords

Single-atom catalysts / biomass valorization / electrocatalysis / photoelectrocatalysis

References

[1] Nanda S,Pant KK,Kozinski JA.Characterization of North American lignocellulosic biomass and biochars in terms of their candidacy for alternate renewable fuels.Bioenerg Res2013;6:663-77

[2] Taarning E,Yang X,Andersen SI.Zeolite-catalyzed biomass conversion to fuels and chemicals.Energy Environ Sci2011;4:793-804

[3] Kavitha S,Kasthuri S.Profitable biomethane production from delignified rice straw biomass: the effect of lignin, energy and economic analysis.Green Chem2020;22:8024-35

[4] Deng W,Fu J.Catalytic conversion of lignocellulosic biomass into chemicals and fuels.Green Energy Environ2023;8:10-114

[5] Madadi M,Sun F.Sustainable lignocellulose fractionation by integrating p-toluenesulfonic acid/pentanol pretreatment with mannitol for efficient production of glucose, native-like lignin, and furfural.Bioresour Technol2023;371:128591

[6] Li X,Yang J.Production of 5-hydroxymethylfurfural and levulinic acid from lignocellulosic biomass and catalytic upgradation.Ind Crop Prod2019;130:184-97

[7] Wang T,Shanks BH.Catalytic dehydration of C₆ carbohydrates for the production of hydroxymethylfurfural (HMF) as a versatile platform chemical.Green Chem2014;16:548-72

[8] Gürbüz EI,Alonso DM,Lim WY.Conversion of hemicellulose into furfural using solid acid catalysts in γ-valerolactone.Angew Chem Int Ed2013;52:1270-4

[9] Devi A,Kour H,Pant D.Lignocellulosic biomass valorization for bioethanol production: a circular bioeconomy approach.Bioenergy Res2022;15:1820-41 PMCID:PMC8819208

[10] Wang M,Lu J.Photo splitting of bio-polyols and sugars to methanol and syngas.Nat Commun2020;11:1083 PMCID:PMC7046649

[11] Yoo CG,Pu Y.The critical role of lignin in lignocellulosic biomass conversion and recent pretreatment strategies: a comprehensive review.Bioresour Technol2020;301:122784

[12] Garedew M,Jackson JE.Electrocatalytic upgrading of phenolic compounds observed after lignin pyrolysis.ACS Sustain Chem Eng2019;7:8375-86

[13] Meng Q,Liu H,Han B.Synthesis of ketones from biomass-derived feedstock.Nat Commun2017;8:14190 PMCID:PMC5290317

[14] Zhou H,Xu SM.Selectively upgrading lignin derivatives to carboxylates through electrochemical oxidative C(OH)-C bond cleavage by a Mn-doped cobalt oxyhydroxide catalyst.Angew Chem Int Ed2021;60:8976-82

[15] Kumar R.Thermochemical production of bio-oil: a review of downstream processing technologies for bio-oil upgrading, production of hydrogen and high value-added products.Renew Sustain Energy Rev2021;135:110152

[16] Pang S.Advances in thermochemical conversion of woody biomass to energy, fuels and chemicals.Biotechnol Adv2019;37:589-97

[17] Liu W,Du X,Chao Z.High efficiency hydrogen evolution from native biomass electrolysis.Energy Environ Sci2016;9:467-72

[18] Du X,Zhang Z.Low-energy catalytic electrolysis for simultaneous hydrogen evolution and lignin depolymerization.ChemSusChem2017;10:847-54

[19] Tang W,Qiu T.Efficient conversion of biomass to formic acid coupled with low energy consumption hydrogen production from water electrolysis.Angew Chem Int Ed2023;62:e202305843

[20] Zhang X,Lee AF.Heterogeneously catalyzed hydrothermal processing of C₅-C₆ sugars.Chem Rev2016;116:12328-68

[21] Zhang B,Yan C,Mu T.Operando forming of lattice vacancy defect in ultrathin crumpled nivw-layered metal hydroxides nanosheets for valorization of biomass.Small2023;19:e2207236

[22] Li S,Wang Y.Doped Mn enhanced NiS electrooxidation performance of HMF into FDCA at industrial-level current density.Adv Funct Mater2023;33:2214488

[23] Cao Y,Ji S.Adsorption site regulation to guide atomic design of ni-ga catalysts for acetylene semi-hydrogenation.Angew Chem Int Ed2020;59:11647-52

[24] Rao P,Fan W.Movable type printing method to synthesize high-entropy single-atom catalysts.Nat Commun2022;13:5071 PMCID:PMC9424199

[25] Zhao H,Yin J.Stabilizing lattice oxygen through Mn doping in NiCo₂O_4-δ spinel electrocatalysts for efficient and durable acid oxygen evolution.Angew Chem Int Ed2024;63:e202402171

[26] Ye Y,Li X.Orbital occupancy modulation to optimize intermediate absorption for efficient electrocatalysts in water electrolysis and zinc-ethanol-air battery.Adv Mater2024;36:e2312618

[27] Wang D,Han C,Xing Z.Atomic and electronic modulation of self-supported nickel-vanadium layered double hydroxide to accelerate water splitting kinetics.Nat Commun2019;10:3899 PMCID:PMC6715676

[28] Liu S,Wu S.A coupled electrocatalytic system with reduced energy input for CO₂ reduction and biomass valorization.Energy Environ Sci2023;16:5305-14

[29] Wu X,Shi X.Multi-site catalysis of high-entropy hydroxides for sustainable electrooxidation of glucose to glucaric acid.Energy Environ Sci2024;17:3042-51

[30] Wu Y,Wu J,Wang C.High-surface area mesoporous Sc₂O₃ with abundant oxygen vacancies as new and advanced electrocatalyst for electrochemical biomass valorization.Adv Mater2024;36:e2311698

[31] Zheng X,Li P.Ir-Sn pair-site triggers key oxygen radical intermediate for efficient acidic water oxidation.Sci Adv2023;9:eadi8025 PMCID:PMC10584348

[32] Yang J,Li J.Engineering a hollow bowl-like porous carbon-confined Ru-MgO hetero-structured nanopair as a high-performance catalyst for ammonia borane hydrolysis.Mater Horiz2024;11:2032-40

[33] Liu WJ,Zhao D.Efficient electrochemical production of glucaric acid and H₂ via glucose electrolysis.Nat Commun2020;11:265 PMCID:PMC6959317

[34] Liu C,Yue K.S-species-evoked high-valence Ni^2+δ of the evolved β-Ni(OH)₂ electrode for selective oxidation of 5-hydroxymethylfurfural.Adv Mater2023;35:e2211177

[35] Zhou P,Chao Y.Partially reduced Pd single atoms on CdS nanorods enable photocatalytic reforming of ethanol into high value-added multicarbon compound.Chem2021;7:1033-49

[36] Zhou P,Lv F.Metal single atom strategy greatly boosts photocatalytic methyl activation and C-C coupling for the coproduction of high-value-added multicarbon compounds and hydrogen.ACS Catal2020;10:9109-14

[37] Yang W,Zhou B.Why is C-C coupling in CO ₂ reduction still difficult on dual-atom electrocatalysts?.ACS Catal2023;13:9695-705

[38] Zhang Z,Ge X.Mixed plastics wastes upcycling with high-stability single-atom Ru catalyst.J Am Chem Soc2023;145:22836-44

[39] Liu J,Yang M.Tackling CO poisoning with single-atom alloy catalysts.J Am Chem Soc2016;138:6396-9

[40] Xia J,Di J.Construction of single-atom catalysts for electro-, photo- and photoelectro-catalytic applications: State-of-the-art, opportunities, and challenges.Mater Today2022;53:217-37

[41] Nakaya Y,Yamazoe S,Furukawa S.Single-atom Pt in intermetallics as an ultrastable and selective catalyst for propane dehydrogenation.Nat Commun2020;11:2838 PMCID:PMC7275083

[42] Cao L,Liu W.Identification of single-atom active sites in carbon-based cobalt catalysts during electrocatalytic hydrogen evolution.Nat Catal2019;2:134-41

[43] Vasconcelos SC,Lima CGS.Single-atom catalysts for the upgrading of biomass-derived molecules: an overview of their preparation, properties and applications.Green Chem2022;24:2722-51

[44] Gan T.Atomically dispersed materials: Ideal catalysts in atomic era.Nano Res2024;17:18-38

[45] Cui T,Ye C.Heterogeneous single atom environmental catalysis: fundamentals, applications, and opportunities.Adv Funct Mater2022;32:2108381

[46] Wang L,Zhang L,Yang J.Perspective of p-block single-atom catalysts for electrocatalysis.Trends Chem2022;4:1135-48

[47] Qi H,Liu F.Highly selective and robust single-atom catalyst Ru₁/NC for reductive amination of aldehydes/ketones.Nat Commun2021;12:3295 PMCID:PMC8172939

[48] Liu Z,Gao X.Rational highly dispersed ruthenium for reductive catalytic fractionation of lignocellulose.Nat Commun2022;13:4716 PMCID:PMC9372153

[49] Li S,Yang J.Selective hydrogenation of 5-(hydroxymethyl)furfural to 5-methylfurfural over single atomic metals anchored on Nb₂O₅.Nat Commun2021;12:584 PMCID:PMC7838200

[50] Liu Y,He Q,He X.Catalytic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran over atomically dispersed ruthenium catalysts.Ind Eng Chem Res2020;59:4333-7

[51] Liu S,van Muyden AP.Oxidative cleavage of β-O-4 bonds in lignin model compounds with a single-atom Co catalyst.Green Chem2019;21:1974-81

[52] Meng G,Zhang W.Tandem catalyzing the hydrodeoxygenation of 5-hydroxymethylfurfural over a Ni₃Fe intermetallic supported Pt single-atom site catalyst.Chem Sci2021;12:4139-46 PMCID:PMC8179463

[53] Lou Y,Liu H.Edge-confined Pt₁/MoS₂ single-atom catalyst promoting the selective activation of carbon-oxygen bond.ChemCatChem2021;13:2783-93

[54] Zhu M,Zhao Y.Ring-opening transformation of 5-hydroxymethylfurfural using a golden single-atomic-site palladium catalyst.ACS Catal2019;9:6212-22

[55] Li Z,Zhang M.Selective hydrogenation on a highly active single-atom catalyst of palladium dispersed on ceria nanorods by defect engineering.ACS Appl Mater Interfaces2020;12:57569-77

[56] Meng W,Xie D.Engineering defective Co₃O₄ containing both metal doping and vacancy in octahedral cobalt site as high performance catalyst for methane oxidation.Mol Catal2024;553:113768

[57] De S,Luque R.Conversion of biomass-derived feedstocks into value-added chemicals over single-atom catalysts.Green Chem2022;24:2267-86

[58] Chen J,Guo F,Huang Y.Single-atom metal catalysts for catalytic chemical conversion of biomass to chemicals and fuels.ACS Catal2024;14:5198-226

[59] Wang D,Yin W.Defect engineering of single-atom catalysts in biomass conversion.Fuel2024;355:129439

[60] Lu Y,Wang H.Toward efficient single-atom catalysts for renewable fuels and chemicals production from biomass and CO₂.Appl Catal B Environ2021;292:120162

[61] Zhuang J.Recent advances of single-atom alloy catalyst: properties, synthetic methods and electrocatalytic applications.Mater Today Catal2023;2:100009

[62] Lu Y,Dong CL.Tuning the selective adsorption site of biomass on Co₃O₄ by Ir single atoms for electrosynthesis.Adv Mater2021;33:e2007056

[63] Ge R,Li Z.Selective electrooxidation of biomass-derived alcohols to aldehydes in a neutral medium: promoted water dissociation over a nickel-oxide-supported ruthenium single-atom catalyst.Angew Chem Int Ed2022;61:e202200211

[64] Gu W,Zhang S.Atomic-interface effect of single-atom Ru/CoO_x for selective electrooxidation of 5-hydroxymethylfurfural.ACS Appl Mater Interfaces2023;15:28036-43

[65] Xu H,Hu W.Single-atoms Ru/NiFe layered double hydroxide electrocatalyst: efficient for oxidation of selective oxidation of 5-hydroxymethylfurfural and oxygen evolution reaction.Appl Catal B Environ2023;339:123157

[66] Zeng L,Sun M.Cooperative Rh-O₅/Ni(Fe) site for efficient biomass upgrading coupled with H₂ production.J Am Chem Soc2023;145:17577-87

[67] Ji K,Xu SM.Electrocatalytic hydrogenation of 5-hydroxymethylfurfural promoted by a Ru₁ Cu single-atom alloy catalyst.Angew Chem Int Ed2022;61:e202209849

[68] Zhou Y,Luo X.A versatile single-copper-atom electrocatalyst for biomass valorization.Appl Catal B Environ2023;324:122218

[69] Wu Y,Chen W.Selective electroreduction of 5-hydroxymethylfurfural to dimethylfuran in neutral electrolytes via hydrogen spillover and adsorption configuration adjustment.Adv Mater2024;36:e2307799

[70] Zhou P,Luan P.Selective electrochemical hydrogenation of furfural to 2-methylfuran over a single atom Cu catalyst under mild pH conditions.Green Chem2021;23:3028-38

[71] Mukadam Z,Pedersen A.Furfural electrovalorisation using single-atom molecular catalysts.Energy Environ Sci2023;16:2934-44

[72] Wang Y,Xie Z.Efficient electrocatalytic oxidation of glycerol via promoted OH* generation over single-atom-bismuth-doped spinel Co₃O₄.ACS Catal2022;12:12432-43

[73] Yu H,Mao Q.Pt single atom captured by oxygen vacancy-rich NiCo layered double hydroxides for coupling hydrogen evolution with selective oxidation of glycerol to formate.Appl Catal B Environ2023;330:122617

[74] Feng X,Feng X.Single-atomic-site platinum steers middle hydroxyl selective oxidation on amorphous/crystalline homojunction for photoelectrochemical glycerol oxidation coupled with hydrogen generation.Adv Funct Mater2024;34:2316238

[75] Tian Z,Wang M.Selective photoelectrochemical oxidation of glucose to glucaric acid by single atom Pt decorated defective TiO₂.Nat Commun2023;14:142 PMCID:PMC9831984

[76] Ayele AA,Adam DB.Electrochemical oxidation of ethylene glycol on TiO₂-supported platinum single-atom catalyst into valuable chemicals in alkaline media.Appl Catal A Gen2022;646:118861

[77] Moges EA,Huang W.Sustainable synthesis of dual single-atom catalyst of Pd-N₄/Cu-N₄ for partial oxidation of ethylene glycol.Adv Funct Mater2022;32:2206887

[78] Chen W,Slater TJA.General synthesis of single atom electrocatalysts via a facile condensation-carbonization process.J Mater Chem A2020;8:25959-69

[79] Ayele AA,Awoke YA.Ni-doped TiO₂ supported Pt single-atom catalyst for partial oxidation of ethylene glycol to high-value chemicals in alkaline media.Mater Today Chem2023;34:101797

[80] Liu R,Yu C,Liu JF.Atomic-level-designed catalytically active palladium atoms on ultrathin gold nanowires.Adv Mater2017;29:1604571

[81] Tiwari JN,Park HJ.Remarkably enhanced catalytic activity by the synergistic effect of palladium single atoms and palladium-cobalt phosphide nanoparticles.Nano Energy2020;78:105166

[82] Li M,Wan C.Single-atom tailoring of platinum nanocatalysts for high-performance multifunctional electrocatalysis.Nat Catal2019;2:495-503

[83] Li S,Wang H.Hybrid palladium nanoparticles and nickel single atom catalysts for efficient electrocatalytic ethanol oxidation.J Mater Chem A2022;10:6129-33

[84] Zhang B,Sheng T.Ordered platinum-bismuth intermetallic clusters with Pt-skin for a highly efficient electrochemical ethanol oxidation reaction.J Mater Chem A2019;7:5214-20

[85] Luo S,Liao Y.A tensile-strained Pt-Rh single-atom alloy remarkably boosts ethanol oxidation.Adv Mater2021;33:e2008508

[86] Zhang G,Guo S.Tuning the selective ethanol oxidation on tensile-trained Pt(110) surface by Ir single atoms.Small2022;18:e2202587

[87] Zhang G,Yang Z.Hydrogen-induced p-d orbital hybridization and tensile strain of PdGa single-atom alloy metallene boosts complete electrooxidation of ethanol.Appl Catal B Environ2024;342:123377

[88] Lan B,Wei RL,Wang QL.Ethanol electrooxidation on rhodium-lead catalysts in alkaline media: high mass activity, long-term durability, and considerable CO₂ selectivity.Small2020;16:e2004380

[89] Zhu C,Wei R,Yang Y.Potential-dependent selectivity of ethanol complete oxidation on rh electrode in alkaline media: a synergistic study of electrochemical ATR-SEIRAS and IRAS.ACS Catal2019;9:4046-53

[90] Chang Q,Lee HJ.Achieving complete electrooxidation of ethanol by single atomic Rh decoration of Pt nanocubes.Proc Natl Acad Sci USA2022;119:e2112109119 PMCID:PMC8931248

[91] Pei A,Zhu L.Nickel hydroxide-supported Ru single atoms and Pd nanoclusters for enhanced electrocatalytic hydrogen evolution and ethanol oxidation.Adv Funct Mater2022;32:2208587

[92] Wang H,Zheng L.PdBi single-atom alloy aerogels for efficient ethanol oxidation.Adv Funct Mater2021;31:2103465

[93] Zhang Z,Wang J.Single-atom catalyst for high-performance methanol oxidation.Nat Commun2021;12:5235 PMCID:PMC8413426

[94] Poerwoprajitno AR,Watt J.A single-Pt-atom-on-Ru-nanoparticle electrocatalyst for CO-resilient methanol oxidation.Nat Catal2022;5:231-7

[95] Chen L,Wang D.Platinum-ruthenium single atom alloy as a bifunctional electrocatalyst toward methanol and hydrogen oxidation reactions.ACS Appl Mater Interfaces2022;14:27814-22

[96] Kong F,Song Y.Selectively coupling Ru single atoms to PtNi concavities for high-performance methanol oxidation via d-band center regulation.Angew Chem Int Ed2022;61:e202207524

[97] Zhuang L,Wang Y.Nitrogen-doped carbon black supported synergistic palladium single atoms and nanoparticles for electrocatalytic oxidation of methanol.Chem Eng J2022;438:135585

[98] Ruan J,Zhao G.Cobalt single atoms enabling efficient methanol oxidation reaction on platinum anchored on nitrogen-doped carbon.Small2022;18:e2107067

[99] Lv J,Yang S,Huang X.Methanol dissociation and oxidation on single Fe atom supported on graphitic carbon nitride.Appl Organom Chem2019;33:e4930

[100] Fan X,Xie L.Surface-enriched single-Bi-atoms tailoring of Pt nanorings for direct methanol fuel cells with ultralow-Pt-loading.Adv Mater2024;36:e2313179

[101] Wei X,Liu C,Deng Y.Ir single atoms doped cuboctahedral Pd for boosted methanol oxidation reaction.Part Part Syst Charact2022;39:2200013

[102] Miao J,Wang X.Efficiently selective C(O-)-C bond cleavage for full lignocellulose upgrading coupled with energy-saving hydrogen production by Ir single-atom electrocatalyst.Appl Catal B Environ2023;336:122937

[103] Cui T,Wang S.Atomically Dispersed Pt-N₃C₁ sites enabling efficient and selective electrocatalytic C-C bond cleavage in lignin models under ambient conditions.J Am Chem Soc2021;143:9429-39

[104] Tong S,Zhou H,Wu Y.Synergistic roles of the CoO/Co heterostructure and Pt single atoms for high-efficiency electrocatalytic hydrogenation of lignin-derived Bio-Oils.Inorg Chem2023;62:19123-34