Recent advances in nickel-based catalysts in eCO₂RR for carbon neutrality

Abstract

The excessive use of nonrenewable energy has brought about serious greenhouse effect. Converting CO₂ into high-value-added chemicals is undoubtedly the best choice to solve energy problems. Due to the excellent cost-effectiveness and dramatic catalytic performance, nickel-based catalysts have been considered as the most promising candidates for the electrocatalytic CO₂ reduction reaction (eCO₂RR). In this work, the electrocatalytic reduction mechanism of CO₂ over Ni-based materials is reviewed. The strategies to improve the eCO₂RR performance are emphasized. Moreover, the research on Ni-based materials for syngas generation is briefly summarized. Finally, the prospects of nickel-based materials in the eCO₂RR are provided with the hope of improving transition-metal-based electrocatalysts for eCO₂RR in the future.

Keywords

carbon energy / carbon neutrality / CO ₂ reduction / electrocatalysis / nickel-based materials

References

[1] Xia D, Zhang L. Coupling coordination degree between coal production reduction and CO₂ emission reduction in coal industry. Energy. 2022; 258: 124902.

[2] Septavaux J, Tosi C, Jame P, Nervi C, Gobetto R, Leclaire J. Simultaneous CO₂ capture and metal purification from waste streams using triple-level dynamic combinatorial chemistry. Nat Chem. 2020; 12 (2): 202- 212.

[3] Tomkinson T, Lee MR, Mark DF, Smith CL. Sequestration of Martian CO₂ by mineral carbonation. Nat Commun. 2013; 4: 2662.

[4] Kampman N, Busch A, Bertier P, et al. Observational evidence confirms modelling of the long-term integrity of CO₂-reservoir caprocks. Nat Commun. 2016; 7: 12268.

[5] Hu J, Hongmanorom P, Chen J, et al. Tandem distributing Ni into CaO framework for isothermal integration of CO₂ capture and conversion. Chem Eng J. 2023; 452: 139460.

[6] Xie Y, Ou P, Wang X, et al. High carbon utilization in CO₂ reduction to multi-carbon products in acidic media. Nat Catal. 2022; 5 (6): 564- 570.

[7] Rapagnani RM, Dunscomb RJ, Fresh AA, Tonks IA. Tunable and recyclable polyesters from CO₂ and butadiene. Nat Chem. 2022; 14 (8): 877- 883.

[8] Yang B, Chen L, Xue S, et al. Electrocatalytic CO₂ reduction to alcohols by modulating the molecular geometry and Cu coordination in bicentric copper complexes. Nat Commun. 2022; 13: 5122.

[9] Shafaat HS, Yang JY. Uniting biological and chemical strategies for selective CO₂ reduction. Nat Catal. 2021; 4 (11): 928- 933.

[10] Xie J, Zhou Z, Wang Y. Metal-CO₂ batteries at the crossroad to practical energy storage and CO₂ recycle. Adv Funct Mater. 2020; 30 (9): 1908285.

[11] Xu M, Sun C, Zhao X, Jiang H, Wang H, Huo P. Fabricated hierarchical CdS/Ni-MOF heterostructure for promoting photocatalytic reduction of CO₂. Appl Surf Sci. 2022; 576: 151792.

[12] Li J, Huang H, Xue W, et al. Self-adaptive dual-metal-site pairs in metal-organic frameworks for selective CO₂ photoreduction to CH₄. Nat Catal. 2021; 4 (8): 719- 729.

[13] Li Y, Hao J, Song H, et al. Selective light absorber-assisted single nickel atom catalysts for ambient sunlight-driven CO₂ methanation. Nat Commun. 2019; 10: 2359.

[14] Wang S, Zhang D, Wang W, et al. Grave-to-cradle upcycling of Ni from electroplating wastewater to photothermal CO₂ catalysis. Nat Commun. 2022; 13: 5305.

[15] Cai M, Wu Z, Li Z, et al. Greenhouse-inspired supra-photothermal CO₂ catalysis. Nat Energy. 2021; 6 (8): 807- 814.

[16] Tan X, Wu S, Li Y, et al. Highly efficient photothermocatalytic CO₂ reduction in Ni/Mg-doped Al₂O₃ with high fuel production rate, large light-to-fuel efficiency, and good durability. Energy Environ Mater. 2022; 5 (2): 582- 591.

[17] Kim HS, Hong SG, Yang J, et al. 3D-Printed interfacial devices for biocatalytic CO₂ conversion at gas-liquid interface. J CO2 Util. 2020; 38: 291- 298.

[18] Barceloux DG, Barceloux D. Nickel. J Toxicol Clin Toxicol. 1999; 37: 239- 258.

[19] Okamoto Y. Surface state and catalytic activity and selectivity of nickel catalysts in hydrogenation reactions: III. Electronic and catalytic properties of nickel catalysts. J Catal. 1980; 64 (2): 397- 404.

[20] Guo K, Wang Y, Huang J, Li H, Peng Y, Xu C. Symbiotic Ni₃Se₄/Ni heterostructure induced by unstable NiSe₂ for enhanced hydrogen generation. Chem Eng J. 2023; 454: 140488.

[21] Subbaraman R, Tripkovic D, Strmcnik D, et al. Enhancing hydrogen evolution activity in water splitting by tailoring Li⁺-Ni(OH)₂-Pt interfaces. Science. 2011; 334 (6060): 1256- 1260.

[22] Wu T, Xu S, Zhang Z, et al. Bimetal modulation stabilizing a metallic heterostructure for efficient overall water splitting at large current density. Adv Sci. 2022; 9 (25): 2202750.

[23] Dutta A, Appel AM, Shaw WJ. Designing electrochemically reversible H₂ oxidation and production catalysts. Nat Rev Chem. 2018; 2 (9): 244- 252.

[24] Anjaneyulu C, Kumar VV, Bhargava SK, Venugopal A. Characteristics of La-modified Ni-Al₂O₃ and Ni-SiO₂ catalysts for CO_x-free hydrogen production by catalytic decomposition of methane. J Energy Chem. 2013; 22 (6): 853- 8860.

[25] Tiwari AP, Lee K, Kim K, Kim J, Novak TG, Jeon S. Conformally coated nickel phosphide on 3D, ordered nanoporous nickel for highly active and durable hydrogen evolution. ACS Sustainable Chem Eng. 2020; 8 (46): 17116- 17123.

[26] Baranton S, Coutanceau C. Nickel cobalt hydroxide nanoflakes as catalysts for the hydrogen evolution reaction. Appl Catal B. 2013; 136-137: 1- 8.

[27] Feng J, Chen M, Zhou P, et al. Reconstruction optimization of distorted FeOOH/Ni hydroxide for enhanced oxygen evolution reaction. Mater Today Energy. 2022; 27: 101005.

[28] Lee S, Banjac K, Lingenfelder M, Hu X. Oxygen isotope labeling experiments reveal different reaction sites for the oxygen evolution reaction on nickel and nickel iron oxides. Angew Chem Int Ed. 2019; 131 (30): 10401- 10405.

[29] Ding Y, Miao BQ, Zhao Y, et al. Direct growth of holey Fe₃O₄-coupled Ni(OH)₂ sheets on nickel foam for the oxygen evolution reaction. Chin J Catal. 2021; 42 (2): 271- 278.

[30] Masa J, Sinev I, Mistry H, et al. Ultrathin high surface area nickel boride (Ni_xB) nanosheets as highly efficient electrocatalyst for oxygen evolution. Adv Energy Mater. 2017; 7 (17): 1700381.

[31] Lee SY, Oh HJ, Kim M, Cho HS, Lee YK. Insights into enhanced activity and durability of hierarchical Fe-doped Ni(OH)₂/Ni catalysts for alkaline oxygen evolution reaction: in situ XANES studies. Appl Catal B. 2023; 324: 122269.

[32] Görlin M, Halldin Stenlid J, Koroidov S, et al. Key activity descriptors of nickel-iron oxygen evolution electrocatalysts in the presence of alkali metal cations. Nat Commun. 2020; 11: 6181.

[33] Li D, Zhang Y, Zhou X, et al. Dynamic active sites on plasma engraved Ni hydroxide for enhanced electro-catalytic urea oxidation. J Energy Chem. 2022; 71: 150- 158.

[34] Hosseini H, Shahrokhian S. Self-supported nanoporous Zn-Ni-Co/Cu selenides microball arrays for hybrid energy storage and electrocatalytic water/urea splitting. Chem Eng J. 2019; 375: 122090.

[35] Dabboussi J, Abdallah R, Santinacci L, et al. Solar-assisted urea oxidation at silicon photoanodes promoted by an amorphous and optically adaptive Ni-Mo-O catalytic layer. J Mater Chem A. 2022; 10 (37): 19769- 19776.

[36] Shilpa N, Pandikassala A, Krishnaraj P, Walko PS, Devi RN, Kurungot S. Co-Ni layered double hydroxide for the electrocatalytic oxidation of organic molecules: an approach to lowering the overall cell voltage for the water splitting process. ACS Appl Mater Interfaces. 2022; 14 (14): 16222- 16232.

[37] Wang Z, Liu W, Bao J, et al. Modulating electronic structure of ternary NiMoV LDH nanosheet array induced by doping engineering to promote urea oxidation reaction. Chem Eng J. 2022; 430: 133100.

[38] Akri M, Zhao S, Li X, et al. Atomically dispersed nickel as coke-resistant active sites for methane dry reforming. Nat Commun. 2019; 10: 5181.

[39] Qiu L, Zhang M, Song Y, et al. Deciphering the degradation discrepancy in Ni-rich cathodes with a diverse proportion of [003] crystallographic textures. Carbon Energy. 2023; 5 (7): e298.

[40] Yan X, Sun W, Fan L, et al. Nickel@ siloxene catalytic nanosheets for high-performance CO₂ methanation. Nat Commun. 2019; 10: 2608.

[41] Si X, Lu R, Zhao Z, et al. Catalytic production of low-carbon footprint sustainable natural gas. Nat Commun. 2022; 13: 258.

[42] Chen W, Xu H, Ma X, Qi L, Zhou Z. Synergistic trimetallic Ni-Cu-Sn catalysts for efficient selective hydrogenation of phenylacetylene. Chem Eng J. 2023; 455: 140565.

[43] Li S, Ma R, Hu J, et al. Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity. Nat Commun. 2022; 13: 2916.

[44] Li S, Ma P, Gao C, et al. Reconstruction-induced NiCu-based catalysts towards paired electrochemical refining. Energy Environ Sci. 2022; 15 (7): 3004- 3014.

[45] Li Z, He D, Yan X, et al. Size-dependent nickel-based electrocatalysts for selective CO₂ reduction. Angew Chem Int Ed. 2020; 132 (42): 18731- 18736.

[46] Hao Q, Zhong H, Wang J, et al. Nickel dual-atom sites for electrochemical carbon dioxide reduction. Nat Synth. 2022; 1 (9): 719- 728.

[47] Wu ZY, Zhu P, Cullen DA, et al. A general synthesis of single atom catalysts with controllable atomic and mesoporous structures. Nat Synth. 2022; 1 (8): 658- 667.

[48] Tan X, Yu C, Cui S, et al. Activity descriptor of Ni, N-Codoped carbon electrocatalyst in CO₂ electroreduction reaction. Chem Eng J. 2022; 433: 131965.

[49] Leverett J, Yuwono JA, Kumar P, et al. Impurity tolerance of unsaturated Ni-NC active sites for practical electrochemical CO₂ reduction. ACS Energy Lett. 2022; 7 (3): 920- 928.

[50] Tan TH, Xie B, Ng YH, et al. Unlocking the potential of the formate pathway in the photo-assisted Sabatier reaction. Nat Catal. 2020; 3 (12): 1034- 1043.

[51] Dong Y, Yang P, Zhao S, Li Y. Reductive cyanation of organic chlorides using CO₂ and NH₃ via Triphos-Ni (I) species. Nat Commun. 2020; 11: 4096.

[52] Chen B, Li B, Tian Z, et al. Enhancement of mass transfer for facilitating industrial-level CO₂ electroreduction on atomic Ni-N₄ sites. Adv Energy Mater. 2021; 11 (40): 2102152.

[53] Möller T, Ju W, Bagger A, et al. Efficient CO₂ to CO electrolysis on solid Ni-N-C catalysts at industrial current densities. Energy Environ Sci. 2019; 12 (2): 640- 647.

[54] Long C, Li X, Guo J, Shi Y, Liu S, Tang Z. Electrochemical reduction of CO₂ over heterogeneous catalysts in aqueous solution: recent progress and perspectives. Small Methods. 2019; 3 (3): 1800369.

[55] Liang S, Huang L, Gao Y, Wang Q, Liu B. Electrochemical reduction of CO₂ to CO over transition metal/N-doped carbon catalysts: the active sites and reaction mechanism. Adv Sci. 2021; 8 (24): 2102886.

[56] Birdja YY, Pérez-Gallent E, Figueiredo MC, Göttle AJ, Calle-Vallejo F, Koper MTM. Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels. Nat Energy. 2019; 4 (9): 732- 745.

[57] Liu S, Yang HB, Hung SF, et al. Elucidating the electrocatalytic CO₂ reduction reaction over a model single-atom nickel catalyst. Angew Chem Int Ed. 2020; 59 (2): 798- 803.

[58] Lin W, Stocker KM, Schatz GC. Mechanisms of hydrogen-assisted CO₂ reduction on nickel. J Am Chem Soc. 2017; 139 (13): 4663- 4666.

[59] Chen J, Wei X, Cai R, et al. Composition-tuned surface binding on CuZn-Ni catalysts boosts CO₂RR selectivity toward CO generation. ACS Mater Lett. 2022; 4 (3): 497- 504.

[60] Zheng Y, Vasileff A, Zhou X, Jiao Y, Jaroniec M, Qiao SZ. Understanding the roadmap for electrochemical reduction of CO₂ to multi-carbon oxygenates and hydrocarbons on copper-based catalysts. J Am Chem Soc. 2019; 141 (19): 7646- 7659.

[61] Calvinho KUD, Laursen AB, Yap KMK, et al. Selective CO₂ reduction to C₃ and C₄ oxyhydrocarbons on nickel phosphides at overpotentials as low as 10 mV. Energy Environ Sci. 2018; 11 (9): 2550- 2559.

[62] Tian J, Shen Y, Liu P, et al. Recent advances of amorphous-phase-engineered metal-based catalysts for boosted electrocatalysis. J Mater Sci Technol. 2022; 127: 1- 18.

[63] Badreldin A, Nabeeh A, Ghouri ZK, et al. Early transition-metal-based binary oxide/nitride for efficient electrocatalytic hydrogen evolution from saline water in different pH environments. ACS Appl Mater Interfaces. 2021; 13 (45): 53702- 53716.

[64] Mahmood N, Yao Y, Zhang JW, Pan L, Zhang X, Zou JJ. Electrocatalysts for hydrogen evolution in alkaline electrolytes: mechanisms, challenges, and prospective solutions. Adv Sci. 2018; 5 (2): 1700464.

[65] Tiwari JN, Dang NK, Sultan S, Thangavel P, Jeong HY, Kim KS. Multi-heteroatom-doped carbon from waste-yeast biomass for sustained water splitting. Nat Sustain. 2020; 3 (7): 556- 563.

[66] Lee JH, Kattel S, Jiang Z, et al. Tuning the activity and selectivity of electroreduction of CO₂ to synthesis gas using bimetallic catalysts. Nat Commun. 2019; 10: 3724.

[67] Wang X, Zhang J, Wang Z, Lin Z, Shen S, Zhong W. Fabricating Ru single atoms and clusters on CoP for boosted hydrogen evolution reaction. Chin J Struct Chem. 2023; 42 (4): 100035.

[68] Huang Y, Hu Z, Huang L, et al. Phosphorus-modified cobalt single-atom catalysts loaded on crosslinked carbon nanosheets for efficient alkaline hydrogen evolution reaction. Nanoscale. 2023; 15 (7): 3550- 3559.

[69] Ju W, Bagger A, Hao GP, et al. Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO₂. Nat Commun. 2017; 8: 944.

[70] Vijay S, Ju W, Brückner S, Tsang SC, Strasser P, Chan K. Unified mechanistic understanding of CO₂ reduction to CO on transition metal and single atom catalysts. Nat Catal. 2021; 4 (12): 1024- 1031.

[71] Wang L, Wang D, Li Y. Single-atom catalysis for carbon neutrality. Carbon Energy. 2022; 4 (6): 1021- 1079.

[72] Fu X, Shi R, Jiao S, Li M, Li Q. Structural design for electrocatalytic water splitting to realize industrial-scale deployment: strategies, advances, and perspectives. J Energy Chem. 2022; 70: 129- 153.

[73] Yang HB, Hung SF, Liu S, et al. Atomically dispersed Ni(I) as the active site for electrochemical CO₂ reduction. Nat Energy. 2018; 3 (2): 140- 147.

[74] Mudchimo T, Takahashi K, Mano P, Sanghiran Lee V, Rungrotmongkol T, Namuangruk S. Understanding the effect of transition metals and vacancy boron nitride catalysts on activity and selectivity for CO₂ reduction reaction to valuable products: A DFT-D3 study. Fuel. 2022; 319: 123808.

[75] Qiu L, Shen S, Ma C, et al. Controllable fabrication of atomic dispersed low-coordination nickel-nitrogen sites for highly efficient electrocatalytic CO₂ reduction. Chem Eng J. 2022; 440: 135956.

[76] Hao Q, Tang Q, Zhong HX, Wang JZ, Liu DX, Zhang XB. Fully exposed nickel clusters with electron-rich centers for high-performance electrocatalytic CO₂ reduction to CO. Sci Bull. 2022; 67 (14): 1477- 1485.

[77] Zhang Y, Li P, Zhao C, et al. Multicarbons generation factory: CuO/Ni single atoms tandem catalyst for boosting the productivity of CO₂ electrocatalysis. Sci Bull. 2022; 67 (16): 1679- 1687.

[78] Ma Z, Zhang X, Wu D, et al. Ni and nitrogen-codoped ultrathin carbon nanosheets with strong bonding sites for efficient CO₂ electrochemical reduction. J Colloid Interface Sci. 2020; 570: 31- 40.

[79] Cheng Y, Zhao S, Li H, et al. Unsaturated edge-anchored Ni single atoms on porous microwave exfoliated graphene oxide for electrochemical CO₂. Appl Catal B. 2019; 243: 294- 303.

[80] Lepre E, Heske J, Nowakowski M, et al. Ni-based electrocatalysts for unconventional CO₂ reduction reaction to formic acid. Nano Energy. 2022; 97: 107191.

[81] Fan Q, Hou P, Choi C, et al. Activation of Ni particles into single Ni-N atoms for efficient electrochemical reduction of CO₂. Adv Energy Mater. 2020; 10 (5): 1903068.

[82] Hwa Jeong G, Chuan Tan Y, Tae Song J, et al. Synthetic multiscale design of nanostructured Ni single atom catalyst for superior CO₂ electroreduction. Chem Eng J. 2021; 426: 131063.

[83] Hossain MD, Huang Y, Yu TH, Goddard III WA, Luo Z. Reaction mechanism and kinetics for CO₂ reduction on nickel single atom catalysts from quantum mechanics. Nat Commun. 2020; 11: 2256.

[84] Zhang Z, Xiao J, Chen XJ, et al. Reaction mechanisms of well-defined metal-N₄ sites in electrocatalytic CO₂ reduction. Angew Chem Int Ed. 2018; 57 (50): 16339- 16342.

[85] Wang T, Huang W, Sun T, et al. Two-dimensional metal-polyphthalocyanine conjugated porous frameworks as promising optical limiting materials. ACS Appl Mater Interfaces. 2020; 12 (41): 46565- 46570.

[86] Wu Y, Jiang Z, Lu X, Liang Y, Wang H. Domino electroreduction of CO₂ to methanol on a molecular catalyst. Nature. 2019; 575 (7784): 639- 642.

[87] Gong S, Wang W, Lu R, et al. Mediating heterogenized nickel phthalocyanine into isolated Ni-N₃ moiety for improving activity and stability of electrocatalytic CO₂ reduction. Appl Catal B. 2022; 318: 121813.

[88] Wei S, Zou H, Rong W, Zhang F, Ji Y, Duan L. Conjugated nickel phthalocyanine polymer selectively catalyzes CO₂-to-CO conversion in a wide operating potential window. Appl Catal B. 2021; 284: 119739.

[89] Yang X, Cheng J, Xuan X, Liu N, Liu J. Boosting defective carbon by anchoring well-defined atomically dispersed Ni-N₄ sites for electrocatalytic CO₂ reduction. ACS Sustainable Chem Eng. 2020; 8 (28): 10536- 10543.

[90] Ma Z, Zhang X, Han X, et al. Synergistic adsorption and activation of nickel phthalocyanine anchored onto ketjenblack for CO₂ electrochemical reduction. Appl Surf Sci. 2021; 538: 148134.

[91] Ma DD, Han SG, Cao C, Li X, Wu XT, Zhu QL. Remarkable electrocatalytic CO₂ reduction with ultrahigh CO/H₂ ratio over single-molecularly immobilized pyrrolidinonyl nickel phthalocyanine. Appl Catal B. 2020; 264: 118530.

[92] Hu MK, Zhou S, Ma DD, Zhu QL. New insight into heterointerfacial effect for heterogenized metallomacrocycle catalysts in executing electrocatalytic CO₂ reduction. Appl Catal B. 2022; 310: 121324.

[93] Chen K, Cao M, Ni G, et al. Nickel polyphthalocyanine with electronic localization at the nickel site for enhanced CO₂ reduction reaction. Appl Catal B. 2022; 306: 121093.

[94] Chen J, Li J, Xu J, Zhu M, Han YF. Phthalocyanine-derived catalysts decorated by metallic nanoclusters for enhanced CO₂ electroreduction. Green Energy Environ. 2023; 8 (2): 444- 451.

[95] Wen Q, Duan J, Wang W, et al. Engineering a local free water enriched microenvironment for surpassing platinum hydrogen evolution activity. Angew Chem Int Ed. 2022; 61 (35): e202206077.

[96] Liang Z, Wang J, Tang P, et al. Molecular engineering to introduce carbonyl between nickel salophen active sites to enhance electrochemical CO₂ reduction to methanol. Appl Catal B. 2022; 314: 121451.

[97] Wang H, Liu G, Chen C, et al. Single-Ni sites embedded in multilayer nitrogen-doped graphene derived from amino-functionalized MOF for highly selective CO₂ electroreduction. ACS Sustainable Chem Eng. 2021; 9 (10): 3792- 3801.

[98] Peng SY, Jin GP, Cui JS, Lv XY, Yu YX, Tang HW. Preparation of nickel hexacyanoferrate/heterogeneous carbon composites for CO₂ continuous electrocatalytic reduction to formic acid. J Environ Chem Eng. 2018; 6 (6): 6931- 6938.

[99] Payra S, Shenoy S, Chakraborty C, Tarafder K, Roy S. Structure-sensitive electrocatalytic reduction of CO₂ to methanol over carbon-supported intermetallic PtZn nano-alloys. ACS Appl Mater Interfaces. 2020; 12 (17): 19402- 19414.

[100] Sun GQ, Zhang W, Liao LL, et al. Nickel-catalyzed electrochemical carboxylation of unactivated aryl and alkyl halides with CO₂. Nat Commun. 2021; 12: 7086.

[101] Chen K, Cao M, Lin Y, et al. Ligand engineering in nickel phthalocyanine to boost the electrocatalytic reduction of CO₂. Adv Funct Mater. 2022; 32 (10): 2111322.

[102] Hamby TB, Lalama MJ, Sevov CS. Controlling Ni redox states by dynamic ligand exchange for electroreductive Csp3-Csp2 coupling. Science. 2022; 376 (6591): 410- 416.

[103] Zhang X, Wang Y, Gu M, et al. Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO₂ reduction. Nat Energy. 2020; 5 (9): 684- 692.

[104] Li K, Wang W, Zheng H, et al. Visualizing highly selective electrochemical CO₂ reduction on a molecularly dispersed catalyst. Mater Today Phys. 2021; 19: 100427.

[105] Wang M, Shi H, Tian M, et al. Single nickel atom-modified phosphorene nanosheets for electrocatalytic CO₂ reduction. ACS Appl Nano Mater. 2021; 4 (10): 11017- 11030.

[106] Han MH, Kim D, Kim S, et al. Real-Time mimicking the electronic structure of N-coordinated Ni single atoms: NiS-enabled electrochemical reduction of CO₂ to CO. Adv Energy Mater. 2022; 12 (35): 2201843.

[107] Zhao S, Guo S, Zhu C, et al. Achieving electroreduction of CO₂ to CH₃OH with high selectivity using a pyrite-nickel sulfide nanocomposite. RSC Adv. 2017; 7 (3): 1376- 1381.

[108] Gao ZH, Wei K, Wu T, et al. A heteroleptic gold hydride nanocluster for efficient and selective electrocatalytic reduction of CO₂ to CO. J Am Chem Soc. 2022; 144 (12): 5258- 5262.

[109] Wang Y, You L, Zhou K. Origin of the N-coordinated single-atom Ni sites in heterogeneous electrocatalysts for CO₂ reduction reaction. Chem Sci. 2021; 12 (42): 14065- 14073.

[110] Su X, Yang XF, Huang Y, Liu B, Zhang T. Single-atom catalysis toward efficient CO₂ conversion to CO and formate products. Acc Chem Res. 2018; 52 (3): 656- 664.

[111] Zhai P, Gu X, Wei Y, et al. Enhanced mass transfer in three-dimensional single-atom nickel catalyst with open-pore structure for highly efficient CO₂ electrolysis. J Energy Chem. 2021; 62: 43- 50.

[112] Lu Y, Wang H, Yu P, et al. Isolated Ni single atoms in nitrogen doped ultrathin porous carbon templated from porous g-C₃N₄ for high-performance CO₂ reduction. Nano Energy. 2020; 77: 105158.

[113] Du J, Chen A, Hou S, Guan J. CNT modified by mesoporous carbon anchored by Ni nanoparticles for CO₂ electrochemical reduction. Carbon Energy. 2022; 4 (6): 1274- 1284.

[114] Cao Z, Su P, Wang X, et al. The structure-activity correlation of single-site Ni catalysts dispersed onto porous carbon spheres toward electrochemical CO₂ reduction. Fuel. 2022; 321: 124043.

[115] Yang H, Lin Q, Zhang C, et al. Carbon dioxide electroreduction on single-atom nickel decorated carbon membranes with industry compatible current densities. Nat Commun. 2020; 11: 593.

[116] Li H, Gan K, Li R, et al. Highly dispersed NiO clusters induced electron delocalization of Ni-N-C catalysts for enhanced CO₂ electroreduction. Adv Funct Mater. 2022; 33 (1): 2208622.

[117] Guo C, Zhang T, Liang X, et al. Single transition metal atoms on nitrogen-doped carbon for CO₂ electrocatalytic reduction: CO production or further CO reduction. Appl Surf Sci. 2020; 533: 147466.

[118] Wang M, Liu S, Chen B, Huang M, Peng C. Co-regulation of intermediate binding and water activation in sulfur-doped bismuth nanosheets for electrocatalytic CO₂ reduction to formate. Chem Eng J. 2023; 451: 139056.

[119] Lu P, Yang Y, Yao J, et al. Facile synthesis of single-nickel-atomic dispersed N-doped carbon framework for efficient electrochemical CO₂ reduction. Appl Catal B. 2019; 241: 113- 119.

[120] Daiyan R, Zhu X, Tong Z, et al. Transforming active sites in nickel-nitrogen-carbon catalysts for efficient electrochemical CO₂ reduction to CO. Nano Energy. 2020; 78: 105213.

[121] Hou Y, Liang YL, Shi PC, Huang YB, Cao R. Atomically dispersed Ni species on N-doped carbon nanotubes for electroreduction of CO₂ with nearly 100% CO selectivity. Appl Catal B. 2020; 271: 118929.

[122] Belmabkhout Y, Bhatt PM, Adil K, et al. Natural gas upgrading using a fluorinated MOF with tuned H₂S and CO₂ adsorption selectivity. Nat Energy. 2018; 3 (12): 1059- 1066.

[123] Zhao C, Dai X, Yao T, et al. Ionic exchange of metal-organic frameworks to access single nickel sites for efficient electroreduction of CO₂. J Am Chem Soc. 2017; 139 (24): 8078- 8081.

[124] Zhao S, Xiao N, Li H, et al. A nickel-nitrogen-doped carbon foam as monolithic electrode for highly efficient CO₂ electroreduction. J CO2 Util. 2021; 49: 101549.

[125] Shao W, Zhang X. Atomic-level engineering of two-dimensional electrocatalysts for CO₂ reduction. Nanoscale. 2021; 13 (15): 7081- 7095.

[126] Wen CF, Mao F, Liu Y, et al. Nitrogen-stabilized low-valent Ni motifs for efficient CO₂ electrocatalysis. ACS Catal. 2020; 10 (2): 1086- 1093.

[127] Helal A, Fettouhi M, Arafat ME, Khan MY, Sanhoob MA. Nickel based metal-organic framework as catalyst for chemical fixation of CO₂ in oxazolidinone synthesis. J CO2 Util. 2021; 50: 101603.

[128] Han SG, Ma DD, Zhou SH, et al. Fluorine-tuned single-atom catalysts with dense surface Ni-N₄ sites on ultrathin carbon nanosheets for efficient CO₂ electroreduction. Appl Catal B. 2021; 283: 119591.

[129] Wang Q, Liu K, Hu K, et al. Attenuating metal-substrate conjugation in atomically dispersed nickel catalysts for electroreduction of CO₂ to CO. Nat Commun. 2022; 13: 6082.

[130] Cheng Y, Zhao S, Johannessen B, et al. Atomically dispersed transition metals on carbon nanotubes with ultrahigh loading for selective electrochemical carbon dioxide reduction. Adv Mater. 2018; 30 (13): 1706287.

[131] Li X, Bi W, Chen M, et al. Exclusive Ni-N₄ sites realize near-unity CO selectivity for electrochemical CO₂ reduction. J Am Chem Soc. 2017; 139 (42): 14889- 14892.

[132] Liu X, Liao L, Xia G, et al. An accurate “metal pre-buried” strategy for constructing Ni-N₂C₂ single-atom sites with high metal loadings toward electrocatalytic CO₂ reduction. J Mater Chem A. 2022; 10 (47): 25047- 25054.

[133] Boppella R, Austeria PM, Kim Y, et al. Pyrrolic N-stabilized monovalent Ni single-atom electrocatalyst for efficient CO₂ reduction: identifying the role of pyrrolic-N and synergistic electrocatalysis. Adv Funct Mater. 2022; 32 (35): 2202351.

[134] Xiong W, Li H, Wang H, et al. Hollow mesoporous carbon sphere loaded Ni-N₄ single-atom: support structure study for CO₂ electrocatalytic reduction catalyst. Small. 2020; 16 (41): 2003943.

[135] Vogt C, Groeneveld E, Kamsma G, et al. Unravelling structure sensitivity in CO₂ hydrogenation over nickel. Nat Catal. 2018; 1 (2): 127- 134.

[136] Zhao R, Wang Y, Ji G, et al. Partially nitrided Ni nanoclusters achieve energy-efficient electrocatalytic CO₂ reduction to CO at ultralow overpotential. Adv Mater. 2023; 35 (5): 2205262.

[137] Jia M, Choi C, Wu TS, et al. Carbon-supported Ni nanoparticles for efficient CO₂ electroreduction. Chem Sci. 2018; 9 (47): 8775- 8780.

[138] Liang M, Liu Y, Huang H, et al. A robust Ni@NCNT-C catalyst for highly efficient electrochemical CO₂ reduction to CO over a wide potential range. Chem Eng J. 2022; 450: 137962.

[139] Du J, Chen A. Ni nanoparticles confined by yolk-shell structure of CNT-mesoporous carbon for electrocatalytic conversion of CO₂: switching CO to formate. J Energy Chem. 2022; 70: 224- 229.

[140] Zheng W, Guo C, Yang J, et al. Highly active metallic nickel sites confined in N-doped carbon nanotubes toward significantly enhanced activity of CO₂ electroreduction. Carbon. 2019; 150: 52- 59.

[141] Ding C, Feng C, Mei Y, et al. Carbon nitride embedded with transition metals for selective electrocatalytic CO₂ reduction. Appl Catal B. 2020; 268: 118391.

[142] Wang Z, Lin Z, Wang Y, et al. Nontrivial topological surface states in Ru₃Sn₇ toward wide pH-range hydrogen evolution reaction. Adv Mater. 2023; 35 (25): 2302007.

[143] Wang H, Jiang Y, Li S, et al. Realizing efficient CN coupling via electrochemical co-reduction of CO₂ and NO₃^- on AuPd nanoalloy to form urea: key CN coupling intermediates. Appl Catal B. 2022; 318: 121819.

[144] Yin S, Zhao J, Wu S, Wang X, Quan Y, Ren J. Electrochemical reduction of CO₂ to CO on bimetallic CoCu-N-C catalyst. J Clean Prod. 2022; 371: 133569.

[145] Frei MS, Mondelli C, García-Muelas R, et al. Nanostructure of nickel-promoted indium oxide catalysts drives selectivity in CO₂ hydrogenation. Nat Commun. 2021; 12: 1960.

[146] Fan Z, Luo R, Zhang Y, et al. Oxygen-bridged indium-nickel atomic pair as dual-metal active sites enabling synergistic electrocatalytic CO₂ reduction. Angew Chem Int Ed. 2023; 135 (7): e202216326.

[147] Zeng Z, Gan LY, Bin Yang H, et al. Orbital coupling of hetero-diatomic nickel-iron site for bifunctional electrocatalysis of CO₂ reduction and oxygen evolution. Nat Commun. 2021; 12: 4088.

[148] Wei X, Cao S, Wei S, et al. Theoretical investigation on electrocatalytic reduction of CO₂ to methanol and methane by bimetallic atoms TM1/TM2-N@Gra (TM= Fe, Co, Ni, Cu). Appl Surf Sci. 2022; 593: 153377.

[149] Yang T, Xie W, Tian N, Liu XH, Zhang X. CuNi alloy nanoparticles embedded in N-doped carbon framework for electrocatalytic reduction of CO₂ to CO. J Alloys Compd. 2022; 904: 164042.

[150] Shen S, Han C, Wang B, Wang Y. Engineering d-band center of nickel in nickel@nitrogen-doped carbon nanotubes array for electrochemical reduction of CO₂ to CO and Zn-CO₂ batteries. Chin Chem Lett. 2022; 33 (8): 3721- 3725.

[151] Zhang X, Liu C, Zhao Y, et al. Atomic nickel cluster decorated defect-rich copper for enhanced C₂ product selectivity in electrocatalytic CO₂ reduction. Appl Catal B. 2021; 291: 120030.

[152] Lu P, Zhang J, He H, et al. Iron/nickel nano-alloy encapsulated in nitrogen-doped carbon framework for CO₂ electrochemical conversion with prominent CO selectivity. J Power Sources. 2020; 449: 227496.

[153] Beheshti M, Kakooei S, Ismail MC, Shahrestani S. Investigation of CO₂ electrochemical reduction to syngas on Zn/Ni-based electrocatalysts using the cyclic voltammetry method. Electrochim Acta. 2020; 341: 135976.

[154] Wei X, Xiao S, Wu R, et al. Activating COOH* intermediate by Ni/Ni₃ZnC_0.7 heterostructure in porous N-doped carbon nanofibers for boosting CO₂ electroreduction. Appl Catal B. 2022; 302: 120861.

[155] Su P, Iwase K, Nakanishi S, Hashimoto K, Kamiya K. Nickel-nitrogen-modified graphene: an efficient electrocatalyst for the reduction of carbon dioxide to carbon monoxide. Small. 2016; 12 (44): 6083- 6089.

[156] Pei J, Wang T, Sui R, et al. N-Bridged Co-N-Ni: new bimetallic sites for promoting electrochemical CO₂ reduction. Energy Environ Sci. 2021; 14 (5): 3019- 3028.

[157] Li Y, Wei B, Zhu M, et al. Synergistic effect of atomically dispersed Ni-Zn pair sites for enhanced CO₂ electroreduction. Adv Mater. 2021; 33 (41): 2102212.

[158] Han H, Im J, Lee M, Choo D. N-bridged Ni and Mn single-atom pair sites: a highly efficient electrocatalyst for CO₂ conversion to CO. Appl Catal B. 2023; 320: 121953.

[159] Cronin SP, Dulovic S, Lawrence JA, et al. Direct synthesis of 1-Butanol with high faradaic efficiency from CO₂ utilizing cascade catalysis at a Ni-enhanced (Cr₂O₃)₃Ga₂O₃ electrocatalyst. J Am Chem Soc. 2023; 145 (12): 6762- 6772.

[160] Li S, Luo W, Gao Q, et al. Strong electronic coupling induced by synergy of dopant and interface in Ru-Ni₃S₂/Ni_xP_y to boost efficient water splitting. Appl Surf Sci. 2023; 637: 157940.

[161] Abdinejad M, Wilm LFB, Dielmann F, Kraatz HB. Electroreduction of CO₂ catalyzed by nickel imidazolin-2-ylidenamino-porphyrins in both heterogeneous and homogeneous molecular systems. ACS Sustainable Chem Eng. 2021; 9 (1): 521- 530.

[162] Zhou Y, Martín AJ, Dattila F, et al. Long-chain hydrocarbons by CO₂ electroreduction using polarized nickel catalysts. Nat Catal. 2022; 5 (6): 545- 554.

[163] Li H, Liu Q. Synthesis of Ni-phyllosilicate assisted by fluoroboric acid for CO₂ methanation. Int J Hydrogen Energy. 2023; 48 (64): 24884- 24893.

[164] Fan Q, Li H, Chen H, Cheng L, Liu Q. Effect of concentration of nickel precursor on the synthesis of Ni phyllosilicate for CO₂ methanation: the promotion of supersaturation. Fuel. 2023; 333: 126440.

[165] Liu E, Liu T, Ma X, Zhang Y. The electrocatalytic performance of Ni-AlO(OH)₃@RGO for the reduction of CO₂ to CO. New J Chem. 2022; 46 (25): 12023- 12033.

[166] Kim Y, Park S, Shin SJ, et al. Time-resolved observation of C-C coupling intermediates on Cu electrodes for selective electrochemical CO₂ reduction. Energy Environ Sci. 2020; 13 (11): 4301- 4311.

[167] Du J, Cheng B, Yuan H, et al. Molecular nickel thiolate complexes for electrochemical reduction of CO₂ to C_1-3 hydrocarbons. Angew Chem Int Ed. 2023; 62 (9): e202211804.

[168] Torelli DA, Francis SA, Crompton JC, et al. Nickel-gallium-catalyzed electrochemical reduction of CO₂ to highly reduced products at low overpotentials. ACS Catal. 2016; 6 (3): 2100- 2104.

[169] Paris AR, Bocarsly AB. Ni-Al films on glassy carbon electrodes generate an array of oxygenated organics from CO₂. ACS Catal. 2017; 7 (10): 6815- 6820.

[170] Li P, Liu J, Bi J, et al. Tuning the efficiency and product composition for electrocatalytic CO₂ reduction to syngas over zinc films by morphology and wettability. Green Chem. 2022; 24 (4): 1439- 1444.

[171] Zou X, Ma C, Li A, et al. Nanoparticle-assisted Ni-Co binary single-atom catalysts supported on carbon nanotubes for efficient electroreduction of CO₂ to syngas with controllable CO/H₂ ratios. ACS Appl Energy Mater. 2021; 4 (9): 9572- 9581.

[172] Proietto F, Li S, Loria A, et al. High-pressure synthesis of CO and syngas from CO₂ reduction using Ni-N-doped porous carbon electrocatalyst. Chem Eng J. 2022; 429: 132251.

[173] Leverett J, Daiyan R, Gong L, et al. Designing undercoordinated Ni-N_x and Fe-Nx on holey graphene for electrochemical CO₂ conversion to syngas. ACS Nano. 2021; 15 (7): 12006- 12018.

[174] He Q, Liu D, Lee JH, et al. Electrochemical conversion of CO₂ to syngas with controllable CO/H₂ ratios over Co and Ni single-atom catalysts. Angew Chem Int Ed. 2020; 59 (8): 3033- 3037.

[175] Deka DJ, Gunduz S, Fitzgerald T, Miller JT, Co AC, Ozkan US. Production of syngas with controllable H₂/CO ratio by high temperature co-electrolysis of CO₂ and H₂O over Ni and Co-doped lanthanum strontium ferrite perovskite cathodes. Appl Catal B. 2019; 248: 487- 503.

[176] Ping D, Huang S, Wu S, et al. LDHs-based bifunctional electrocatalyst for effective tunable syngas generation via CO₂ reduction. Int J Hydrogen Energy. 2022; 47 (56): 23653- 23660.

[177] Li J, Xu J, Zhao J, et al. Modulation of oxygen-etching for generating nickel single atoms for efficient electroreduction of CO₂ to syngas (CO/H₂). J Catal. 2023; 421: 332- 341.

[178] Kim YE, Kim B, Lee W, et al. Highly tunable syngas production by electrocatalytic reduction of CO₂ using Ag/TiO₂ catalysts. Chem Eng J. 2021; 413: 127448.

[179] Ma C, Zou X, Li A, et al. Rapid flame synthesis of carbon doped defective ZnO for electrocatalytic CO₂ reduction to syngas. Electrochim Acta. 2022; 411: 140098.

[180] Sun F, Qin J, Wang Z, et al. Energy-saving hydrogen production by chlorine-free hybrid seawater splitting coupling hydrazine degradation. Nat Commun. 2021; 12: 4182.

[181] Zhang L, Wang Z, Qiu J. Energy-saving hydrogen production by seawater electrolysis coupling sulfion degradation. Adv Mater. 2022; 34 (16): 2109321.

[182] Gu J, Liu S, Ni W, Ren W, Haussener S, Hu X. Modulating electric field distribution by alkali cations for CO₂ electroreduction in strongly acidic medium. Nat Catal. 2022; 5 (4): 268- 276.

[183] Wang L, Nitopi S, Wong AB, et al. Electrochemically converting carbon monoxide to liquid fuels by directing selectivity with electrode surface area. Nat Catal. 2019; 2 (8): 702- 708.

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