Synthesis of 2D NiFe-Nx-C materials for electrocatalytic CO2 reduction

Abstract In order to reduce the energy barrier of CO₂ activation at Ni-N sites and solve the problem of CO poisoning at Fe-N sites, an ultra-thin two-dimensional carbon-based catalyst (ZNF-900) with NiFe-N_x active sites was synthesized by limited solvent growth and pyrolysis methods. The ZNF-900 has ultra-high selectivity (FE_CO>97%) and CO partial current density (j_CO=37.3 mA·cm^-2) for electrocatalytic CO₂ reduction to CO. By XPS, Raman, EIS, Tafel slope and other analytic methods, it is proved that there is a synergistic promoting effect between Ni and Fe, which promotes the adsorption of CO₂ molecules and the desorption of CO products on the surface of catalysts.

	Service

	Email this article
	Add to my bookshelf
	Add to citation manager
	Email Alert
	RSS
	Articles by authors
	LI Jing
	LI Yang
	FAN Xiaobin
	ZHANG Fengbao
	ZHANG Guoliang
	XIA Qing
	PENG Wenchao

Keywords： two-dimensional carbon-based catalyst synergistic catalysis CO₂ reduction electrocatalysis

Received 2022-05-19;

About author:

Cite this article:

LI Jing, LI Yang, FAN Xiaobin, ZHANG Fengbao, ZHANG Guoliang, XIA Qing, PENG Wenchao.Synthesis of 2D NiFe-N_x-C materials for electrocatalytic CO₂ reduction[J] Chemcial Industry and Engineering, 2024,V41(2): 12-23

[1] COX P M, BETTS R A, JONES C D, et al. Acceleration of global warming due to carbon-cycle feedbacks in a coupled climate model[J]. Nature, 2000, 408(6809): 184-187
[2] COKOJA M, BRUCKMEIER C, RIEGER B, et al. Transformation of carbon dioxide with homogeneous transition-metal catalysts: A molecular solution to a global challenge?[J]. Angewandte Chemie International Edition, 2011, 50(37): 8510-8537
[3] ARESTA M, DIBENEDETTO A. Utilisation of CO₂ as a chemical feedstock: Opportunities and challenges[J]. Dalton Transactions, 2007(28): 2975-2992
[4] SONG C. Global challenges and strategies for control, conversion and utilization of CO₂ for sustainable development involving energy, catalysis, adsorption and chemical processing[J]. Catalysis Today, 2006, 115(1/2/3/4): 2-32
[5] WANG W, WANG S, MA X, et al. Recent advances in catalytic hydrogenation of carbon dioxide[J]. Chemical Society Reviews, 2011, 40(7): 3703-3727
[6] BIRDJA Y Y, PÉREZ-GALLENT E, FIGUEIREDO M C, et al. Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels[J]. Nature Energy, 2019, 4(9): 732-745
[7] DE ARQUER F P G, DINH C T, OZDEN A, et al. CO₂ electrolysis to multicarbon products at activities greater than 1 A·cm^-2[J]. Science, 2020, 367(6478): 661-666
[8] GAO D, ARÁN-AIS R M, JEON H S, et al. Rational catalyst and electrolyte design for CO₂ electroreduction towards multicarbon products[J]. Nature Catalysis, 2019, 2(3): 198-210
[9] ROSS M B, DE LUNA P, LI Y, et al. Designing materials for electrochemical carbon dioxide recycling[J]. Nature Catalysis, 2019, 2(8): 648-658
[10] ZHANG Y, SETHURAMAN V, MICHALSKY R, et al. Competition between CO₂ reduction and H₂ evolution on transition-metal electrocatalysts[J]. ACS Catalysis, 2014, 4(10): 3742-3748
[11] KIM D, RESASCO J, YU Y, et al. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold-copper bimetallic nanoparticles[J]. Nature Communications, 2014, 5(1): 1-8
[12] WAN X, LIU X, LI Y, et al. Fe-N-C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells[J]. Nature Catalysis, 2019, 2(3): 259-268
[13] ZHAO K, NIE X, WANG H, et al. Selective electroreduction of CO₂ to acetone by single copper atoms anchored on N-doped porous carbon[J]. Nature Communications, 2020, 11(1): 1-10
[14] FENG D, ZHU Y, CHEN P, et al. Recent advances in transition-metal-mediated electrocatalytic CO₂ reduction: From homogeneous to heterogeneous systems[J]. Catalysts, 2017, 7(12): 373
[15] HANSEN H A, VARLEY J B, PETERSON A A, et al. Understanding trends in the electrocatalytic activity of metals and enzymes for CO₂ reduction to CO[J]. The Journal of Physical Chemistry Letters, 2013, 4(3): 388-392
[16] LI M, WANG H, LUO W, et al. Heterogeneous single-atom catalysts for electrochemical CO₂ reduction reaction[J]. Advanced Materials, 2020, 32(34)
[17] LI X, ZENG Y, TUNG C, et al. Unveiling the in situ generation of a monovalent Fe(I) site in the single-Fe-atom catalyst for electrochemical CO₂ reduction[J]. ACS Catalysis, 2021, 11(12): 7292-7301
[18] HUANG L, ZHANG X, HAN Y, et al. In situ synthesis of ultrathin metal-organic framework nanosheets: A new method for 2D metal-based nanoporous carbon electrocatalysts[J]. Journal of Materials Chemistry A, 2017, 5(35): 18610-18617
[19] LU B, LIU Q, CHEN S. Electrocatalysis of single-atom sites: Impacts of atomic coordination[J]. ACS Catalysis, 2020, 10(14): 7584-7618
[20] LIANG S, HUANG L, GAO Y, et al. Electrochemical reduction of CO₂ to CO over transition metal/N-doped carbon catalysts: The active sites and reaction mechanism[J]. Advanced Science, 2021, 8(24): 2102886
[21] ZHANG H, CHENG W, LUAN D, et al. Atomically dispersed reactive centers for electrocatalytic CO₂ reduction and water splitting[J]. Angewandte Chemie International Edition, 2021, 60(24): 13177-13196
[22] HUANG Q, WEI K, XIA H. Investigations in the recrystallization of evolved gases from pyrolysis process of melamine[J]. Journal of Thermal Analysis and Calorimetry, 2019, 138(6): 3897-3903
[23] QU Y, CHEN B, LI Z, et al. Thermal emitting strategy to synthesize atomically dispersed Pt metal sites from bulk Pt metal[J]. Journal of the American Chemical Society, 2019, 141(11): 4505-4509
[24] ZHU Y, SUN W, LUO J, et al. A cocoon silk chemistry strategy to ultrathin N-doped carbon nanosheet with metal single-site catalysts[J]. Nature Communications, 2018, 9(1): 1-9
[25] WANG X, CHEN Z, ZHAO X, et al. Regulation of coordination number over single Co sites: Triggering the efficient electroreduction of CO₂[J]. Angewandte Chemie, 2018, 130(7): 1962-1966
[26] GONG Y, JIAO L, QIAN Y, et al. Regulating the coordination environment of MOF-templated single-atom nickel electrocatalysts for boosting CO₂ reduction[J]. Angewandte Chemie International Edition, 2020, 59(7): 2705-2709
[27] GU Y, WU H, XIONG Z, et al. The electrocapacitive properties of hierarchical porous reduced graphene oxide templated by hydrophobic CaCO₃ spheres[J]. Journal of Materials Chemistry A, 2014, 2(2): 451-459
[28] LUONG D X, BETS K V, ALI ALGOZEEB W, et al. Gram-scale bottom-up flash graphene synthesis[J]. Nature, 2020, 577(7792): 647-651
[29] SUN Z, YAN Z, YAO J, et al. Growth of graphene from solid carbon sources[J]. Nature, 2010, 468(7323): 549-552
[30] YANG H, LIN Q, ZHANG C, et al. Carbon dioxide electroreduction on single-atom nickel decorated carbon membranes with industry compatible current densities[J]. Nature Communications, 2020, 11(1): 1-8
[31] JU W, BAGGER A, HAO G, et al. Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO₂[J]. Nature Communications, 2017, 8(1): 1-9
[32] YANG H, HUNG S F, LIU S, et al. Atomically dispersed Ni(i) as the active site for electrochemical CO₂ reduction[J]. Nature Energy, 2018, 3(2): 140-147
[33] ZHANG H, LI J, XI S, et al. A graphene-supported single-atom FeN₅ catalytic site for efficient electrochemical CO₂ reduction[J]. Angewandte Chemie (International Ed in English), 2019, 58(42): 14871-14876
[34] ZENG Z, GAN L, YANG H, et al. Orbital coupling of hetero-diatomic nickel-iron site for bifunctional electrocatalysis of CO₂ reduction and oxygen evolution[J]. Nature Communications, 2021, 12(1): 1-11
[35] YANG X, TAT T, LIBANORI A, et al. Single-atom catalysts with bimetallic centers for high-performance electrochemical CO₂ reduction[J]. Materials Today, 2021, 45: 54-61
[36] 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[J]. Nano Energy, 2020, 77: 105158
[37] FAN Q, HOU P, CHOI C, et al. Activation of Ni particles into single Ni-N atoms for efficient electrochemical reduction of CO₂[J]. Advanced Energy Materials, 2020, 10(5): 1903068
[38] RONG X, WANG H, LU X, et al. Controlled synthesis of a vacancy-defect single-atom catalyst for boosting CO₂ electroreduction[J]. Angewandte Chemie International Edition, 2020, 59(5): 1961-1965
[39] GU J, HSU C S, BAI L, et al. Atomically dispersed Fe³⁺ sites catalyze efficient CO₂ electroreduction to CO[J]. Science, 2019, 364: 1091-1094
[40] WANG X, CHEN Z, ZHAO X, et al. Regulation of coordination number over single Co sites: Triggering the efficient electroreduction of CO₂[J]. Angewandte Chemie International Edition, 2018, 57(7): 1944-1948
[41] CHEN Z, ZHANG X, LIU W, et al. Amination strategy to boost the CO₂ electroreduction current density of M-N/C single-atom catalysts to the industrial application level[J]. Energy & Environmental Science, 2021, 14(4): 2349-2356
[42] WANG X, CHEN Z, ZHAO X, et al. Regulation of coordination number over single Co sites: Triggering the efficient electroreduction of CO₂[J]. Angewandte Chemie, 2018, 130(7): 1962-1966
[43] GONG Y, JIAO L, QIAN Y, et al. Regulating the coordination environment of MOF-templated single-atom nickel electrocatalysts for boosting CO₂ reduction[J]. Angewandte Chemie, 2020, 132(7): 2727-2731