Single-Ni-atoms on nitrogenated humic acid based porous carbon for CO₂ electroreduction

Abstract

We proposed a facile synthesis of single-Ni-atom catalysts on low-cost porous carbon using a calcination method at the temperatures of 850–1000 °C, which were used for CO₂ electrochemical reduction to CO. The porous carbon was prepared by carbonizing cheap and abundant humic acid. The structural characterizations of the as-synthesized catalysts and their electrocatalytic performances were analyzed. The results showed that the single-Ni-atom catalyst activated at 950 °C showed an optimum catalytic performance, and it reached a CO Faradaic efficiency of 91.9% with a CO partial current density of 6.9 mA·cm⁻² at −0.9 V vs. reversible hydrogen electrode (RHE). Additionally, the CO Faradaic efficiency and current density of the optimum catalyst changed slightly after 8 h of continuous operation, suggesting that it possessed an excellent stability. The structure-activity relations indicate that the variation in the CO₂ electrochemical reduction performance for the as-synthesized catalysts is ascribed to the combined effects of the increase in the content of pyrrolic N, the evaporation of Ni and N, the decrease in pore volume, and the change in graphitization degree.

Key words： CO₂ electroreduction; single-Ni-atom catalysts; humic acid based porous carbon

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 22308006 and 22278001), the Anhui Province Major Industrial Innovation Plan (Grant No. AHZDCYCX-LSDT2023-04), the University Synergy Innovation Program of Anhui Province (Grant No. GXXT-2022-006), the Natural Science Foundation of Anhui Provincial Education Department (Grant No. KJ2021A0407), the Youth Natural Science Foundation of Anhui University of Technology (Grant No. QZ202216), and Undergraduate Innovation and Entrepreneurship Training Program of Anhui Province (Grant No. S202310360214).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2411-7 and is accessible for authorized users.

References

1 Long C , Liu X , Wan K , Jiang Y , An P , Yang C , Wu G , Wang W , Guo J , Li L . . Regulating reconstruction of oxide-derived Cu for electrochemical CO₂ reduction toward n-propanol. Science Advances, 2023, 9(43): eadi6119

2 Zhang Y , Yu C , Tan X , Cui S , Li W , Qiu J . Recent advances in multilevel nickel-nitrogen-carbon catalysts for CO₂ electroreduction to CO. New Carbon Materials, 2021, 36(1): 19–33

3 Bo J , Li M , Zhu X , Ge Q , Han J , Wang H . Bamboo-like N-doped carbon nanotubes encapsulating M(Co, Fe)-Ni alloy for electrochemical production of syngas with potential-independent CO/H₂ ratios. Frontiers of Chemical Science and Engineering, 2022, 16(4): 498–510

4 Li J , Pršlja P , Shinagawa T , Martín Fernández A J , Krumeich F , Artyushkova K , Atanassov P , Zitolo A , Zhou Y , García-Muelas R . . Volcano trend in electrocatalytic CO₂ reduction activity over atomically dispersed metal sites on nitrogen-doped carbon. ACS Catalysis, 2019, 9(11): 10426–10439

5 Zhao Y , Wang X , Sang X , Zheng S , Yang B , Lei L , Hou Y , Li Z . Spin polarization strategy to deploy proton resource over atomic-level metal sites for highly selective CO₂ electrolysis. Frontiers of Chemical Science and Engineering, 2022, 16(12): 1772–1781

6 Möller T , Ju W , Bagger A , Wang X , Luo F , Thanh T N , Varela A S , Rossmeisl J , Strasser P . Efficient CO₂ to CO electrolysis on solid Ni–N–C catalysts at industrial current densities. Energy & Environmental Science, 2019, 12(2): 640–647

7 Long C , Wan K , Qiu X , Zhang X , Han J , An P , Yang Z , Li X , Guo J , Shi X . . Single site catalyst with enzyme-mimic micro-environment for electroreduction of CO₂. Nano Research, 2022, 15(3): 1817–1823

8 Ju W , Bagger A , Hao G P , Varela A S , Sinev I , Bon V , Roldan Cuenya B , Kaskel S , Rossmeisl J , Strasser P . Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO₂. Nature Communications, 2017, 8(1): 944

9 Sa Y J , Jung H , Shin D , Jeong H Y , Ringe S , Kim H , Hwang Y J , Joo S H . Thermal transformation of molecular Ni²⁺–N₄ sites for enhanced CO₂ electroreduction activity. ACS Catalysis, 2020, 10(19): 10920–10931

10 Varela A S , Ranjbar Sahraie N , Steinberg J , Ju W , Oh H S , Strasser P . Metal-doped nitrogenated carbon as an efficient catalyst for direct CO₂ electroreduction to CO and hydrocarbons. Angewandte Chemie International Edition, 2015, 54(37): 10758–10762

11 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

12 Yan C , Li H , Ye Y , Wu H , Cai F , Si R , Xiao J , Miao S , Xie S , Yang F . . Coordinatively unsaturated nickel-nitrogen sites towards selective and high-rate CO₂ electroreduction. Energy & Environmental Science, 2018, 11(5): 1204–1210

13 Jiang K , Siahrostami S , Zheng T , Hu Y , Hwang S , Stavitski E , Peng Y , Dynes J , Gangisetty M , Su D . . Isolated Ni single atoms in graphene nanosheets for high-performance CO₂ reduction. Energy & Environmental Science, 2018, 11(4): 893–903

14 Daiyan R , Zhu X , Tong Z , Gong L , Razmjou A , Liu R S , Xia Z , Lu X , Dai L , Amal R . Transforming active sites in nickel-nitrogen-carbon catalysts for efficient electrochemical CO₂ reduction to CO. Nano Energy, 2020, 78: 105213

15 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 Chemistry & Engineering, 2020, 8(28): 10536–10543

16 Boppella R , Austeria P M , Kim Y , Kim E , Song I , Eom Y , Kumar D P , Balamurugan M , Sim E , Kim D H . . Pyrrolic N-stabilized monovalent Ni single-atom electrocatalyst for efficient CO₂ reduction: identifying the role of pyrrolic-N and synergistic electrocatalysis. Advanced Functional Materials, 2022, 32(35): 2202351

17 Wu J , Yadav R M , Liu M , Sharma P P , Tiwary C S , Ma L , Zou X , Zhou X D , Yakobson B I , Lou J . . Achieving highly efficient, selective, and stable CO₂ reduction on nitrogen-doped carbon nanotubes. ACS Nano, 2015, 9(5): 5364–5371

18 Sharma P P , Wu J , Yadav R M , Liu M , Wright C J , Tiwary C S , Yakobson B I , Lou J , Ajayan P M , Zhou X D . Nitrogen-doped carbon nanotube arrays for high-efficiency electrochemical reduction of CO₂: on the understanding of defects, defect density, and selectivity. Angewandte Chemie International Edition, 2015, 54(46): 13701–13705

19 Jiang K , Siahrostami S , Akey A J , Li Y , Lu Z , Lattimer J , Hu Y , Stokes C , Gangishetty M , Chen G . . Transition-metal single atoms in a graphene shell as active centers for highly efficient artificial photosynthesis. Chem, 2017, 3(6): 950–960

20 Mo Z , Ajmal S , Tabish M , Kumar A , Yasin G , Zhao W . Metal-organic frameworks-based advanced catalysts for anthropogenic CO₂ conversion toward sustainable future. Fuel Processing Technology, 2023, 244: 107705

21 Zheng T , Jiang K , Ta N , Hu Y , Zeng J , Liu J , Wang H . Large-scale and highly selective CO₂ electrocatalytic reduction on nickel single-atom catalyst. Joule, 2019, 3(1): 265–278

22 Wang C , Cheng T , Zhang D , Pan X . Electrochemical properties of humic acid and its novel applications: A tip of the iceberg. Science of the Total Environment, 2023, 863: 160755

23 Huang G , Kang W , Xing B , Chen L , Zhang C . Oxygen-rich and hierarchical porous carbons prepared from coal based humic acid for supercapacitor electrodes. Fuel Processing Technology, 2016, 142: 1–5

24 Zhong M , Gao S , Zhou Q , Yue J , Ma F , Xu G . Characterization of char from high temperature fluidized bed coal pyrolysis in complex atmospheres. Particuology, 2016, 25: 59–67

25 Li Y , Adli N M , Shan W , Wang M , Zachman M J , Hwang S , Tabassum H , Karakalos S , Feng Z , Wang G . . Atomically dispersed single Ni site catalysts for high-efficiency CO₂ electroreduction at industrial-level current densities. Energy & Environmental Science, 2022, 15(5): 2108–2119

26 Liang S , Jiang Q , Wang Q , Liu Y . Revealing the real role of nickel decorated nitrogen-doped carbon catalysts for electrochemical reduction of CO₂ to CO. Advanced Energy Materials, 2021, 11(36): 2101477

27 Li X , Bi W , Chen M , Sun Y , Ju H , Yan W , Zhu J , Wu X , Chu W , Wu C . . Exclusive Ni–N₄ sites realize near-unity CO selectivity for electrochemical CO₂ reduction. Journal of the American Chemical Society, 2017, 139(42): 14889–14892

28 Sun Z , Ma T , Tao H , Fan Q , Han B . Fundamentals and challenges of electrochemical CO₂ reduction using two-dimensional materials. Chem, 2017, 3(4): 560–587

29 Lu Q , Rosen J , Zhou Y , Hutchings G S , Kimmel Y C , Chen J G , Jiao F . A selective and efficient electrocatalyst for carbon dioxide reduction. Nature Communications, 2014, 5(1): 3242

30 Gao M R , Liang J X , Zheng Y R , Xu Y F , Jiang J , Gao Q , Li J , Yu S H . An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation. Nature Communications, 2015, 6(1): 5982

31 Liu X C , Hu J , Xie R L , Fang B , Cui P . Formation mechanism of solid product produced from co-pyrolysis of Pingdingshan lean coal with organic matter in Huadian oil shale. Frontiers of Chemical Science and Engineering, 2021, 15(2): 363–372

32 Yang M , Wang L , Li M , Hou T , Li Y . Structural stability and O₂ dissociation on nitrogen-doped graphene with transition metal atoms embedded: a first-principles study. AIP Advances, 2015, 5(6): 067136

33 Yang H B , Hung S F , Liu S , Yuan K , Miao S , Zhang L , Huang X , Wang H Y , Cai W , Chen R . . Atomically dispersed Ni(I) as the active site for electrochemical CO₂ reduction. Nature Energy, 2018, 3(2): 140–147

34 Brazzolotto D , Gennari M , Queyriaux N , Simmons T R , Pécaut J , Demeshko S , Meyer F , Orio M , Artero V , Duboc C . Nickel-centred proton reduction catalysis in a model of [NiFe] hydrogenase. Nature Chemistry, 2016, 8(11): 1054–1060

35 Ebner S , Jaun B , Goenrich M , Thauer R K , Harmer J . Binding of coenzyme B induces a major conformational change in the active site of methyl-coenzyme M reductase. Journal of the American Chemical Society, 2010, 132(2): 567–575

36 Jia Q , Ramaswamy N , Hafiz H , Tylus U , Strickland K , Wu G , Barbiellini B , Bansil A , Holby E F , Zelenay P . . Experimental observation of redox-induced Fe–N switching behavior as a determinant role for oxygen reduction activity. ACS Nano, 2015, 9(12): 12496–12505

37 Yu J Q , Guo Q H , Ding L , Gong Y , Yu G S . Studying effects of solid structure evolution on gasification reactivity of coal chars by in-situ Raman spectroscopy. Fuel, 2020, 270: 117603

38 Xiong Y K , Jin L J , Yang H , Li Y , Hu H Q . Insight into the aromatic ring structures of a low-rank coal by step-wise oxidation degradation. Fuel Processing Technology, 2020, 210: 106563

39 Li X J , Hayashi J I , Li C Z . FT-Raman spectroscopic study of the evolution of char structure during the pyrolysis of a Victorian brown coal. Fuel, 2006, 85(12–13): 1700–1707

40 Ni W , Liu Z , Zhang Y , Ma C , Deng H , Zhang S , Wang S . Electroreduction of carbon dioxide driven by the intrinsic defects in the carbon plane of a single Fe–N₄ site. Advanced Materials, 2021, 33(1): e2003238

41 Liu X , Li G , Zhao H , Ye Y , Xie R , Zhao Z , Lei Z , Cui P . Changes in caking properties of caking bituminous coals during low-temperature pyrolysis process. Fuel, 2022, 321: 124023

42 Lu L , Sahajwalla V , Harris D . Characteristics of chars prepared from various pulverized coals at different temperatures using drop-tube furnace. Energy & Fuels, 2000, 14(4): 869–876

43 Liu X C , Fang B , Zhao Z G , Xie R L , Lei Z , Ling Q , Cui P . Modification mechanism of caking and coking properties of Shenmu subbituminous coal by low-temperature rapid pyrolysis treatment. Journal of Iron and Steel Research International, 2019, 26(10): 1052–1060

44 Ghosh D , Periyasamy G , Pandey B , Pati S K . Computational studies on magnetism and the optical properties of transition metal embedded graphitic carbon nitride sheets. Journal of Materials Chemistry. C, Materials for Optical and Electronic Devices, 2014, 2(37): 7943–7951

45 Li S , Zhao S , Lu X , Ceccato M , Hu X M , Roldan A , Catalano J , Liu M , Skrydstrup T , Daasbjerg K . Low-valence Zn^δ+ (0 < δ < 2) single-atom material as highly efficient electrocatalyst for CO₂ reduction. Angewandte Chemie International Edition, 2021, 60(42): 22826–22832

46 Jia M , Choi C , Wu T S , Ma C , Kang P , Tao H , Fan Q , Hong S , Liu S , Soo Y L . . Carbon-supported Ni nanoparticles for efficient CO₂ electroreduction. Chemical Science, 2018, 9(47): 8775–8780

47 Wang F , Miao Z , Mu J , Zhao Y , Liang M , Meng J , Wu X , Zhou P , Zhao J , Zhuo S . . A Ni nanoparticles encapsulated in N-doped carbon catalyst for efficient electroreduction CO₂: identification of active sites for adsorption and activation of CO₂ molecules. Chemical Engineering Journal, 2022, 428: 131323