Recent advances in multilevel nickel-nitrogen-carbon catalysts for CO2 electroreduction to CO
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摘要: 电化学CO2还原（ECR）作为一种清洁的CO2转化技术，倍受关注。开发高效的电催化剂是影响和决定ECR技术发展的关键。碳基材料具有来源丰富、比表面积高、孔隙率大、维数尺度多和活性位点可调等优点，是理想的ECR电催化剂之一。其中，金属镍-氮-碳（Ni-N-C）材料由于其活性位点丰富、选择性高等特点，在ECR生成CO的过程中展现出巨大的优势和应用潜力。本文介绍了ECR反应的基本原理和主要性能参数，综述了近年来国内外有关多尺度Ni-N-C催化剂在ECR反应生成CO中的研究进展。详细介绍了Ni-N-C催化剂碳骨架/基底的种类，主要包括小尺度碳质材料、一维（1D）碳质材料、二维（2D）碳质材料和纳米多孔碳质材料。讨论了Ni-N-C催化剂在电还原CO2生成CO应用过程中存在的问题。最后，展望了Ni-N-C催化剂在ECR体系中的挑战与应用前景。Abstract: As an emerging CO2 conversion technology, the electrochemical CO2 reduction (ECR) reaction has received widespread attention. For the ECR process, the accurate and rational design of electrocatalysts is essential and significant for improving the catalytic performance. Carbon-based materials are considered one of the promising electrocatalysts for ECR because of their variety of abundant sources, high specific surface area, high porosity, and multilevel dimensionality and tunable active sites. Furthermore, doping by heteroatoms and introducing metal atoms in the frameworks or substrates of the carbon materials are effective strategies for further improving the ECR activity. Particularly, nickel-nitrogen-carbon (Ni-N-C) materials show excellent reactivities for the ECR to CO and have the potential for large-scale applications. We summarize the recent development of Ni-N-C catalysts with a multilevel structure for the ECR to CO and also the key principles and primary parameters of the ECR. Furthermore, the rational and precise design of multilevel Ni-N-C catalysts on different carbon frameworks or substrates is discussed and presented, especially including carbon quantum dots, one dimensional (1D) carbon-based materials, two dimensional (2D) carbon-based materials and nanoporous carbon-based materials. The effects of microstructure on ECR performance are also analyzed. Finally, the challenges and outlook for Ni-N-C catalysts in an ECR system are presented. This review provides some new insights and guidelines for rationally designing and preparing Ni-N-C catalysts with a multilevel structure and high performance.
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Figure 1. The number of papers on ECR in the past ten years. The data source is the search result of Web of Science, where the key words for the data of the blue bars and the orange bars are electrochemical CO2 reduction, electrochemical CO2 reduction to CO, respectively. The inset is the percentage of papers involving the electrocatalysts in ECR to CO.
Figure 2. Schematic mechanism for CO2 conversion to CO via ECR process (gray ball: catalyst, orange ball: active site, blue ball: C, red ball: O and yellow ball: H).
Figure 3. Carbon frameworks for multilevel Ni-N-C catalysts applied in ECR to produce CO.
Figure 4. (a) The synthesis process for Ni1-N/CNT, (b) the image of HAADF-STEM for the Ni1-N/CNT (The red circles indicated the Ni single atoms), (c) free energy diagrams of Ni-N5, Fe-N5, and Co-N5 configurations for ECR at 0 V (vs. RHE) and (d) Free energy diagrams of Ni-N5, Fe-N5, and Co-N5 configurations for HER[27]. Copyright 2020, Wiley-VCH.
Figure 5. (a) Schematic of ECR process over the Au-CDots-C3N4 catalyst[28] (Copyright 2018, American Chemical Society), (b) the process of syngas generation over the Co3O4-CDots-C3N4 catalyst[29] (Copyright 2017, Nature Publishing Group) and (c) diagram for the ECR reaction mechanism over the p-Ag/CQD composite[30] (Copyright 2019, The Royal Society of Chemistry).
Figure 6. (a) Illustration for the schematic on the synthesis of H-CPs, (b) good mechanical properties of H-CPs before and after press[33] (Copyright 2019, Elsevier), (c) structure diagram for Fe-N/CNT@GNR catalyst obtained by unzipping the CNTs[34] (Copyright 2020, American Chemical Society), (d) diagram for the synthesis process of PyNiPc/CNT and (e) comparison of UV–vis spectra for PyNiPc/CNT, CNTs and PyNiPc[35] (Copyright 2020, Elsevier).
Figure 7. (a) HAADF-STEM image of Ni–NG, where the red circles presented the Ni single atoms, (b) schematic illustration for MEA, (c) the model of three kinds of N species (gray ball: carbon atom, black ball: pyridinic-N, blue ball: pyrrolic-N, pink ball: graphitic-N and white ball: hydrogen atom)[41] (Copyright 2018, The Royal Society of Chemistry), (d) scanning electron microscope (SEM) and atomic force microscope (AFM) (inset) images of A-Ni-NSG[42] (Copyright 2018, Springer Nature), and (e) schematic diagram of the ion adsorption process on the surface of NG[44] (Copyright 2018, Wiley-VCH).
Figure 8. (a) The preparation process of the Ni-N-MEGO catalyst and (b) TEM image of the Ni-N-MEGO catalyst[50] (Copyright 2019, Elsevier).
Figure 9. (a) The synthesis of Ni SAs/N-C, (b) N2 adsorption/desorption isotherms for Ni SAs/N-C, Ni NPs/N-C, pyrolyzed ZIF-8 and ZIF-8, (c) CO2 adsorption isotherms for Ni SAs/N-C, Ni NPs/N-C, and pyrolyzed ZIF-8[56] (Copyright 2017, American Chemical Society), (d) schematic illustration on the synthesis of C-ZnxNiy ZIF-8, (e) the structure models of different Ni-N sites, (f) free energy diagrams for ECR derived from DFT calculation, (g) free energy diagrams for HER derived from DFT calculation[57] (Copyright 2018, The Royal Society of Chemistry), (h) schematic illustration on the synthesis of SE-Ni SAs@ PNC[58] (Copyright 2018, Wiley-VCH), (i) schematic of the synthesis of carbon catalysts using copper doped ZIF-8 as a precursor, (j) the adsorption capacity of CuZIF-derived catalysts for CO2 and (k) the result of charging j differences Δj with different scan rates over various electrocatalysts[59] (Copyright 2019, American Chemical Society).
Table 1. The standard electrode potentials for the main half reactions of ECR.
Product Reaction equation Eo(vs. RHE) CO CO2+2H++2e−→CO(g)+H2O –0.10 V Formic acid CO2+2H++2e−→HCOOH(aq) –0.12 V Hydrocarbon CO2+8H++8e−→CH4(g)+2H2O 0.17 V CO2+12H++12e−→C2H4(g)+4H2O 0.08 V Alcohol CO2+6H++6e−→CH3OH(aq)+H2O 0.03 V 2CO2+12H++12e−→C2H5OH(aq)+3H2O 0.09 V 
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