富电子中心完全暴露镍团簇催化剂高性能电催化CO2还原合成CO|Science Bulletin

Science Bulletin, 2022, 67(14): 1477-1485

https://doi.org/10.1016/j.scib.2022.06.006

Article

Fully exposed nickel clusters with electron-rich centers for high-performance electrocatalytic CO₂ reduction to CO

富电子中心完全暴露镍团簇催化剂高性能电催化CO₂还原合成CO

郝琦, 汤淇, 钟海霞, 王家志, 刘冬雪, 张新波

研究简介

单原子催化剂（SAC）因其最大化的金属原子利用率、独特的电子结构和优异的催化性能在电催化领域引起越来越多的关注。然而，对于需要同时活化不同反应物/中间体的反应来说，孤立的位点是不利的。完全暴露的金属簇催化剂（FECC），继承了SACs和金属纳米颗粒的优点，可以在其多原子位点上协同吸附和活化反应物/中间物，在电催化反应中显示了巨大的前景。中科院长春应用化学研究所张新波研究员课题组开发了一种简便的方法，从团簇到单原子尺度来调节Ni物种的原子分散度，以实现高效的CO₂还原。所制备的Ni FECC在CO合成中表现出了高达99%的法拉第效率，347.2 mA cm^-2的高CO分电流密度，以及在20 h电解下的优异稳定性。理论计算表明，多原子中心的构建和硫原子掺杂共同加速了反应动力学，从而提高了电化学CO₂还原合成CO的活性与选择性。

Fig. 1. (a) Schematic synthesis procedure of Ni FECC. (b–e) High-resolution HAADF-STEM images of NiNSC-700 (b), NiNSC-800 (c), NiNsc-900 (d) and NiNSC-1000 (e). (f-j) Low-resolution HAADF-STEM and corresponding EDS mapping of NiNSC-900.

Fig. 2. (a) Ni K-edge XANES profiles and (b) EXAFS spectra of Ni foil, NiO, NiS, NiNSC-700, NiNSC-800, NiNSC-900 and NiNSC-1000. (c) Experiment data and fitted data of NiNSC-900 at R space. (d) High-resolution Ni 2p spectra of NiNSC-700, NiNSC-800, NiNSC-900, and NiNSC-1000.

Fig. 3.  (a, d) LSV curves of N, S Ni NPs, NiNSC-700, NiNSC-800, NiNsc-900, and NiNSC-1000 under CO₂ and Ar saturated electrolytes in H-cell (a) and flow cell (d). (b, e) FE_CO for N, S Ni NPs, NiNSC-700, NiNSC-800, NiNsc-900 and NiNSC-1000 in H-cell (b) and flow cell (e). (c, f) j_CO for N, S Ni NPs, NiNSC-700, NiNSC-800, NiNsc-900 and NiNSC-1000 in H-cell (c) and flow cell (f). (g, h) Long-time durability of NiNSC-900 at –0.6 V vs. RHE. in H-cell (g) and at –0.5 V vs. RHE in a flow cell (h).

Fig. 4. (a) Free energy profiles of CO₂ electrocatalysis on NiN₄, NiN₃S, Ni₂N₄S_2, and Ni₃N₃S₃sites. (b) Free energy of *COOH and CO (g) in CO₂ electrocatalysis and Bader charge for NiN₄, NiN₃S, Ni₂N₄S_2, and Ni₃N₃S₃. (c–f) The differential charge density maps of the *COOH intermediate on NiN₄ (c), NiN₃S (d), Ni₂N₄S₂ (e), and Ni₃N₃S₃ (f) sites.

Qi Hao, Qi Tang, Hai-Xia Zhong, Jia-Zhi Wang, Dong-Xue Liu, Xin-Bo Zhang. Fully exposed nickel clusters with electron-rich centers for high-performance electrocatalytic CO₂ reduction to CO. Science Bulletin, 2022, 67(14): 1477-1485