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论文类型：期刊论文

发表时间：2021-03-18

发表刊物：ACS SUSTAINABLE CHEMISTRY & ENGINEERING

卷号：8

期号：35

页面范围：13430-13439

ISSN号：2168-0485

关键字：electrocatalytic nitrogen fixation; cobalt coordinated with nitrogen; structure activity relationship; reaction pathway; rate-determining step; Co-N-x active centers

摘要：Electrocatalytic ammonia (NH3) synthesis under ambient temperature and pressure is an emerging sustainable method for dinitrogen (N-2) fixation, providing a potential environmentally benign pathway for N-2 fixation using renewable power of electricity. However, this strategy is subjected to the low activity of electrocatalysts. In this work, a Co-N-x-C hybrid derived from the metal-organic framework with built-in Co-N-x active sites was fabricated. A high NH3 yield (37.6 mu g mg(-1) h(-1) at -0.9 V vs a reversible hydrogen electrode) and favorable faradaic efficiency (17.6% at -0.3 V vs a reversible hydrogen electrode) were achieved in a 0.05 M H2SO4 electrolyte. The dominating coordination environment of Co-N-x was finally determined by combining X-ray absorption fine structure spectroscopy and theoretical calculation. Co-N-3 demonstrated pivotal active centers that facilitated N-2 adsorption, lowered the free energy of the rate-determining step, inhibited hydrogen evolution reaction, and promoted the N-2 reduction reaction (N2RR). The hierarchical pore structure of catalysts also promoted N-2 adsorption, and the produced high pressure contributed to the further reaction of N-2 fixation. This work also provides a new strategy for developing cost-effective electrocatalytic materials for N2RR.