Amorphization activated FeB2 porous nanosheets enable efficient electrocatalytic N2 fixation
Amorphization activated FeB2 porous nanosheets enable efficient electrocatalytic N2 fixation
复制标题
非晶化活化的 FeB2 多孔纳米片可实现高效的电催化 N-2 固定
DOI：
10.1016/j.jechem.2020.05.009
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发表时间：
2021-02-01
影响因子：
13.1
通讯作者：
Liu, Wuming
中科院分区：
文献类型：
--
作者：
Chu, Ke;Gu, Weicong;Liu, Wuming
为氮还原反应（NRR）设计活性、耐用且具有成本效益的催化剂对于可持续的电化学NH3合成具有至关重要的意义。过渡金属二硼化物（TMB 2）是一种新型的NRR催化剂，但目前还缺乏直接的实验证据。在此，我们提出了第一个实验证明，无定形FeB 2多孔纳米片（a-FeB 2 PNS）可以是一种高效的NRR催化剂，其表现出39.8 μ g h（-1）mg（-1）（-0.3 V）的NH3产率和16.7%（-0.2 V）的法拉第效率，显着优于其结晶对应物和大多数现有的NRR催化剂。第一性原理计算表明，非晶化可以诱导a-FeB 2的d-带中心升高，从而促进活性Fe位与 * N2 H中间体之间的d-2 pi* 耦合，从而增强 * N2 H稳定性，降低反应势垒。该研究有助于开发和理解地球丰富的TMB 2基催化剂用于电催化固定N-2。(C)2020科学出版社、中国科学院大连化学物理研究所。由ELSEVIER B. V.和科学出版社出版。All rights reserved.
Designing active, robust and cost-effective catalysts for the nitrogen reduction reaction (NRR) is of paramount significance for sustainable electrochemical NH3 synthesis. Transition-metal diborides (TMB2) have been recently theoretically predicted to be a new class of potential NRR catalysts, but direct experimental evidence is still lacking. Herein, we present the first experimental demonstration that amorphous FeB2 porous nanosheets (a-FeB2 PNSs) could be a highly efficient NRR catalyst, which exhibited an NH3 yield of 39.8 mu g h(-1) mg(-1) (-0.3 V) and a Faradaic efficiency of 16.7% (-0.2 V), significantly outperforming their crystalline counterpart and most of existing NRR catalysts. First-principle calculations unveiled that the amorphization could induce the upraised d-band center of a-FeB2 to boost d-2 pi* coupling between the active Fe site and *N2H intermediate, resulting in enhanced *N2H stabilization and reduced reaction barrier. Out study may facilitate the development and understanding of earth-abundant TMB2-based catalysts for electrocatalytic N-2 fixation. (C) 2020 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.