Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering
Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering
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DOI：
10.1016/j.nanoen.2019.104384
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发表时间：
2020-02
期刊：
影响因子：
17.6
通讯作者：
Fuping Pan;Boyang Li;Erik Sarnello;Sooyeon Hwang;Yang Gang;Xuhui Feng;Xianmei Xiang;Nadia Mohd Adli-Nadia
中科院分区：
文献类型：
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作者：
Fuping Pan;Boyang Li;Erik Sarnello;Sooyeon Hwang;Yang Gang;Xuhui Feng;Xianmei Xiang;Nadia Mohd Adli-Nadia
开发富土高效的二氧化碳还原反应催化剂(CO2RR)对二氧化碳电化学法转化为增值产品具有重要意义。尽管对铁氮共掺碳(Fe-N-C)催化剂进行了大量的研究，但由于性能和对催化机理的了解有限，仍然存在巨大的挑战。本研究报道了一种提高Fe-N-C的电催化CO_2RR活性的一般策略，通过共聚辅助合成方法，引入S原子来同时设计碳的载体结构和活性Fe-N位的电子性质。N、S共聚单体的使用显著增加了微孔数量和比表面积，使Fe-N原子致密，提高了利用效率。第一性原理计算表明，S调制提高了Fe3d的费米能，增加了Fe-N4的Fe原子上的电荷密度，从而通过加强Fe中心与关键COOH*中间体之间的结合作用，提高了本征催化反应活性和CO2还原的选择性。这些综合的结构和电子方面的优点赋予了Fe-NS-C突出的活性(例如，在490 mV的过电位下，CO法拉第效率达到98%)和稳定性(30h内没有失活)，使其成为迄今报道的最活跃的Fe-N-C之一。这一发现提供了一种创新的设计策略，使先进的二氧化碳转化催化剂的设计成为可能。
Developing earth-abundant efficient catalysts for CO2reduction reaction (CO2RR) is of paramount importance for electrochemical conversion of CO2into value-added products. Despite numerous studies on iron and nitrogen codoped carbon (Fe-N-C) catalysts, grand challenges exist due to limited performance and understanding of catalytic mechanisms. This study reports a general strategy to boost electrocatalytic CO2RR activity of Fe-N-C with the incorporation of S atoms to engineer carbon support structure and electronic properties of active Fe–N sites simultaneously via a copolymer-assisted synthetic approach. The employment of N,S comonomers significantly increases the numbers of micropores and surface area, enabling dense atomic Fe–N and enhanced utilization efficiency. The first-principles calculations reveal that S modulation upraises the Fermi energy of Fe 3d and increases charge density on Fe atoms of Fe–N4, thereby enhancing intrinsic catalytic reactivity and selectivity for CO2reduction by strengthening the binding interaction between the Fe site and key COOH* intermediate. These integrated structural and electronic merits endow Fe-NS-C with outstanding activity (e.g., CO Faradaic efficiency of 98% at an overpotential of 490 mV) and stability (without deactivation in 30 h), ranking it one of the most active Fe-N-C reported to date. The finding offers an innovative design strategy to enable the design of advanced catalysts for CO2conversion.