Sulfur defect-rich WS2−x nanosheet electrocatalysts for N2 reduction

硫缺陷工程设计的WS2−x纳米片电催化剂用于还 原N2

Abstract

Seeking catalysts with high electrocatalytic activity for ambient-condition N2 reduction reaction (NRR) remains an ongoing challenge due to the chemical inertness of N2. Herein, defect-rich WS2 nanosheets (WS2−x) were designed as an efficient electrocatalyst for NRR, which were prepared via vulcanizing the oxygen-vacancy-rich tungsten oxide in a vacuum tube. The sulfur defects were conducive to the adsorption and activation of N2. In neutral electrolyte of 0.1 mol L−1 Na2SO4 at −0.60 V vs. reversible hydrogen electrode, such WS2−x offered a high Faradaic efficiency of 12.1% with a NH3 generation rate of 16.38 µg h−1 mgcat−1.

摘要

由于N2的化学惰性, 实现高效的N2还原反应(NRR)亟需发展 高活性的电催化剂. 本文中, 我们设计了富含缺陷的WS2纳米片 (WS2−x)作为NRR的有效电催化剂, 该催化剂是在合成具有氧空位 的二维WO3纳米片的基础上通过真空封管法硫化方法制备而成. 这种单层的WS2纳米片是由S-W-S夹心阵列组成的类石墨烯结构, 具有高电子迁移率, 中等带隙和丰富的活性位点, 同时硫缺陷有利 于N2的吸附和活化. 在相对于可逆氢电极为−0.60 V的Na2SO4 (0.1 mol L−1)中性电解质中, 使用该WS2−x催化剂可得到12.1%的法 拉第效率和16.38 µg h−1 mgcat.−1的产氨量.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21874079), the Natural Science Foundation for Outstanding Young Scientists of Shandong Province (ZR2018JL011), the Key R&D Project of Shandong Province (GG201809230180), Taishan Scholars Program of Shandong Province (tsqn201909088), the Outstanding Youth Innovation Team of Universities in Shandong Province (2019KJA027), and the Science & Technology Fund Planning Project of Shandong Colleges and Universities (J16LA13 and J18KA112).

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Correspondence to Yuanhong Xu 许元红 or Jinghong Li 李景虹.

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Author contributions

Xu Y and Li J conceived the idea and wrote the manuscript. Ma L and Kong W carried out the synthesis, characterization and performance measurements and wrote the manuscript. Jin Z, Han Y, Sun J, and Liu J participated in the general discussion. Liu M contributed to the data analysis. Xu Y and Li J revised the manuscript.

Conflict of interest

The authors declare no conflict of interest.

Liangyu Ma is a Master candidate under the guidance of Professor Yuanhong Xu at Qingdao University. Her research focuses on the synthesis of transition metal nanomaterials and their application in nitrogen reduction.

Wenhan Kong received his MSc degree from Qingdao University in 2020. Currently, he is pursuing PhD degree at the South China University of Technology. His research focuses on nitrogen reduction and energy storage in 2D transition metal nanomaterials.

Yuanhong Xu is currently a professor at Qingdao University, China. She received her PhD in analytical chemistry from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (2009) supervised by Prof. Erkang Wang. From 2010 to 2011, she obtained the “Humboldt Research Fellowship for Postdoctoral Researchers” and did postdoctoral research in Prof. Hermann Wätzig’s group at TU Braunschweig, Germany. She joined Qingdao University in 2014. Her current scientific interests are in designing quantum dots from 2D materials for biosensors, fluorescent imaging and catalysis.

Jinghong Li is a professor at the Department of Chemistry, Tsinghua University, China. He received his PhD degree from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences in 1996. He joined the faculty of Tsinghua University in 2004. His current research interests include electroanalytical chemistry, bio-electrochemistry and sensors, physical electrochemistry and interfacial electrochemistry, electrochemical materials science and nanoscopic electrochemistry.

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Ma, L., Kong, W., Liu, M. et al. Sulfur defect-rich WS2−x nanosheet electrocatalysts for N2 reduction. Sci. China Mater. (2021). https://doi.org/10.1007/s40843-020-1572-3

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Keywords

  • electrocatalysis
  • nitrogen reduction reaction
  • transition metal sulfide
  • WS2−x
  • sulfur vacancy