Balancing hydrogen adsorption/desorption by orbital modulation for efficient hydrogen evolution catalysis

Feng Li; Gao-Feng Han; Hyuk-Jun Noh; Jong-Pil Jeon; Ishfaq Ahmad; Shanshan Chen; Changduk Yang; Yunfei Bu; Zhengping Fu; Yalin Lu; Jong-Beom Baek

doi:10.1038/s41467-019-12012-z

Balancing hydrogen adsorption/desorption by orbital modulation for efficient hydrogen evolution catalysis

Nat Commun. 2019 Sep 6;10(1):4060. doi: 10.1038/s41467-019-12012-z.

Authors

Feng Li¹, Gao-Feng Han¹, Hyuk-Jun Noh¹, Jong-Pil Jeon¹, Ishfaq Ahmad¹, Shanshan Chen^{2

3}, Changduk Yang³, Yunfei Bu⁴, Zhengping Fu⁵, Yalin Lu⁶, Jong-Beom Baek⁷

Affiliations

¹ School of Energy and Chemical Engineering/Center for Dimension-Controllable Organic Frameworks, Ulsan National Institute of Science and Technology (UNIST), 50 UNIST, Ulsan, 44919, South Korea.
² MOE Key Laboratory of Low-grade Energy Utilization Technologies and Systems, CQU-NUS Renewable Energy Materials & Devices Joint Laboratory, School of Energy & Power Engineering, Chongqing University, Chongqing, 400044, P. R. China.
³ Department of Energy Engineering, School of Energy and Chemical Engineering, Perovtronics Research Center, Low Dimensional Carbon Materials Center, Ulsan National Institute of Science and Technology (UNIST), 50 UNIST, Ulsan, 44919, South Korea.
⁴ School of Environmental Science and Engineering, Nanjing University of Information Science and Technology, 219 Ningliu, Nanjing, Jiangsu, 210044, P. R. China. yunfei.bu@nuist.edu.cn.
⁵ CAS Key Laboratory of Materials for Energy Conversion, Hefei National Laboratory for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 96 Jinzhai, Hefei, Anhui, 230026, P. R. China. fuzp@ustc.edu.cn.
⁶ CAS Key Laboratory of Materials for Energy Conversion, Hefei National Laboratory for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 96 Jinzhai, Hefei, Anhui, 230026, P. R. China.
⁷ School of Energy and Chemical Engineering/Center for Dimension-Controllable Organic Frameworks, Ulsan National Institute of Science and Technology (UNIST), 50 UNIST, Ulsan, 44919, South Korea. jbbaek@unist.ac.kr.

Abstract

Hydrogen adsorption/desorption behavior plays a key role in hydrogen evolution reaction (HER) catalysis. The HER reaction rate is a trade-off between hydrogen adsorption and desorption on the catalyst surface. Herein, we report the rational balancing of hydrogen adsorption/desorption by orbital modulation using introduced environmental electronegative carbon/nitrogen (C/N) atoms. Theoretical calculations reveal that the empty d orbitals of iridium (Ir) sites can be reduced by interactions between the environmental electronegative C/N and Ir atoms. This balances the hydrogen adsorption/desorption around the Ir sites, accelerating the related HER process. Remarkably, by anchoring a small amount of Ir nanoparticles (7.16 wt%) in nitrogenated carbon matrixes, the resulting catalyst exhibits significantly enhanced HER performance. This includs the smallest reported overpotential at 10 mA cm^-2 (4.5 mV), the highest mass activity at 10 mV (1.12 A mg_Ir^-1) and turnover frequency at 25 mV (4.21 H₂ s^-1) by far, outperforming Ir nanoparticles and commercial Pt/C.

Abstract

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