Material design for converting an oxidative-type BiVO4 catalyst into a reductive BiV(S,O)4−x sulfo-oxide catalyst for nitrogen photoreduction to ammonia

Xiaoyun Chen; Pengkun Zhang; Dong-Hau Kuo; Qinhan Wu; Adugna Boke Abdeta; Binghong Wu; Zhengjie Su; Longyan Chen; Osman Ahmed Zelekew; Jinguo Lin

doi:10.1039/D3TA04428A

Material design for converting an oxidative-type BiVO₄ catalyst into a reductive BiV(S,O)_4−x sulfo-oxide catalyst for nitrogen photoreduction to ammonia†

Xiaoyun Chen,

*^a Pengkun Zhang,^a Dong-Hau Kuo,

*^b Qinhan Wu,^a Adugna Boke Abdeta,

^a Binghong Wu,^a Zhengjie Su,^a Longyan Chen,^a Osman Ahmed Zelekew

^c and Jinguo Lin*^a

Author affiliations

* Corresponding authors

^a College of Materials Engineering, Fujian Agriculture and Forestry University, Fuzhou 350002, China
E-mail: fjlinjg@126.com, fjchenxy@126.com

^b Department of Materials Science and Engineering, Graduate Institute of Energy and Sustainability Technology, National Taiwan University of Science and Technology, Taipei 10607, Taiwan
E-mail: dhkuo@mail.ntust.edu.tw

^c Department of Materials Science and Engineering, Adama Science and Technology University, Adama, Ethiopia

Abstract

Herein, we demonstrated S²⁻ anion incorporation into BiVO₄ for converting an oxidative-type BiVO₄ photocatalyst into a reductive-type BiV(S,O)_4−x (labeled BiVOS) sulfo-oxide photocatalyst for efficient N₂ fixation under an ambient environment. BiVOS-2 not only exhibited the highest NH₃ production rate of 563.6 μmol g⁻¹ h⁻¹ without sacrificial agents and with durable stability but also had an apparent quantum efficiency (AQE) of 2.18% at 420 nm and a solar-to-ammonia (STA) conversion efficiency of 0.071% in pure water under AM1.5G light irradiation. At the same time, the sulfur-free BiVO₄ can't realize N₂ to NH₃ conversion. The S²⁻ doping introduced Vo, which converted V⁵⁺ around Vo into V⁴⁺ to keep the electrical neutrality. The active atoms V⁴⁺ were exposed and activated N₂, and the electron hopping between V⁵⁺ and V⁴⁺ improved electron transfer. Density functional theory (DFT) calculation indicates that S²⁻ anion doping can enhance adsorption energy, elongate the N [triple bond, length as m-dash] N bond of the adsorbed N₂ molecule, and facilitate electron transfer to the antibonding orbital of the N₂ molecule, leading the BiVOS sulfo-oxide catalyst to have excellent N₂ fixation activity. This study provides a promising method for converting an oxidative-type catalyst into a reductive catalyst to extend material applications.

Journal of Materials Chemistry A

Material design for converting an oxidative-type BiVO₄ catalyst into a reductive BiV(S,O)_4−x sulfo-oxide catalyst for nitrogen photoreduction to ammonia†

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Material design for converting an oxidative-type BiVO₄ catalyst into a reductive BiV(S,O)_4−x sulfo-oxide catalyst for nitrogen photoreduction to ammonia

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Journal of Materials Chemistry A