Enhanced localized electron density from PdCu nanoparticle loading on a defective TiO2 support for selective nitrate electroreduction to ammonia

Haoran Wu; Heng Guo; Fengying Zhang; Peng Yang; Jiaxin Liu; Yuantao Yang; Zhen-Feng Huang; Chenyuan Zhu; Weitao Wang; Xin Tu; Guidong Yang; Ying Zhou

doi:10.1039/D3TA04155G

Enhanced localized electron density from PdCu nanoparticle loading on a defective TiO₂ support for selective nitrate electroreduction to ammonia†

Haoran Wu,^a Heng Guo,

*^ab Fengying Zhang,^ab Peng Yang,^a Jiaxin Liu,^a Yuantao Yang,^a Zhen-Feng Huang,

^c Chenyuan Zhu,^d Weitao Wang,^d Xin Tu,*^d Guidong Yang

^e and Ying Zhou

*^ab

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* Corresponding authors

^a State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, China
E-mail: heng.guo@swpu.edu.cn, yzhou@swpu.edu.cn

^b School of New Energy and Materials, Southwest Petroleum University, Chengdu, China

^c Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Centre of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

^d Department of Electrical Engineering and Electronics, University of Liverpool, Liverpool L69 3GJ, UK
E-mail: xin.tu@liv.ac.uk

^e XJTU-Oxford Joint International Research Laboratory of Catalysis, School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, China

Abstract

The electrocatalytic nitrate (NO₃⁻) reduction reaction (NITRR) to synthesize ammonia (NH₃) offers a promising method for both pollution abatement and chemical production. However, the sluggish multi-electron/proton-involved steps limit ammonia selectivity and yield. Herein, we loaded PdCu nanoparticles (PdCu NPs) onto defective TiO₂ to regulate the localized electron density for selective NH₃ synthesis. Our results show a significant increase in NH₃ yield and selectivity (112.0 to 322.7 μmol cm⁻² h⁻¹ and 34.6 to 80.1%, respectively), induced by the introduction of PdCu NPs. Importantly, in situ and operando investigations combined with density functional theory (DFT) calculations reveal that PdCu NPs enhance the localized electron density at oxygen vacancies. This regulated electron density suppresses N–N coupling and accelerates N–H bonding processes, thus modulating NH₃ selectivity. This unique insight based on localized electron density control provides a rational design strategy for metal-defect support catalysts in ammonia production using electrochemical processes.

Journal of Materials Chemistry A

Enhanced localized electron density from PdCu nanoparticle loading on a defective TiO₂ support for selective nitrate electroreduction to ammonia†

Abstract

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Enhanced localized electron density from PdCu nanoparticle loading on a defective TiO₂ support for selective nitrate electroreduction to ammonia

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Journal of Materials Chemistry A