Driving selective photoelectrocatalytic oxidation of seawater to oxygen via regulating interfacial water structures on titanium oxides

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis Pub Date : 2025-05-01 DOI:10.1016/S1872-2067(24)60282-2

Qisen Jia , Yanan Wang , Yan Zhao , Zhenming Tian , Luyao Ren , Xuejing Cui , Guangbo Liu , Xin Chen , Wenzhen Li , Luhua Jiang

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引用次数: 0

Abstract

Photoelectrocatalytic (PEC) seawater splitting as a green and sustainable route to harvest hydrogen is attractive yet hampered by low activity of photoanodes and unexpected high selectivity to the corrosive and toxic chlorine. Especially, it is full of challenges to unveil the key factors influencing the selectivity of such complex PEC processes. Herein, by regulating the energy band and surface structure of the anatase TiO₂ nanotube array photoanode via nitrogen-doping, the seawater PEC oxidation shifts from Cl^– oxidation reaction (ClOR) dominant on the TiO₂ photoanode (61.6%) to oxygen evolution reaction (OER) dominant on the N-TiO₂ photoanode (62.9%). Comprehensive investigations including operando photoelectrochemical FTIR and DFT calculations unveil that the asymmetric hydrogen-bonding water at the N-TiO₂ electrode/electrolyte interface enriches under illumination, facilitating proton transfer and moderate adsorption strength of oxygen-intermediates, which lowers the energy barrier for the OER yet elevates the energy barrier for the ClOR, resulting to a promoted selectivity towards the OER. The work sheds light on the underlying mechanism of the PEC water oxidation processes, and highlights the crucial role of interfacial water on the PEC selectivity, which could be regulated by controlling the energy band and the surface structure of semiconductors.

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通过调节钛氧化物上的界面水结构驱动海水选择性光电催化氧化成氧

光电催化（PEC）海水分解作为一种绿色和可持续的氢气收集途径是有吸引力的，但受到光阳极活性低和对腐蚀性和有毒氯的高选择性的限制。特别是，要揭示影响这种复杂催化裂化过程选择性的关键因素充满了挑战。本文通过氮掺杂调节锐钛矿型TiO2纳米管阵列光阳极的能带和表面结构，使海水PEC氧化从以Cl -氧化反应（ClOR）为主的TiO2光阳极（61.6%）转变为以析氧反应（OER）为主的N-TiO2光阳极（62.9%）。包括operando光电化学FTIR和DFT计算在内的综合研究揭示了N-TiO2电极/电解质界面处的不对称氢键水在光照下富集，有利于质子转移和氧中间体的中等吸附强度，从而降低了OER的能垒，提高了ClOR的能垒，从而提高了OER的选择性。该研究揭示了PEC水氧化过程的潜在机制，并强调了界面水对PEC选择性的关键作用，这种选择性可以通过控制半导体的能量带和表面结构来调节。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chinese Journal of Catalysis 工程技术-工程：化工

CiteScore

25.80

自引率

10.30%

发文量

235

审稿时长

1.2 months

期刊介绍： The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.