{"title":"通过掺杂钼促进活性氧化镍的形成,实现高效氧气进化","authors":"Liuqing Wang, Jinsheng Li, Qinglei Meng, Meiling Xiao, Changpeng Liu, Wei Xing and Jianbing Zhu","doi":"10.1039/D4CY00314D","DOIUrl":null,"url":null,"abstract":"<p >The insufficient performance of non-noble metal catalysts in alkaline media is a prominent issue that limits the widespread adoption of electrocatalytic water splitting. In this study, we present an efficient Mo doping strategy to boost the electrocatalytic performance of NiFe layered double hydroxide (LDH) through modulating the electronic structure of active Ni sites. The optimized Mo doped NiFe-LDH (denoted as NiFeMo-2) exhibits significantly improved activity, showing a smaller overpotential of 262 mV at 10 mA cm<small><sup>−2</sup></small> compared to NiFe-LDH (344 mV). X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) spectra demonstrate that the incorporation of Mo not only increases the electron cloud density of Ni, but also induces more oxygen vacancies. Due to these structural modifications, the oxygen evolution reaction (OER) kinetics is dramatically enhanced, confirmed by <em>in situ</em> electrochemical impedance spectroscopy (EIS). Moreover, <em>in situ</em> Raman spectroscopy shows that the Mo doping can facilitate the formation of active NiOOH species at a lower potential, thus accelerating the OER kinetics. The <em>in situ</em> differential electrochemical mass spectrometry (DEMS) technique with <small><sup>18</sup></small>O isotope labelling, tetraalkylammonium cation (TMA<small><sup>+</sup></small>) chemical probe, and ethanol oxidation reaction suggest that the NiFeMo-LDH catalyst primarily follows the adsorbate evolution mechanism (AEM) pathway, the promoted dehydrogenation process with the modulation of *OH adsorption. This study reports a high-performance non-noble metal OER electrocatalyst and unveils the origins of metal doping to enhance the OER kinetics.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4000,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Facilitating active NiOOH formation via Mo doping towards high-efficiency oxygen evolution†\",\"authors\":\"Liuqing Wang, Jinsheng Li, Qinglei Meng, Meiling Xiao, Changpeng Liu, Wei Xing and Jianbing Zhu\",\"doi\":\"10.1039/D4CY00314D\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The insufficient performance of non-noble metal catalysts in alkaline media is a prominent issue that limits the widespread adoption of electrocatalytic water splitting. In this study, we present an efficient Mo doping strategy to boost the electrocatalytic performance of NiFe layered double hydroxide (LDH) through modulating the electronic structure of active Ni sites. The optimized Mo doped NiFe-LDH (denoted as NiFeMo-2) exhibits significantly improved activity, showing a smaller overpotential of 262 mV at 10 mA cm<small><sup>−2</sup></small> compared to NiFe-LDH (344 mV). X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) spectra demonstrate that the incorporation of Mo not only increases the electron cloud density of Ni, but also induces more oxygen vacancies. Due to these structural modifications, the oxygen evolution reaction (OER) kinetics is dramatically enhanced, confirmed by <em>in situ</em> electrochemical impedance spectroscopy (EIS). Moreover, <em>in situ</em> Raman spectroscopy shows that the Mo doping can facilitate the formation of active NiOOH species at a lower potential, thus accelerating the OER kinetics. The <em>in situ</em> differential electrochemical mass spectrometry (DEMS) technique with <small><sup>18</sup></small>O isotope labelling, tetraalkylammonium cation (TMA<small><sup>+</sup></small>) chemical probe, and ethanol oxidation reaction suggest that the NiFeMo-LDH catalyst primarily follows the adsorbate evolution mechanism (AEM) pathway, the promoted dehydrogenation process with the modulation of *OH adsorption. This study reports a high-performance non-noble metal OER electrocatalyst and unveils the origins of metal doping to enhance the OER kinetics.</p>\",\"PeriodicalId\":66,\"journal\":{\"name\":\"Catalysis Science & Technology\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.4000,\"publicationDate\":\"2024-06-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Catalysis Science & Technology\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/cy/d4cy00314d\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Catalysis Science & Technology","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/cy/d4cy00314d","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
非贵金属催化剂在碱性介质中的性能不足是限制电催化分水技术广泛应用的一个突出问题。在本研究中,我们提出了一种高效的钼掺杂策略,通过调节活性镍位点的电子结构来提高镍铁层双氢氧化物(LDH)的电催化性能。优化后的掺杂钼的镍铁层双氢氧化物(NiFe-LDH,代号为 NiFeMo-2)的活性得到了显著提高,与镍铁层双氢氧化物(NiFe-LDH,代号为 344 mV)相比,在 10 mA cm-2 的条件下,过电位仅为 262 mV。X 射线光电子能谱(XPS)和电子顺磁共振(EPR)光谱表明,掺入 Mo 不仅增加了镍的电子云密度,还诱导了更多的氧空位。原位电化学阻抗光谱(EIS)证实,由于这些结构改性,氧进化反应(OER)动力学显著增强。此外,原位拉曼光谱显示,钼掺杂能在较低电位下促进活性 NiOOH 物种的形成,从而加速了氧演化反应的动力学过程。利用 18O 同位素标记、四烷基铵阳离子(TMA+)化学探针和乙醇氧化反应进行的原位差分电化学质谱(DEMS)技术表明,NiFeMo-LDH 催化剂主要遵循吸附剂进化机制(AEM)途径,即在*OH 吸附调控下的促进脱氢过程。本研究报告了一种高性能非贵金属 OER 电催化剂,并揭示了金属掺杂增强 OER 动力学的起源。
Facilitating active NiOOH formation via Mo doping towards high-efficiency oxygen evolution†
The insufficient performance of non-noble metal catalysts in alkaline media is a prominent issue that limits the widespread adoption of electrocatalytic water splitting. In this study, we present an efficient Mo doping strategy to boost the electrocatalytic performance of NiFe layered double hydroxide (LDH) through modulating the electronic structure of active Ni sites. The optimized Mo doped NiFe-LDH (denoted as NiFeMo-2) exhibits significantly improved activity, showing a smaller overpotential of 262 mV at 10 mA cm−2 compared to NiFe-LDH (344 mV). X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) spectra demonstrate that the incorporation of Mo not only increases the electron cloud density of Ni, but also induces more oxygen vacancies. Due to these structural modifications, the oxygen evolution reaction (OER) kinetics is dramatically enhanced, confirmed by in situ electrochemical impedance spectroscopy (EIS). Moreover, in situ Raman spectroscopy shows that the Mo doping can facilitate the formation of active NiOOH species at a lower potential, thus accelerating the OER kinetics. The in situ differential electrochemical mass spectrometry (DEMS) technique with 18O isotope labelling, tetraalkylammonium cation (TMA+) chemical probe, and ethanol oxidation reaction suggest that the NiFeMo-LDH catalyst primarily follows the adsorbate evolution mechanism (AEM) pathway, the promoted dehydrogenation process with the modulation of *OH adsorption. This study reports a high-performance non-noble metal OER electrocatalyst and unveils the origins of metal doping to enhance the OER kinetics.
期刊介绍:
A multidisciplinary journal focusing on cutting edge research across all fundamental science and technological aspects of catalysis.
Editor-in-chief: Bert Weckhuysen
Impact factor: 5.0
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