基于钒-镍（铁）双金属氮（磷）化物催化析氢及有机物选择性氧化的双功能催化剂

The efficient coupling of hydrogen evolution reaction (HER) and organic selective oxidation reaction (OSOR) is an effective way to produce hydrogen from water splitting in company with to synthesize value-added chemicals, but the preparation of high-efficient HER and OSOR bifunctional catalysts is still a big challenge. Vanadium (V) is considered as an important catalytic material due to its abundant reserve, variable valence and good stability. The combination of vanadium with other transition metals and the tightly integrating of catalysts on the collector to accelerate the charge transfer can significantly improve their catalytic performance. Based on the above analyses, in this project, the vanadium will be combined with the transition metals (Ni, Fe) through an in-situ releasing strategy by using the transition metal ions (Ni, Fe) that slowly released from the current collectors (Ni or Fe foam). The V-Ni (Fe) bimetallic nitrides (phosphides) are obtained by controlling niridation (phosphorization) conditions. The combination of TEM, XPS etc. will be used to analyze the microstructure and interface interaction of the catalyst. The electrocatalytic performance for HER and OSOR will be tested by using linear sweep voltammetry etc. The combination of chromatography, mass spectrometry etc. will be used to analyze the conversion and selectivity of the organic reaction. A series of techniques will be performed to comprehend the relationship between the structure and electrochemical performance and to give some basic for designing high-efficient HER and OSOR bifunctional catalysts.

析氢反应（HER）和有机物选择性氧化反应（OSOR）的有效偶联是实现分解水制氢和增值化学品合成的有效途径，但制备高效的HER和OSOR双功能催化剂依然是挑战。钒具有储量丰富、价态多变及稳定性好等优点，是一类重要的催化材料。将钒与其它金属复合，同时使催化剂与集流体紧密结合以加速传荷过程，可以显著提升其催化性能。基于以上分析，本项目拟通过集流体（泡沫Ni、Fe）原位缓慢释放过渡金属离子（Ni、Fe）的策略使V与Ni、Fe后过渡金属结合，并通过控制氮（磷）化条件获得与基底紧密接触的钒-镍（铁）双金属氮（磷）化物。结合TEM、XPS等手段分析材料结构及界面作用。采用线性扫描伏安等方法研究材料对HER及OSOR的电催化性能，利用色谱及质谱等技术分析有机物反应转化率和选择性。结合多种方法揭示材料结构与催化活性之间的关系，为设计高效HER及OSOR双功能催化剂提供数据支持。

析氢反应（HER）和有机物选择性氧化反应（OSOR）的有效偶联是实现分解水制氢和增值化学品合成的有效途径，但制备高效的HER和OSOR双功能催化剂依然是挑战。本项目基于钒储量丰富、价态多变及稳定性好等众多优点，提出利用集流体（泡沫Ni、Fe）原位缓慢释放过渡金属离子（Ni、Fe）使V与Ni、Fe后过渡金属结合，控制氮（磷）化条件获得与基底紧密接触的钒-镍（铁）双金属氮（磷）化物。我们通过调控集流体种类、溶液酸度、钒源与释放的后过渡金属的比例等，获得了一系列与基底紧密接触的钒-镍（铁）双金属氮（磷）化物，并进行了HER和OSOR性能的测试，我们发现调控协同前后过渡金属的电子结构，构建异质界面有利于提高催化反应活性。此外，结合多种方法揭示了材料结构与催化活性之间的关系，为设计高效HER及OSOR双功能催化剂提供了数据支持。在项目支持下，在Angew. Chem. In. Ed.，Adv. Mater.，J. Mater. Chem. A，Nano Res.等国内外重要学术杂志发表SCI论文19篇，论文被引用600余次，2篇论文入选ESI高被引论文，申请发明专利5项，培养硕士4人。