氢循环与氢经济：廉价金属催化材料设计的催化理论基础

Industrially important hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) exhibit low reaction kinetics in basic environment. In acidic environment, hydrogen binding energy (HBE) is the only descriptor for the reactivity of HOR/HER. However, the key intermediate, adsorbed hydrogen (Had), seems not correlated to pH value. The explanation for this phenomenon is current under debate. This is no theory that can explain all the experimental observations. To widely adopt hydrogen economy, it is crucial to unambiguously find out the origin of the low activity of HOR/HER in base. Our hypothesis is that: in basic environment, HBE is not the key for activity; it is therefore possible to reduce the reaction barrier by controlling the configuration of water molecule or by introduction of hydroxyl group (OH) directed reaction pathway. We propose to employ strain to tune the adsorption properties, to use electrochemistry-spectrometry-quartz microbalance to precisely measure the adsorbed intermediates. The proposed research offers the insight for the key factors that influence HOR/HER in base. Based on the obtained knowledge, we would be able to design high-performance HOR/HER catalysts, providing the fundament of catalysis for solar-to-hydrogen conversion.

具有重要工业意义的氢氧化/氢生成（HOR/HER）在碱性体系下反应速率低下。酸性条件下，氢催化剂只需要一个指标即可解释其反应活性并可以此优化催化剂，即氢吸附能。然而关键的中间体——Had却与pH值并没有关系。这如何解释，成为了电化学界的争端焦点。目前没有任何理论能够支持所有的实验现象。明确无误的找出令催化过程变慢的因素并合理解决对应问题对于氢经济至关重要。我们的理论是：在碱性环境中，催化剂对氢的结合能并不重要；碱性环境下可由控制水分子构型或引入由氢氧基团（OH）主导的反应途径来达到降低反应能垒从而实现高pH值下的催化剂优化。我们提出以材料应力（strain）控制物质吸附、以电化学方法-光谱技术-石英微天平联用准确量化吸附物，从而深入探索影响氢反应在碱液中进行的真实因素，并以基础研究结果为指导，设计高效氢催化剂，为利用太阳能制氢提供催化剂基础。

具有重要工业意义的氢氧化/氢生成（HOR/HER）在碱性体系下反应速率低下。酸性条件下，氢催化剂只需要一个指标即可解释其反应活性并可以此优化催化剂，即氢吸附能。然而关键的中间体——Had却与pH值并没有关系。这如何解释，成为了电化学界的争端焦点。目前没有任何理论能够支持所有的实验现象。我们发现，碱性环境下可由控制水分子构型或引入由氢氧基团（OH）主导的反应途径来达到降低反应能垒从而实现高pH值下的催化剂优化。并以基础研究结果为指导，设计高效氢催化剂，为电解水制氢提供催化剂基础。在该项目支持下，我们发表科技论文25篇，其中包括Nature Catalysis一篇（封面）、PNAS一篇、JACS一篇、Adv.Mater.一篇，Nano Lett.三篇。申请中国专利8项，美国专利2项。