功能材料：电解有机小分子制氢

Hydrogen economy is a promising replacement of current fossil fuel economy for its high efficiency and its clean cycle which may be accomplished with renewable energy. However, the production of hydrogen, especially by electrolysis of water, is hindered by the high energy consumption. This proposal employs electrolysis of small organic molecules to replace the electrolysis of water. Because of the significantly reduced overpotential and a much lower anodic oxidation potential, electrolysis of small organic molecules such as formic acid, methanol, and ethanol only requires 1/3~1/2 of voltage that electrolysis of water operates. In the electrooxidation of methanol and formic acid, our strategy is to modify the electronic structure of electrocatalyst by cheap materials, in order to enhance the OH adsorption and alleviate CO adsorption, hence, to improve the electrolysis efficiency. In electrooxidation of ethanol, we propose to focus on C-C activation by using Ru. Finally, we will use the knowledge obtained from fundamental research to guide design of catalyst and construction of electrolysis devices.

氢经济由于清洁和高效的优点，而且可利用可再生能源协助完成氢循环，有可能在将来取代目前的化石能源经济。但产氢，尤其是电分解水产氢，还存在着能耗过高的问题。本项目利用具有较低电势和过电位(即活化能垒)的有机小分子电催化分解过程取代需要较高氧化电势和过电位的水氧化过程，从而将电解制氢的运行电压降低到电解水所需电压的三分之一到一半的水平，极大的提高了电解制氢的电流效率，降低了过程能耗。在作为阳极反应的甲酸和甲醇氧化中，我们拟以廉价材料对催化剂的电子结构修饰，适当提高OH吸附强度同时降低CO吸附强度，以此增强bifunctional机制，从而增进反应效率。在乙醇氧化中，我们重点关注C-C活化以实现乙醇全氧化。具体的手段是利用Ru对乙醇的特殊吸附方式，辅以廉价过渡金属修饰，活化C-C键，并弱化CO的吸附。最终我们将用基础研究所得知识指导催化剂材料合成制备，设计并搭建电解有机小分子制氢的实用装置。

氢经济是一个有望取代现有化石能源体系的新能源体系，其真正的实施依赖于可再生能源驱动的可持续性氢气来源，以及替代现有化石能源体系所能提供的化工生产功能。在该项目资助下, 我们探索了廉价费贵金属析氢反应电催化剂；将无经济价值且高能耗的氧气电极半反应以可增值的有机物氧化反应取代，在产氢的同时实现了产品升值；我们设计了电化学有机物重整制氢途径，探索了其中相关反应的科学基础；我们设计从环境大量可得的小分子出发，生产目前由石油化工所提供的相关产品，弥补了氢经济原本不能提供化工产品的缺陷；我们开发了一系列锂金属电池材料，实现高效安全的储能。相关工作发表在9篇科技论文上，包括Nature Catalysis一篇（封面）、PNAS一篇、JACS一篇、Adv.Mater.一篇，申请中国专利8项，美国专利2项。