石墨烯光电催化制氢超分子复合体系的构筑

The effective and mass conversion from solar energy to hydrogen energy is one of the most important pathways and feasible approaches to release the energy crisis for the sustainable development of human economy and society. Nowadays, the solar energy conversion techniques for photo/electrochemical hydrogen evolution are always being limited by the high price of noble metal catalysts and their combination with practical photosensitizers, therefore, the key point in solving this problem is to realize a low cost and high efficiency hydrogen generation system driven by visible light or electricity. This proposal intends to design and construct supramolecular graphene composites for photo/electrochemical hydrogen evolution via the introduction of ammonium cations, benzenesulfonic anions, water-soluble Jeffamine® M polymers, as well as phosphine ligand and mercapto group, developing a series of utilization methods for the chemical modification of graphene. Through chemical modification, physical adsorption and intermolecular assembly, we would make supramolecular graphene composites with diverse function units such as hydrogenase, quantum dots, base metal Fe/Co/Ni/Cu complexes, organic dyes and so on, fabricate graphenic electrodes and prototype device, and improve the efficiency for hydrogen evolution by the adjustment of energy level matching between catalysts and photosensitizers. Our main goal is to create a type of novel, reproducible, inexpensive and practicable techniques in the field of photo/electrochemical hydrogen production.

实现太阳能向氢能的大规模有效转化，是从根本上解决人类经济和社会可持续发展核心能源问题的重要可行方案之一。现有太阳能光电催化制氢技术一直受到贵金属产氢催化剂经济性差、催化剂与光敏材料体系整合难度高的制约，因此，进一步研发廉价、高效的光(电)驱产氢体系是解决实用化问题的关键。本项目拟构筑石墨烯光电催化产氢超分子复合体系。将铵基正离子、苯磺酸基负离子、水溶性高分子中性链段、膦配体及巯基等各种基团引入石墨烯，拓展一系列高效、实用的石墨烯化学修饰方法。通过化学修饰、物理吸附、分子组装等多种手段在石墨烯上引入氢化酶、量子点、铁/钴/镍/铜等廉价金属配合物催化剂、小分子光敏染料等功能化单元，发展新型石墨烯超分子复合体系和电极的制备方法，构筑原型器件，并通过各种官能团结构调节催化单元与敏化单元之间的能带匹配程度，提高效率，开创一类重复性好、低成本、且具有一定实用价值的光电催化制氢技术。

针对太阳能光电催化制氢技术一直受到贵金属产氢催化剂经济性差、催化剂与光敏材料体系整合难度高的制约，本项目借助石墨烯优异的电子传输、延迟、中继性能，构筑了多个石墨烯光电催化产氢超分子复合体系。利用环氧氨解反应，我们拓展了一类简单、高效、实用的石墨烯“湿化学”修饰方法，能够将铵基正离子、苯磺酸基负离子、聚醚胺Jeffamine® M高分子中性链段、寡肽序列等各种基团引入石墨烯表面，得到具有良好溶液制程特性的石墨烯材料，能够分别采用旋涂-干燥-高温烧结或层层组装方式得到石墨烯复合电极。通过化学修饰、物理吸附、分子组装等多种手段，我们在石墨烯上引入了量子点、镍/钴/铁/锰等廉价金属配合物催化剂、小分子光敏染料等功能化单元，发展了石墨烯超分子复合体系的制备方法，组合构筑了可光电催化制氢的原型器件，通过调节官能团结构调节单元能带，优化了催化单元与敏化单元之间的能带匹配，提高了原型器件的光电催化制氢效率，开创了一类重复性好、低成本、且具有一定实用价值的光电催化制氢技术。