石墨烯基复合制氢催化剂的设计、制备、与光催化剂组装及其协同效应

Conversion of solar energy into chemical fuel hydrogen by photocatalytic water splitting is an ideal way to solve the energy crisis. Exploring low-cost, resource-rich hydrogen evolution reaction (HER) catalysts to replace precious metal Pt, and assembling them synergistically with photocatalysts are important scientific issues to be solved before the application of the photocatalytica hydrogen evolution. This project will chemically couple graphene with HER-catalyst active ingredients (transition metals and their complexes, WS2, graphitic C3N4) to produce synergistic effects and to prepare efficient HER composite catalysts. Graphene as a wire is used to link a HER catalyst with a photocatalyst to assemble synergistically the both by designing suitable nanostructures, which promotes charge transfer between the both and improves the diffusion and reaction of reactant species at the surface of the composite photocatalyst, greatly enhancing the activity and stability of the composite photocatalyst for hydrogen production. My group has carried out the following research works: chemically coupling graphene with metal nickel to prepare the HER catalyst with synergistic effect, simultaneously assembling MoS2 and CdS on graphene for synergistic photocatalytic hydrogen evolution, and the photocatalytic hydrogen production with graphitic C3N4 as a photocatalyst and so on. These preliminary works have laid a good foundation to carry out this project. To conducte this project is of positive significance to solve energy shortage, and also contributes to deepening the theoretical understanding for design, preparation and assembly of efficient photocatalysts.

通过光催化分解水将太阳能转化为化学燃料氢是解决能源危机的理想途径。探索廉价、资源丰富的放氢催化剂（HER催化剂）替代贵金属Pt，并与光催化剂进行协同组装是光催化制氢要解决的重要科学问题。本项目拟用石墨烯和HER催化剂活性成分(过渡金属及配合物、WS2、石墨状C3N4)进行化学耦合，产生协同效应，制备高效的HER复合催化剂。用石墨烯作为“导线”，设计合适的纳米结构，将HER催化剂与光催化剂连接起来，实现协同性组装，促进两者之间的电荷转移和反应物种在催化剂表面的扩散与反应，大大提高复合光催化剂的制氢活性和稳定性。本课题组已开展了石墨烯与金属镍化学耦合制备具有协同效应的HER催化剂，将MoS2与CdS同时组装到石墨烯上产生协同的光催化制氢，以及石墨状C3N4光催化制氢等前期工作，为本项目奠定了基础。开展本项目研究对解决能源问题具有积极意义，也有助于深化对高效光催化剂设计、制备和组装的理论认识。

通过光催化分解水将太阳能转化为燃料氢，是解决能源短缺和环境污染最理想的途径。本项目开展了石墨烯基复合制氢催化剂的设计、制备、与光催化剂的组装及其协同效应研究。研究内容包括:1）将石墨烯和过渡金属(Fe, Co和Ni) 及化合物复合,以及过渡金属硼化物表面修饰过渡金属簇或表面氧化物/氢氧化物，设计制备高性能的HER（析氢反应）复合催化剂；阐明石墨烯基复合催化剂的形成机理和双组分产生HER协同效应的构效关系。2）在此基础上，将复合HER催化剂与光催化剂协同组装，构建高效光催化制氢反应体系；阐明了光生电荷在光催化剂和HER复合催化剂之间转移的规律及界面催化反应机理，为开发新的高效光催化制氢催化剂提供理论基础。3）基于半导体光催化剂导电各向异性，开展了定向异质结光催化剂的设计与组装研究，首次提出各向异性异质结的新慨念，制备了高效半导体光催化剂，为开发高效异质结半导体光催化剂提供了新的思路。.本项目研究成果在Appl. Catal. B: Environ., J. Mater. Chem. A, Chem. Eng. J., ACS Appl. Mater. Interfaces等高水平期刊上发表学术论文14篇，其中9篇发论文为中科院SCI分类一区；取得系列学术研究成果，特别是提出双组分协同HER催化剂设计的新思路、石墨烯复合HER催化剂材料设计与制备新方法、以及基于半导体光催化剂导电性各向异性提出的各向异性异质结新概念等，推动光催化和电催化分解水研究，受到了学术界的关注，已被引用251次（web of Science），2篇论文为ESI高被论文。发明了石墨烯及石墨烯基金属纳米结构复合物的新制备方法，获得3件国家发明专利，所采用的方法和制备的材料具有应用价值。获得1项江西省自然科学奖二等奖。