负载贵金属的超薄硫化锌纳米片催化剂的合成与研究

The construction of CO-PROX catalysts with high selectivity, high conversion, and long lifetime in the low-temperature hydrogen-rich atmosphere to reduce the cost of hydrogen purification is a major challenge. This project is devoted to the development of a new kind of noble metal-metal sulfide nanosheet composite catalyst, and to the study of its catalytic performance and reaction mechanism in CO-PROX reaction. Based on the previous research results of the applicant's research group, ZnS Nano-sheets were selected as catalyst carriers, and their advantages such as large specific surface area and fast charge transfer speed were fully utilized to provide load anchors for precious metals Pt and Au. Through different precious metal loading methods and different loadings, the size, valence state and electronic structure of noble metal nanoclusters are regulated, the controllable preparation of noble metal-support interface on the sub-nanometer/atomic level is realized. By investigating the catalytic performance of the composite catalyst in the CO-PROX reaction, the elementary reaction step is established to reveal the influence of the interaction between the noble metal and the noble metal-support on the catalytic performance, which provided a new idea for the development of high performance and high stability hydrogen purification catalyst.

构建具有高选择性、高转化率、长寿命的低温富氢气氛CO优先氧化（CO-PROX）催化剂从而降低氢气提纯成本是一项重大挑战。本项目致力于开发一类全新的贵金属-金属硫化物纳米片复合催化剂，研究其在CO-PROX反应中的催化性能与反应机理。结合申请人课题组前期的研究结果，选择ZnS纳米片作为催化剂载体，发挥其比表面积大、电荷转移速度快等优点，为贵金属Pt、Au提供负载锚点。通过不同贵金属负载方法、负载量，对贵金属纳米团簇的尺寸、价态和电子结构等进行调控，实现对贵金属-载体界面亚纳米/原子级别的可控制备。通过考察复合催化剂在CO-PROX反应中的催化性能，建立基元反应步骤，揭示贵金属、贵金属-载体间相互作用对催化性能的影响，为开发设计高性能高稳定性的氢气提纯催化剂提供新思路。

构建具有高选择性、高转化率、长寿命的催化剂始终是一项充满挑战的课题，具有高催化活性的反应位点往往因为自身能量过高而难以稳定存在，影响催化剂的稳定性。本课题通过热蒸发气相合成技术，开发了一类全新的贵金属-金属硫化物纳米片复合催化剂，选择ZnS纳米片作为催化剂载体，发挥其比表面积大、电荷转移速度快等优点，为贵金属提供负载锚点。通过不同贵金属负载方法、负载量，对贵金属纳米团簇的尺寸、价态和电子结构等进行调控，实现了贵金属-载体界面亚纳米/原子级别的可控制备；通过对催化反应条件及机理的研究，发现催化剂表面氧数量大幅度增加导致表面活性Pd物种以Pd4+为主；在前期工作结果的指导下进行拓展，利用搅拌摩擦焊制备技术在铁基底上诱导生成高能的Cu(100)和(110)表面，将Fe刻蚀后得到的自支撑Cu催化电极具有优异的酸性HER性能。