溶剂热助乙二醇还原法制备Pt/C催化剂过程中酸碱配位机制及工艺参数优化

doi:10.1016/S1872-2067(19)63456-X

催化学报 ›› 2020, Vol. 41 ›› Issue (5): 820-829.DOI: 10.1016/S1872-2067(19)63456-X

溶剂热助乙二醇还原法制备Pt/C催化剂过程中酸碱配位机制及工艺参数优化

曾融蓉^a, 王昆^a, 邵伟^b, 赖俊杭^a, 宋树芹^a, 王毅^a

a 中山大学, 材料科学与工程学院, 化学工程与技术学院, 化学学院, 广东省低碳化学与过程节能重点实验室, 广东广州 510275, 中国;
b 滑铁卢大学化学工程系, 滑铁卢, 加拿大

收稿日期:2019-11-20 修回日期:2019-12-18 出版日期:2020-05-18 发布日期:2019-12-31
通讯作者: 宋树芹, 王毅
基金资助:
国家自然科学基金（21576300，21576299，21978331，21975292，21905311）；国家重点研发计划（2016YFB0101204）；广东省高层次人才特殊支持计划项目（2016TQ03N322）；高校基本科研业务费青年教师重点培育项目（17lgzd14，19lgpy136，19lgpy116）；中国博士后科学基金（2019M653142）.

Investigation on the coordination mechanism of Pt-containing species and qualification of the alkaline content during Pt/C preparation via a solvothermal polyol method

Rongrong Zeng^a, Kun Wang^a, Wei Shao^b, Junhang Lai^a, Shuqin Song^a, Yi Wang^a

a The Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province, School of Materials Science and Engineering, School of Chemical Engineering and Technology, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, Guangdong, China;
b Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1, Canada

Received:2019-11-20 Revised:2019-12-18 Online:2020-05-18 Published:2019-12-31
Contact: S1872-2067(19)63456-X
Supported by:
The work was supported by the National Natural Science Foundation of China (21576300, 21576299, 21978331, 21975292, 21905311), the National Key Research and Development Program of China (2016YFB0101200), the Guangzhou Science and Technology Project (201707010079), the Fundamental Research Funds for Central Universities (17lgzd14, 19lgpy136, and 19lgpy116), and the Tip-top Scientific and Technical Innovative Youth Talents of Guangdong special support program (2016TQ03N322) and the China Postdoctoral Science Foundation (2019M653142).

摘要/Abstract

摘要： 质子交换膜燃料电池（PEMFCs）能量转换率高，反应产物仅为H₂O、不造成污染，是一种极具发展前景的能源转换装置.然而，PEMFCs的阴极氧还原反应（ORR）动力学缓慢、过电位高.由于Pt对ORR中间产物脱吸附能适中，因此，Pt/C成为电催化ORR的商业化催化剂，对其制备技术的研究成为该领域的研究热点.乙二醇（EG）还原法制备碳载Pt基催化剂是一种常见方法，EG作为还原剂的同时，还起到保护剂和分散剂的作用，使制备的催化剂具有均一性.
EG在外界能量的活化下，分解生成H₂O和CH₃CHO，CH₃CHO作为还原剂将H₂PtCl₆还原生成Pt单质颗粒，同时生成的CH₃COO^-由于静电排斥可以防止Pt粒子团聚.常见的外界能量的活化方法有脉冲微波法、回流法、溶剂热法等，其中溶剂热法采用高压釜作为反应容器，抗干扰能力强，工艺操作简单、反应快速、耗能较少、成本低廉，极易于实现工业化生产；值得注意的是，无论使用何种方法对Pt前驱体混合液给予活化能使其发生还原，其碱的含量都会对最终所得催化剂的电催化ORR活性有着显著的影响，因此，通过跟踪前驱体混合液中含Pt物种的变化路径，揭示催化剂制备过程中的碱调控机理，实现加入碱的定量化，对于大规模制备高效Pt/C催化剂具有重要的意义.
因此，本文采用溶剂热助EG还原法合成Pt/C催化剂的技术，创新联用UV-vis和H⁺浓度探针技术，揭示了前驱体混合液中含Pt物种的配位过程，实现了加入碱的定量化.发现当m（NaOH）：m（Pt）达到2：1时，Pt配位完成；进而通过优化反应温度、反应时间等参数，成功制备了高效Pt/C催化剂：当反应温度为140℃，反应时间为2h时，所得催化剂在酸性条件下，相对于商业化Pt/C具有更高的电催化ORR活性，其起始ORR还原电位达到0.95V（商业化Pt/C为0.90V），半波电位为0.82V（商业化Pt/C为0.75V），该工作对于工业化大批量生产高效Pt/C催化剂具有重要的意义.

关键词: Pt/C, 氧还原反应, 溶剂热助乙二醇还原法, 电催化活性

Abstract: A solvothermal assisted ethylene glycol reduction method is a common technology for Pt/C catalysts preparation. Here, the coordination mechanism of the Pt-containing species is deeply studied by innovatively adopting the ultraviolet-visible spectroscopy technology and H⁺ concentration detector. Moreover, the amount of NaOH that effectively coordinates Pt⁴⁺ has been tentatively qualified and the heating parameters during the preparation process of Pt/C have also been optimized. As investigated, the optimized 20-(1/22)-140-2 Pt/C (20 wt%Pt; m(Pt):m(NaOH)=1/22; heating temperature:140℃, heating time:2 h) exhibits higher electrocatalytic activity towards oxygen reduction reaction (ORR) than the commercial 20 wt% Pt/C (E-TEK) in acidic media. This work provides a theoretical reserve and technical accumulation for industrialized mass production of highly efficient Pt/C catalysts for ORR in proton exchange membrane fuel cells.

Key words: Pt/C, Oxygen reduction reaction, Solvothermal assisted ethylene glycol reduction method, Electrocatalytic activity

曾融蓉, 王昆, 邵伟, 赖俊杭, 宋树芹, 王毅. 溶剂热助乙二醇还原法制备Pt/C催化剂过程中酸碱配位机制及工艺参数优化[J]. 催化学报, 2020, 41(5): 820-829.

Rongrong Zeng, Kun Wang, Wei Shao, Junhang Lai, Shuqin Song, Yi Wang. Investigation on the coordination mechanism of Pt-containing species and qualification of the alkaline content during Pt/C preparation via a solvothermal polyol method[J]. Chinese Journal of Catalysis, 2020, 41(5): 820-829.

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溶剂热助乙二醇还原法制备Pt/C催化剂过程中酸碱配位机制及工艺参数优化

Investigation on the coordination mechanism of Pt-containing species and qualification of the alkaline content during Pt/C preparation via a solvothermal polyol method

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