Graphene-confined ultrafast radiant heating for high-loading subnanometer metal cluster catalysts

Ye-Chuang Han; Jun Yi; Beibei Pang; Ning Wang; Xu-Cheng Li; Tao Yao; Kostya S Novoselov; Zhong-Qun Tian

doi:10.1093/nsr/nwad081

Graphene-confined ultrafast radiant heating for high-loading subnanometer metal cluster catalysts

Natl Sci Rev. 2023 Mar 23;10(6):nwad081. doi: 10.1093/nsr/nwad081. eCollection 2023 Jun.

Authors

Ye-Chuang Han^{1

2}, Jun Yi^{1

2}, Beibei Pang³, Ning Wang⁴, Xu-Cheng Li^{1

2}, Tao Yao³, Kostya S Novoselov^{1

5}, Zhong-Qun Tian^{1

2}

Affiliations

¹ State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Graphene Industry and Engineering Research Institute, School of Electronic Science and Engineering, Xiamen University, Xiamen 361005, China.
² Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen 361005, China.
³ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China.
⁴ Faculty of Environment and Life, Beijing University of Technology, Beijing 100124, China.
⁵ Institute for Functional Intelligent Materials, National University of Singapore, Singapore 117544, Singapore.

Abstract

Thermally activated ultrafast diffusion, collision and combination of metal atoms comprise the fundamental processes of synthesizing burgeoning subnanometer metal clusters for diverse applications. However, so far, no method has allowed the kinetically controllable synthesis of subnanometer metal clusters without compromising metal loading. Herein, we have developed, for the first time, a graphene-confined ultrafast radiant heating (GCURH) method for the synthesis of high-loading metal cluster catalysts in microseconds, where the impermeable and flexible graphene acts as a diffusion-constrained nanoreactor for high-temperature reactions. Originating from graphene-mediated ultrafast and efficient laser-to-thermal conversion, the GCURH method is capable of providing a record-high heating and cooling rate of ∼10⁹°C/s and a peak temperature above 2000°C, and the diffusion of thermally activated atoms is spatially limited within the confinement of the graphene nanoreactor. As a result, due to the kinetics-dominant and diffusion-constrained condition provided by GCURH, subnanometer Co cluster catalysts with high metal loading up to 27.1 wt% have been synthesized by pyrolyzing a Co-based metal-organic framework (MOF) in microseconds, representing one of the highest size-loading combinations and the quickest rate for MOF pyrolysis in the reported literature. The obtained Co cluster catalyst not only exhibits an extraordinary activity similar to that of most modern multicomponent noble metal counterparts in the electrocatalytic oxygen evolution reaction, but is also highly convenient for catalyst recycling and refining due to its single metal component. Such a novel GCURH technique paves the way for the kinetically regulated, limited diffusion distance of thermally activated atoms, which in turn provides enormous opportunities for the development of sophisticated and environmentally sustainable metal cluster catalysts.

Keywords: graphene-confined; high-loading metal clusters; photothermal conversion; solid catalysts; ultrafast radiant heating.