Ang, Z. Z., Pereira, V., Ng, L. S., Chong, C., Li, H., Yu, H., & Lee, H. K. (2025). Photothermal–Plasmonic Catalysis at Liquid–Liquid Interfaces: Enhancing and Steering Biphasic Reactions with Light. ACS Catalysis, 15(15), 13458–13469. https://doi.org/10.1021/acscatal.5c04540
Abstract:
Phase-boundary catalysis strategically positions heterogeneous nanocatalysts at immiscible liquid–liquid interfaces to facilitate reactions between reactants with polarity disparity. However, current designs are limited by low catalytic activity, poor interfacial stability, difficulty in heating without disrupting the catalyst layer, and hydrolytic degradation of reactive intermediates in water. Herein, we achieve efficient phase-boundary catalysis by employing nanoporous gold bowls (NPGBs) with strong plasmonic and photothermal properties to control and enhance interfacial reactions using light. Our strategy integrates two key concepts: (1) NPGBs act as photothermal nanoheaters, localizing heat at the liquid–liquid interface to drive reactions while preserving the stability of the interfacial layer; (2) they also function as plasmonic catalysts, generating hot carriers to accelerate reactions and direct chemical pathways. Using the reduction of 4-nitroaniline by NaBH4 as a model, this approach achieves ∼36-fold increase in reactant consumption and reaching up to 92% conversion to para-phenylenediamine under optimal conditions. Mechanistic investigations show that 90% of the catalytic enhancement arises from plasmonic and photothermal effects, with hot electrons enriching active surface hydride species by suppressing undesired hydrolysis to H2. This work underscores the immense potential of photothermal–plasmonic catalysis to advance and manipulate multiphasic reactions using light for diverse chemical, environmental, and energy applications.
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Funding Info:
This research / project is supported by the Agency for Science, Technology and Research - Manufacturing, Trade, and Connectivity Individual Research Grant
Grant Reference no. : MTC IRG M23M6c0098
This research / project is supported by the Agency for Science, Technology and Research - Advanced Manufacturing and Engineering (AME) Young Individual Research Grant
Grant Reference no. : AME YIRG A2084c0158
This research / project is supported by the Ministry of Education, Singapore - Academic Research Fund Tier 1
Grant Reference no. : AcRF Tier1 RS13/20
This research / project is supported by the Ministry of Education, Singapore - Academic Research Fund Tier 1
Grant Reference no. : AcRF Tier1 RG4/21
This research / project is supported by the National University of Singapore - Center of Hydrogen Innovation
Grant Reference no. : CHI-P2022-05