TY - JOUR
T1 - Control of Chemical Reaction Pathways by Light-Matter Coupling
AU - Devasia, Dinumol
AU - Das, Ankita
AU - Mohan, Varun
AU - Jain, Prashant K.
PY - 2021/4/20
Y1 - 2021/4/20
N2 - Because plasmonic metal nanostructures combine strong light absorption with catalytically active surfaces, they have become platforms for the light-assisted catalysis of chemical reactions. The enhancement of reaction rates by plasmonic excitation has been extensively discussed. This review focuses on a less discussed aspect: the induction of new reaction pathways by light excitation. Through commentary on seminal reports, we describe the principles behind the optical modulation of chemical reactivity and selectivity on plasmonic metal nanostructures. Central to these phenomena are excited charge carriers generated by plasmonic excitation, which modify the energy landscape available to surface reactive species and unlock pathways not conventionally available in thermal catalysis. Photogenerated carriers can trigger bond dissociation or desorption in an adsorbate-selective manner, drive charge transfer and multielectron redox reactions, and generate radical intermediates. Through one or more of these mechanisms, a specific pathway becomes favored under light. By improved control over these mechanisms, light-assisted catalysis can be transformational for chemical synthesis and energy conversion.
AB - Because plasmonic metal nanostructures combine strong light absorption with catalytically active surfaces, they have become platforms for the light-assisted catalysis of chemical reactions. The enhancement of reaction rates by plasmonic excitation has been extensively discussed. This review focuses on a less discussed aspect: the induction of new reaction pathways by light excitation. Through commentary on seminal reports, we describe the principles behind the optical modulation of chemical reactivity and selectivity on plasmonic metal nanostructures. Central to these phenomena are excited charge carriers generated by plasmonic excitation, which modify the energy landscape available to surface reactive species and unlock pathways not conventionally available in thermal catalysis. Photogenerated carriers can trigger bond dissociation or desorption in an adsorbate-selective manner, drive charge transfer and multielectron redox reactions, and generate radical intermediates. Through one or more of these mechanisms, a specific pathway becomes favored under light. By improved control over these mechanisms, light-assisted catalysis can be transformational for chemical synthesis and energy conversion.
UR - http://www.scopus.com/inward/record.url?scp=85104503582&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85104503582&partnerID=8YFLogxK
U2 - 10.1146/annurev-physchem-090519-045502
DO - 10.1146/annurev-physchem-090519-045502
M3 - Review article
C2 - 33481640
SN - 0066-426X
VL - 72
SP - 423
EP - 443
JO - Annual Review of Physical Chemistry
JF - Annual Review of Physical Chemistry
ER -