Dynamic Control of Photocatalytic Proton Reduction through the Mechanical Actuation of a Hydrogel Host Matrix

Yang, Muwen; Xiong, Qinsi; Kodaimati, Mohamad S.; Jiang, Xinyi; Schweitzer, Neil M.; Schatz, George C.; Weiss, Emily A.

doi:10.1021/acs.jpclett.1c03713

Title: Dynamic Control of Photocatalytic Proton Reduction through the Mechanical Actuation of a Hydrogel Host Matrix

Journal Article · 15 December 2021 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.1c03713 · OSTI ID:1865127

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^[2]; Kodaimati, Mohamad S. ^[2]; Jiang, Xinyi ^[2];

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^[2]

Northwestern Univ., Evanston, IL (United States); Northwestern University
Northwestern Univ., Evanston, IL (United States)

This paper describes a photocatalytic hydrogen evolution system that is dynamically and reversibly responsive to the pH of the surrounding solution through actuation of a micro-hydrogel (microgel) matrix that hosts the photocatalysts (CdSe/CdS nanorods). Here, the reversible actuation occurs within 0.7 s (swelling) and 1.7 s (contraction). A ΔpH of 0.01 relative to the pK_a of the tertiary amine on the microgel polymer (7.27) results in a reversible change in the average diameter of the microgel hosts by a factor of 2.5 and a change in the photocatalytic turnover frequency (TOF) by a factor of five. Kinetic isotope effect and photoluminescence quenching experiments reveal that the scavenging of the photoexcited hole by sulfite ions is the rate-limiting step and leads to the observed response of the TOF to pH through actuation of the microgel. Molecular dynamics simulations quantify a greater local concentration of sulfite hole scavengers for pH < pK_a.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-03ER15457; SC0000989

OSTI ID:: 1865127

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 50 Vol. 12; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Reaction mechanisms
Photocatalysis
Ions
Gels
Composites
actuation
composites
gels
ions
microgel
molecular dynamics
photocatalysis
reaction mechanisms
self-regulation

Title: Dynamic Control of Photocatalytic Proton Reduction through the Mechanical Actuation of a Hydrogel Host Matrix

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