Ni/TiO ₂ Interfaces Enhance Benzaldehyde Selectivity in the Photocatalytic Dehydrogenation of Benzyl Alcohol
6 affiliations
- 1Department of Chemical and Environmental Engineering
- 2Yale University
- 3Energy Sciences Institute
- 4Department of Chemistry
- 5Princeton University
- 6Lam Research Corporation
Abstract
The selective conversion of alcohols to carbonyls (ketones and aldehydes) plays an important role in chemical manufacturing. Photocatalytic acceptorless dehydrogenation offers a light-driven alternative for producing value-added aldehydes and H 2 under mild conditions and with easy separation and high molar efficiency. However, using semiconductor photocatalysts to achieve high selectivity and long-term stability under prolonged high-intensity illumination remains challenging. In this work, we developed CdS/TiO 2 /Ni photocatalysts by depositing TiO 2 onto CdS nanoparticle panels via atomic layer deposition (ALD), followed by Ni cocatalyst photodeposition, for the acceptorless dehydrogenation of benzyl alcohol to benzaldehyde and H 2 . Diluting the benzyl alcohol concentration to a practical range of ~10 vol% (1 M) further increased benzaldehyde selectivity to ~95%. Ni photodeposition and zeta-potential measurements suggest that TiO 2 coatings progressively modify Cd 2+ -associated surface sites through Ti 3+ /Ti 4+ incorporation, altering adsorption kinetics and contributing to the reduced activity. This extends the photocatalyst’s lifespan from ~23 to 60 hours and increases cumulative benzaldehyde and H 2 production. TiO 2 thin-film coatings have emerged as a promising strategy to protect semiconductor photocatalysts while modifying surface active sites and reaction kinetics, and their stability-activity trade-off showing lower initial-stage activity beyond 15-cycle ALD will be discussed alongside proposed mechanisms. This work establishes a semiconductor/coating/cocatalyst design architecture that highlights the importance of engineering surface adsorption and active-site environments, alongside charge-separation strategies based on band-edge energetics and charge-carrier dynamics, to jointly optimize photocatalytic activity and product selectivity for targeted chemical synthesis.
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BibTeX
@misc{kludze2026nitio,
title = {{Ni/TiO ₂ Interfaces Enhance Benzaldehyde Selectivity in the Photocatalytic Dehydrogenation of Benzyl Alcohol}},
author = {Atsu Kludze and Haoqing Su and Fang Yuan and Abrar Sheikh and Jake Heinlein and Saumya Gulati and Leslie Schoop and Shu Hu},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15011181/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011181/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Ni/TiO ₂ Interfaces Enhance Benzaldehyde Selectivity in the Photocatalytic Dehydrogenation of Benzyl Alcohol
AU - Atsu Kludze
AU - Haoqing Su
AU - Fang Yuan
AU - Abrar Sheikh
AU - Jake Heinlein
AU - Saumya Gulati
AU - Leslie Schoop
AU - Shu Hu
PY - 2026
DA - 2026/10/28
PB - ChemRxiv
DO - 10.26434/chemrxiv.15011181/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011181/v1
AB - The selective conversion of alcohols to carbonyls (ketones and aldehydes) plays an important role in chemical manufacturing. Photocatalytic acceptorless dehydrogenation offers a light-driven alternative for producing value-added aldehydes and H 2 under mild conditions and with easy separation and high molar efficiency. However, using semiconductor photocatalysts to achieve high selectivity and long-term stability under prolonged high-intensity illumination remains challenging. In this work, we developed CdS/TiO 2 /Ni photocatalysts by depositing TiO 2 onto CdS nanoparticle panels via atomic layer deposition (ALD), followed by Ni cocatalyst photodeposition, for the acceptorless dehydrogenation of benzyl alcohol to benzaldehyde and H 2 . Diluting the benzyl alcohol concentration to a practical range of ~10 vol% (1 M) further increased benzaldehyde selectivity to ~95%. Ni photodeposition and zeta-potential measurements suggest that TiO 2 coatings progressively modify Cd 2+ -associated surface sites through Ti 3+ /Ti 4+ incorporation, altering adsorption kinetics and contributing to the reduced activity. This extends the photocatalyst’s lifespan from ~23 to 60 hours and increases cumulative benzaldehyde and H 2 production. TiO 2 thin-film coatings have emerged as a promising strategy to protect semiconductor photocatalysts while modifying surface active sites and reaction kinetics, and their stability-activity trade-off showing lower initial-stage activity beyond 15-cycle ALD will be discussed alongside proposed mechanisms. This work establishes a semiconductor/coating/cocatalyst design architecture that highlights the importance of engineering surface adsorption and active-site environments, alongside charge-separation strategies based on band-edge energetics and charge-carrier dynamics, to jointly optimize photocatalytic activity and product selectivity for targeted chemical synthesis.
ER -