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Efficient Solar-Driven Hydrogen Transfer by Bismuth-Based Photocatalyst with Engineered Basic Sites

Dai, Yitao, Li, Chao, Shen, Yanbin, Zhu, Shujie, Hvid, Mathias S., Wu, Lai-Chin, Skibsted, Jørgen, Li, Yongwang, Niemantsverdriet, J. W. Hans, Besenbacher, Flemming, Lock, Nina, Su, Ren
Journal of the American Chemical Society 2018 v.140 no.48 pp. 16711-16719
bismuth, hydrogen, industrial applications, irradiation, light, nitrobenzenes, oxidation, photocatalysis, photocatalysts, quinones, solar radiation, thiols
Photocatalytic organic conversions involving a hydrogen transfer (HT) step have attracted much attention, but the efficiency and selectivity under visible light irradiation still needs to be significantly enhanced. Here we have developed a noble metal-free, basic-site engineered bismuth oxybromide [Bi₂₄O₃₁Br₁₀(OH)δ] that can accelerate the photocatalytic HT step in both reduction and oxidation reactions, i.e., nitrobenzene to azo/azoxybenzene, quinones to quinols, thiones to thiols, and alcohols to ketones under visible light irradiation and ambient conditions. Remarkably, quantum efficiencies of 42% and 32% for the nitrobenzene reduction can be reached under 410 and 450 nm irradiation, respectively. The Bi₂₄O₃₁Br₁₀(OH)δ photocatalyst also exhibits excellent performance in up-scaling and stability under visible light and even solar irradiation, revealing economic potential for industrial applications.