State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
Department of Chemistry, Tsinghua University, 30 Shuangqing Road, Beijing 100084, China.
J Am Chem Soc. 2022 May 4;144(17):7720-7730. doi: 10.1021/jacs.2c00465. Epub 2022 Mar 30.
Photoelectrocatalytic (PEC) glycerol oxidation offers a sustainable approach to produce dihydroxyacetone (DHA) as a valuable chemical, which can find use in cosmetic, pharmaceutical industries, etc. However, it still suffers from the low selectivity (≤60%) that substantially limits the application. Here, we report the PEC oxidation of glycerol to DHA with a selectivity of 75.4% over a heterogeneous photoanode of BiO nanoparticles on TiO nanorod arrays (BiO/TiO). The selectivity of DHA can be maintained at ∼65% under a relatively high conversion of glycerol (∼50%). The existing p-n junction between BiO and TiO promotes charge transfer and thus guarantees high photocurrent density. Experimental combined with theoretical studies reveal that BiO prefers to interact with the middle hydroxyl of glycerol that facilitates the selective oxidation of glycerol to DHA. Comprehensive reaction mechanism studies suggest that the reaction follows two parallel pathways, including electrophilic OH* (major) and lattice oxygen (minor) oxidations. Finally, we designed a self-powered PEC system, achieving a DHA productivity of 1.04 mg cm h with >70% selectivity and a H productivity of 0.32 mL cm h. This work may shed light on the potential of PEC strategy for biomass valorization toward value-added products via PEC anode surface engineering.
光电催化（PEC）甘油氧化为生产二羟丙酮（DHA）提供了一种可持续的方法，DHA 是一种有价值的化学品，可用于化妆品、制药等行业。然而，它的选择性（≤60%）仍然较低，这极大地限制了其应用。在此，我们报告了在 BiO 纳米粒子/TiO 纳米棒阵列异质光阳极上 PEC 氧化甘油生产 DHA 的选择性为 75.4%。在甘油的相对较高转化率（约 50%）下，DHA 的选择性可维持在约 65%。BiO 和 TiO 之间现有的 p-n 结促进了电荷转移，从而保证了高光电流密度。实验结合理论研究表明，BiO 优先与甘油的中羟基相互作用，从而有利于甘油选择性氧化生成 DHA。综合反应机理研究表明，反应遵循两条平行途径，包括亲电 OH*（主要）和晶格氧（次要）氧化。最后，我们设计了一个自供电的 PEC 系统，实现了 1.04 mg cm h 的 DHA 生产率和 >70%的选择性，以及 0.32 mL cm h 的 H 生产率。这项工作可能为通过 PEC 阳极表面工程将生物质增值为附加值产品的 PEC 策略提供了新的思路。
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