近日，陕西师范大学陈煜团队实现了Pt-Bi₂O₃对末端羟基氧化定向转化甘油为甘油酸的吸附构型控制。相关论文发表在2025年5月27日出版的《科学进展》杂志上。

甘油是生物柴油生产的副产品，可以通过电催化反应有效地转化为有价值的化学品。研究组使用电偶置换法成功合成了装饰在氧化铋（Bi₂O₃）纳米片（PtBi-DONS）上的铂（Pt）纳米晶体，其最佳Pt:Bi比为1:1。Pt₁Bi₁ DONS对甘油电氧化具有显著的电催化性能，实现了优异的催化活性（在0.67 V下电流为0.82 A mgPt^-1，与可逆氢电极（RHE）相比），对C₃产物，特别是甘油酸的选择性高达96.6%。

卓越的性能源于两个关键因素：（1）Bi₂O₃到Pt的电子转移产生了富含电子的Pt位点，抑制了C-C键的断裂；（2）Bi₂O₃通过多个羟基相互作用促进了有利的甘油吸附构型。使用操作光谱和电化学阻抗光谱的机理研究表明，Pt和Bi₂O₃之间的协同作用促进了快速电荷转移和稳定的中间体形成。此外，与单醇相比，PtBi-DONS在氧化其他多元醇方面表现出优异的通用性。

附：英文原文

Title: Adsorption configuration control on Pt-Bi2O3 for the oriented conversion of glycerol to glyceric acid via terminal hydroxyl oxidation

Author: Xue Xiao, Xuan Ai, Yu Chen

Issue&Volume: 2025/05/27

Abstract: Glycerol, a byproduct of biodiesel production, can be efficiently converted into valuable chemicals through electrocatalytic reaction. In this study, platinum (Pt) nanocrystals decorated on bismuth oxide (Bi2O3) nanosheets (PtBi DONS) with an optimal Pt:Bi ratio of 1:1 were successfully synthesized using a galvanic replacement method. Pt1Bi1 DONS exhibit remarkable electrocatalytic performance for glycerol electrooxidation, achieving an excellent catalytic activity (current of 0.82 A mgPt–1 at 0.67 V vs. reversible hydrogen electrode (RHE)) and an exceptional selectivity of 96.6% for C3 products, particularly glyceric acid. The superior performance stems from two key factors: (1) electron transfer from Bi2O3 to Pt creates electron-rich Pt sites that suppress C–C bond cleavage and (2) Bi2O3 facilitates favorable glycerol adsorption configurations through multiple hydroxyl group interactions. Mechanistic studies using operando spectroscopy and electrochemical impedance spectroscopy revealed that the synergistic effect between Pt and Bi2O3 promotes rapid charge transfer and stable intermediate formation. Moreover, PtBi DONS showed excellent versatility in oxidizing other polyols compared with monoalcohols.

DOI: 10.1016/j.scib.2025.05.032

Source: https://www.sciencedirect.com/science/article/abs/pii/S2095927325005729