Substituting the oxygen evolution reaction with the thermodynamically favorable glycerol oxidation reaction (GOR) in water splitting offers a promising approach to produce high-value chemicals in addition to hydrogen. However, the GOR suffers from the especially low selectivity towards the most-favored and value-added C₃ products, and the current density of the GOR still remains unsatisfactory. Herein, we successfully prepared a novel self-supported honeycomb-like PtAu alloy catalyst on Ni foam (hp-PtAu/NF) for efficient electrocatalytic upgrading of glycerol to C₃ chemicals at the anode coupled with cathodic H₂ production. The hp-PtAu/NF anode shows high selectivity values for GOR conversion toward lactate and for total C₃ products (70% and 95%, respectively) at 0.4 V vs. RHE. Impressively, 62% selectivity for C₃ products over the hp-PtAu/NF electrode has been obtained at 1.6 V vs. RHE with an attractively high current density of 921.5 mA cm⁻², compared to that (0.85%) on Pt/NF. Electrochemical in situ characterizations and theoretical calculations show that the introduction of Au can significantly facilitate the adsorption of hydroxyl species, thus elevating the GOR performance of hp-PtAu/NF. Meanwhile, the adsorption of glycerol molecule on the catalyst has been optimized to be a configuration of one terminal C atom, rather than two C atoms, being bonded on the catalyst surface by alloying Au with Pt, which effectively prevents the C–C bond from breaking into C₂ or C₁ chemicals and formation of poisonous carbonaceous intermediates, ensuring the high activity and C₃ selectivity of the GOR over hp-PtAu/NF at enhanced current densities. This work illuminates the adsorption modulation mechanism of hp-PtAu/NF alloy catalyst and provides a promising electrocatalytic system for the co-production of value-added C₃ products and H₂ by a low-cost GOR approach in aqueous solutions.

中文翻译：

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PtAu 合金化调节羟基和底物吸附用于甘油电氧化生成 C3 产物


在水分解中，用热力学上有利的甘油氧化反应（GOR）代替析氧反应，为生产除氢气之外的高价值化学品提供了一种有前途的方法。然而，GOR对最受青睐和增值的C ₃ 产品的选择性特别低，并且GOR的电流密度仍然不令人满意。在此，我们成功地在泡沫镍上制备了一种新型自支撑蜂窝状 PtAu 合金催化剂 (hp-PtAu/NF)，用于在阳极结合阴极 H < b2> 生产。 hp-PtAu/NF 阳极在 0.4 V vs. RHE 下对 GOR 转化为乳酸和总 C ₃ 产物表现出高选择性值（分别为 70% 和 95%）。令人印象深刻的是，与 hp-PtAu/NF 电极相比，C ₃ 产品在 1.6 V vs. RHE 下获得了 62% 的选择性，电流密度高达 921.5 mA cm ⁻² ，极具吸引力，与 Pt/NF 的 (0.85%) 相比。电化学原位表征和理论计算表明，Au的引入可以显着促进羟基物质的吸附，从而提高hp-PtAu/NF的GOR性能。同时，甘油分子在催化剂上的吸附被优化为一个末端C原子的构型，而不是两个C原子，通过Au与Pt合金键合在催化剂表面，有效地阻止了C-C键的形成。分解 C ₂ 或 C ₁ 化学物质并形成有毒碳质中间体，确保 GOR 相对于 hp-PtAu/NF 具有高活性和 C ₃ 选择性在增强的电流密度下。 这项工作阐明了 hp-PtAu/NF 合金催化剂的吸附调节机制，并为联产增值 C ₃ 产物和 H ₂ 提供了一种有前景的电催化系统。水溶液中的低成本 GOR 方法。