Department of Chemistry and Biochemistry, San Francisco State University, 1600 Holloway Ave., San Francisco, California 94132, USA.
J Chem Phys. 2022 Aug 28;157(8):081101. doi: 10.1063/5.0106914.
Plasmon-mediated electrocatalysis based on plasmonic gold nanoparticles (Au NPs) has emerged as a promising approach to facilitate electrochemical reactions with the introduction of light to excite the plasmonic electrodes. We have investigated the electrochemical oxidation of 4-(hydroxymethyl)benzoic acid (4-HMBA) on gold (Au), nickel (Ni), and platinum (Pt) metal working electrodes in alkaline electrolytes. Au has the lowest onset potential for catalyzing the electrooxidation of 4-HMBA among the three metals in base, whereas Pt does not catalyze the electrooxidation of 4-HMBA under alkaline conditions, although it is conventionally a good electrocatalyst for alcohol oxidation. Both 4-carboxybenzaldehyde and terephthalic acid are detected as the products of electrochemical oxidation of 4-HMBA on the Au working electrode by high-performance liquid chromatography . The electrodeposited Au NPs on indium tin oxide (ITO)-coated glass is further utilized as the working electrode for the 4-HMBA electrooxidation. With its broad absorption in the visible and near-infrared range, we show that the Au NPs on the ITO electrode could enhance the electrochemical oxidation of 4-HMBA under green and red LED light illuminations (505 and 625 nm). A possible reaction mechanism is proposed for the electrochemical oxidation of 4-HMBA on Au working electrodes in an alkaline electrolyte.
基于等离子体金纳米粒子 (Au NPs) 的等离子体介导的电催化已成为一种很有前途的方法，可以通过引入光来激发等离子体电极来促进电化学反应。我们研究了在碱性电解质中，金（Au）、镍（Ni）和铂（Pt）金属工作电极上 4-（羟甲基）苯甲酸（4-HMBA）的电化学氧化。在三种金属中，Au 具有最低的起始电位，可催化 4-HMBA 的电氧化，而 Pt 在碱性条件下不催化 4-HMBA 的电氧化，尽管它通常是醇氧化的良好电催化剂。通过高效液相色谱法，在 Au 工作电极上电化学氧化 4-HMBA 的产物被检测为 4-羧基苯甲醛和对苯二甲酸。进一步将氧化铟锡 (ITO) 涂层玻璃上的电沉积 Au NPs 用作 4-HMBA 电氧化的工作电极。由于其在可见光和近红外范围内的宽吸收，我们表明，ITO 电极上的 Au NPs 可以增强在绿光和红光 LED 光照（505 和 625nm）下 4-HMBA 的电化学氧化。提出了一种在碱性电解质中 Au 工作电极上电化学氧化 4-HMBA 的可能反应机制。
