Xu Kaiyang, Liang Lecheng, Li Tong, Bao Mujie, Yu Zhipeng, Wang Jingwei, Thalluri Sitaramanjaneya Mouli, Lin Fei, Liu Quanbing, Cui Zhiming, Song Shuqin, Liu Lifeng
Guangzhou Key Laboratory of Clean Transportation Energy Chemistry, Guangdong Provincial Key Laboratory of Plant Resources Biorefinery, School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou, 510006, China.
Jieyang Branch of Chemistry and Chemical Engineering, Guangdong Laboratory (Rongjiang Laboratory), Jieyang, 515200, China.
Adv Mater. 2024 Aug;36(31):e2403792. doi: 10.1002/adma.202403792. Epub 2024 May 27.
Seawater electrolysis is a potentially cost-effective approach to green hydrogen production, but it currently faces substantial challenges for its high energy consumption and the interference of chlorine evolution reaction (ClER). Replacing the energy-demanding oxygen evolution reaction with methanol oxidation reaction (MOR) represents a promising alternative, as MOR occurs at a significantly low anodic potential, which cannot only reduce the voltage needed for electrolysis but also completely circumvents ClER. To this end, developing high-performance MOR catalysts is a key. Herein, a novel quaternary PtPdCuGa/C intermetallic nanoparticle (i-NP) catalyst is reported, which shows a high mass activity (11.13 A mg ), a large specific activity (18.13 mA cm ), and outstanding stability toward alkaline MOR. Advanced characterization and density functional theory calculations reveal that the introduction of atomically distributed Pd in PtCuGa intermetallic markedly promotes the oxidation of key reaction intermediates by enriching electron concentration around Pt sites, resulting in weak adsorption of carbon-containing intermediates and favorable adsorption of synergistic OH groups near Pd sites. MOR-assisted seawater electrolysis is demonstrated, which continuously operates under 1.23 V for 240 h in simulated seawater and 120 h in natural seawater without notable degradation.
海水电解是一种潜在的具有成本效益的绿色制氢方法,但目前因其高能耗和析氯反应(ClER)的干扰而面临重大挑战。用甲醇氧化反应(MOR)取代耗能的析氧反应是一种很有前景的替代方案,因为MOR在显著较低的阳极电位下发生,这不仅可以降低电解所需的电压,还能完全避免ClER。为此,开发高性能的MOR催化剂是关键。在此,报道了一种新型的四元PtPdCuGa/C金属间纳米颗粒(i-NP)催化剂,它表现出高质量活性(11.13 A mg)、大比活性(18.13 mA cm)以及对碱性MOR具有出色的稳定性。先进的表征和密度泛函理论计算表明,在PtCuGa金属间化合物中引入原子分布的Pd通过富集Pt位点周围的电子浓度显著促进了关键反应中间体的氧化,导致含碳中间体的弱吸附以及Pd位点附近协同OH基团的有利吸附。展示了MOR辅助的海水电解,其在模拟海水中于1.23 V下连续运行240小时,在天然海水中连续运行120小时,且无明显降解。