Solvent molecules form surface redox mediators in situ and cocatalyze O<sub>2</sub> reduction on Pd

doi:10.1126/science.abc1339

GSTDTAP > 气候变化

DOI	10.1126/science.abc1339
	Solvent molecules form surface redox mediators in situ and cocatalyze O₂ reduction on Pd
	Jason S. Adams; Ashwin Chemburkar; Pranjali Priyadarshini; Tomas Ricciardulli; Yubing Lu; Vineet Maliekkal; Abinaya Sampath; Stuart Winikoff; Ayman M. Karim; Matthew Neurock; David W. Flaherty
	2021-02-05
发表期刊	Science
出版年	2021
英文摘要	The role of solvents participating directly in thermal catalytic reactions is clearer for homogeneous catalysis than for heterogeneous catalysis. Adams et al. studied the formation of hydrogen peroxide from hydrogen and oxygen on palladium nanoparticles by measuring the kinetic isotope effect and performing density functional theory simulations in aqueous and organic solvents. Methanol formed chemisorbed hydroxymethyl intermediates. These surface redox mediators transferred electrons and protons to adsorbed oxygen species and were regenerated by oxidizing chemisorbed hydrogen atoms. However, water molecules heterolytically oxidized hydrogen to generate solvated protons and surface electrons that reduced oxygen. Science , this issue p. [626][1] Solvent molecules influence the reactions of molecular hydrogen and oxygen on palladium nanoparticles. Organic solvents activate to form reactive surface intermediates that mediate oxygen reduction through pathways distinct from reactions in pure water. Kinetic measurements and ab initio quantum chemical calculations indicate that methanol and water cocatalyze oxygen reduction by facilitating proton-electron transfer reactions. Methanol generates hydroxymethyl intermediates on palladium surfaces that efficiently transfer protons and electrons to oxygen to form hydrogen peroxide and formaldehyde. Formaldehyde subsequently oxidizes hydrogen to regenerate hydroxymethyl. Water, on the other hand, heterolytically oxidizes hydrogen to produce hydronium ions and electrons that reduce oxygen. These findings suggest that reactions of solvent molecules at solid-liquid interfaces can generate redox mediators in situ and provide opportunities to substantially increase rates and selectivities for catalytic reactions. [1]: /lookup/doi/10.1126/science.abc1339
领域	气候变化 ; 资源环境
URL	查看原文
引用统计	被引频次：81[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://119.78.100.173/C666/handle/2XK7JSWQ/314054
专题	气候变化资源环境科学
推荐引用方式 GB/T 7714	Jason S. Adams,Ashwin Chemburkar,Pranjali Priyadarshini,et al. Solvent molecules form surface redox mediators in situ and cocatalyze O₂ reduction on Pd[J]. Science,2021.
APA	Jason S. Adams.,Ashwin Chemburkar.,Pranjali Priyadarshini.,Tomas Ricciardulli.,Yubing Lu.,...&David W. Flaherty.(2021).Solvent molecules form surface redox mediators in situ and cocatalyze O₂ reduction on Pd.Science.
MLA	Jason S. Adams,et al."Solvent molecules form surface redox mediators in situ and cocatalyze O₂ reduction on Pd".Science (2021).