期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 139, 期 33, 页码 11537-11543出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b05184
关键词
-
资金
- European Research Council [291482]
- Swiss National Science Foundation [140709]
- Swiss Federal Office for Energy (project PECHouse 3) [SI/500090-03]
- COLCIENCIAS
- EU [658270]
- EPRSC
- Engineering and Physical Sciences Research Council [1230594] Funding Source: researchfish
- Marie Curie Actions (MSCA) [658270] Funding Source: Marie Curie Actions (MSCA)
The kinetics of photoelectrochemical (PEC) oxidation of methanol, as a model organic substrate, on alpha-Fe2O3 photoanodes are studied using photoinduced absorption spectroscopy and transient photocurrent measurements. Methanol is oxidized on alpha-Fe2O3 to formaldehyde with near unity Faradaic efficiency. A rate law analysis under quasi-steady-state, conditions of PEC methanol oxidation indicates that rate of reaction is second order in the density of surface holes on hematite and independent of the applied potential. Analogous data on anatase TiO2 photoanodes indicate similar second-order kinetics for methanol oxidation with a second-order rate constant 2 orders of magnitude higher than that on alpha-Fe2O3. Kinetic isotope effect studies determine that the rate constant for methanol oxidation on alpha-Fe2O3 is retarded similar to 20-fold by H/D substitution. Employing these data, we propose a mechanism for methanol oxidation under 1 sun irradiation on these metal oxide surfaces and discuss the implications for the efficient PEC methanol oxidation to formaldehyde and concomitant hydrogen evolution.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据