Solar fuels: photoelectrosynthesis of CO from CO2 at p-type Si using Fe porphyrin electrocatalysts.
Solar fuels: photoelectrosynthesis of CO from CO2 at p-type Si using Fe porphyrin electrocatalysts.
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DOI：
10.1002/chem.201300764
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发表时间：
2013-09
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影响因子：
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通讯作者：
Khalaf M. Alenezi;S. Ibrahim;Peiyi Li;C. Pickett
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文献类型：
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作者：
Khalaf M. Alenezi;S. Ibrahim;Peiyi Li;C. Pickett
在 CF3CH2OH 作为质子源和 0.1 M [NBu4][BF4]/MeCN/5% DMF (v/v) 作为电解质的情况下，使用内消旋四苯基卟啉 Fe(III) 氯化物，可以在硼掺杂、氢封端的 p 型硅电极上驱动 CO2 光电催化转化为 CO。在多色光照射下，光电催化作用的光电压约为暗反应的正光电压 650 mV。产生的一氧化碳的电流效率 >90%，并且对氢气的形成具有高选择性。相对于 SCE，-1.1 V 下的典型光电化学电流密度为 3 mA cm(-2)，并且在 6 小时内实现了 175 次转换。循环伏安数据与 -1.2 V 相对于 SCE 下 p 型 Si 光电催化的周转频率 k(Si)(obs)=0.24×10(4) s(-1) 一致，这与在 -1.85 V 相对于 SCE 下在黑暗中玻璃碳上电催化的 k(Si)(obs)=1.03×10(4) s(-1) 一致。
Photoelectrocatalytic conversion of CO2 to CO can be driven at a boron-doped, hydrogen terminated, p-type silicon electrode using a meso-tetraphenylporphyrin Fe(III) chloride in the presence of CF3CH2OH as a proton source and 0.1 M [NBu4][BF4]/MeCN/5% DMF (v/v) as the electrolyte. Under illumination with polychromatic light, the photoelectrocatalysis operates with a photovoltage of about 650 mV positive of that for the dark reaction. Carbon monoxide is produced with a current efficiency >90% and with a high selectivity over H2 formation. Photoelectrochemical current densities of 3 mA cm(-2) at -1.1 V versus SCE are typical, and 175 turnovers have been attained over a 6 h period. Cyclic voltammetric data are consistent with a turnover frequency of k(Si)(obs)=0.24×10(4) s(-1) for the photoelectrocatalysis at p-type Si at -1.2 V versus SCE this compares with k(Si)(obs)=1.03×10(4) s(-1) for the electrocatalysis in the dark on vitreous carbon at a potential of -1.85 V versus SCE.