关于1967年的一篇光催化文献的讨论？众所周知，1972年Fujishima与Honda在单晶TiO2半导体电极上发现水的光电催化氧化、还原反应。（AKIRA FUJISHIMA, KENICHI HONDA. Electrochemical Photolysis of Water at a Semiconductor Electrode[J]. Nature, 1972, 238(5358): 37-38）,一般引用文献的时候也会把这边文献当做光催化的起点。但是我查到1967年的一篇ZnO光催化的文献，要早五年发表，为什么引用的却比较少呢？相比Fujishima的研究成果，这篇文献的欠缺之处在哪里？Title: Chemical Role of Holes and Electrons in ZnO Photocatalysis Author: Morrison, S. R.; Freund, T.Source: Journal of Chemical Physics, 1967, 47(1543): 1542-1551Abstract:??The role of the electronic properties of a semiconductor in heterogeneous catalysis and electrochemistry was experimentally investigated on single‐crystal ZnO. It was shown quantitatively that the availability of electrons and holes at the surface is dominant in the mechanism of a heterogeneously catalyzed reaction. Chemical rate measurements as well as in situ solid‐state measurements were carried out in an aqueous medium for the reaction: HCOOH+O2→H2O2+CO2, photocatalyzed by ZnO. Two new experimental electrochemical methods for semiconductor surface reactions were developed: ``current doubling'' and measurement of ``unfilled'' electronic surface states by the capacitance. They were devised to characterize reactive sorbed species. The detailed catalytic mechanism was based on studies of individual reaction steps under three solid‐state surface conditions: (1) only holes reacting, (2) only electrons reacting, and (3) both holes and electrons reacting. The first two correspond to the ZnO being an electrochemical anode and cathode, respectively; the last corresponds to ordinary catalysis when the hole current is balanced by the electron current so that the net current is zero. It was shown that the over‐all catalyzed reaction is not simply the sum of individual oxidation and reduction reactions which occur with only holes or only electrons, respectively, but involves a surface intermediate formed when both holes and electrons are present.查看更多3个回答 . 20人已关注
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