A Full-Spectrum Visible-Light-Responsive Organophotocatalyst Film for Removal of Trimethylamine
A Full-Spectrum Visible-Light-Responsive Organophotocatalyst Film for Removal of Trimethylamine
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DOI：
10.1002/cssc.201100064
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发表时间：
2011-01-01
期刊：
影响因子：
8.4
通讯作者：
Imaya, Hiroshi
中科院分区：
文献类型：
--
作者：
Nagai, Keiji;Abe, Toshiyuki;Imaya, Hiroshi
在紫外光照射下，二氧化钛半导体表面光催化降解有机化合物为解决各种环境问题提供了一种实用的解决方案。[1，2]然而，它的主要缺点是在可见光下无效：锐钛矿型二氧化钛的带隙为3.3 eV，这需要<；380 nm的波长来激发。只有不到5%的入射到地球表面的太阳流量在这个区域内。有机和无机材料都是将可见光转化为太阳能的候选材料。[3-6]最近开发的一些光催化剂在可见光下表现出很高的反应活性，[7-10]而其中一些在低照度下表现出活性，例如室内照明。此外，几种可见光激活的光催化剂已经被开发成覆盖整个可见光区域直到750 nm，它们的光催化量子效率在可见光谱的长波长区域下降。[3，10]由茂金属衍生物(3，4，9，10-茂四甲基双苯并咪唑，PTCBI)和酞菁(H2Pc)组成的有机p/n双层膜通常被用作干燥体系的光伏材料，[11-14]，我们发现这种结合在PTCBI中作为红外光的反射镜，[15]，也就是说，它无需接触电极就可以工作。在潮湿的除氧条件下，ITO/PTCBI/H_2Pc/电解液和ITO/H_2Pc/PTCBI/电解液组合分别起到光阳极和光阴极的作用。[16]此外，在可见光照射下，氧的析出具有很小的偏置(约+0.4V vs.Ag/AgCl)，特别是通过在H_2Pc表面负载Ir氧化物催化剂[17]或将钴离子插入到酞菁中，催化周转数为3.5 103。[18]尽管自从Honda和Fujishima报道了用UV-响应型TiO2电极光电化学分解水以来，人们做出了巨大的努力来创建光化学能转换系统，[19]这些是有机半导体在可见光照射下诱导化学计量水裂解的第一个例子。放氧量表明有机材料在水相和氧化环境中的稳定性。
The photocatalytic degradation of organic compounds on a TiO2 semiconductor surface under UV irradiation offers a practical solution to a variety of environmental problems.[1, 2] However, a major disadvantage is its ineffectiveness under visible light: the band gap of anatase TiO2 is 3.3 eV, which requires wavelengths of< 380 nm for excitation. Less than 5% of the solar flux incident on the Earth’s surface lies within this regime. Organic as well as inorganic materials are candidates for the photocatalytic conversion of visible light into solar energy.[3–6] A number of recently developed photocatalysts exhibit a high reactivity under visible light,[7–10] while a few of them are active at low levels of illumination, such a interior lighting. Furthermore, several visible-light-activated photocatalysts have been developed to cover the entire visible region up to 750 nm, and their photocatalytic quantum efficiencies decrease in the longwavelength region of the visible spectrum.[3, 10] An organic p/n bilayer composed of a perylene derivative (3, 4, 9, 10-perylenetetracarboxyl-bisbenzimidazole, PTCBI) and phthalocyanine (H2Pc) is typically used as a photovoltaic material in dry systems,[11–14] and we have found that this combination acts as a mirror for infrared light based on free electrons in PTCBI,[15] that is, it works without contact electrodes. In wet, deaerated conditions the ITO/PTCBI/H2Pc/electrolyte and ITO/H2Pc/PTCBI/electrolyte combinations function as photoanode and photocathode, respectively.[16] Moreover, oxygen evolution occurs with a small bias (ca.+ 0.4 V vs. Ag/AgCl) under visible-light illumination, particularly by loading an iridium oxide catalyst on the H2Pc surface [17] or inserting a cobalt ion into phthalocyanine, with a catalytic turnover number of 3.5 103.[18] Despite tremendous efforts to create a photochemical energy conversion system ever since Honda and Fujishima reported photoelectrochemical water splitting by a UV-responsive TiO2 electrode,[19] these are the first examples of stoichiometric water splitting induced by an organic semiconductor under visible-light irradiation. The oxygen evolution indicates the stability of the organic materials in an aqueous phase as well as in an oxidative environment.