Liu Ning, Zhou Xuemei, Nguyen Nhat Truong, Peters Kristina, Zoller Florian, Hwang Imgon, Schneider Christopher, Miehlich Matthias E, Freitag Detlef, Meyer Karsten, Fattakhova-Rohlfing Dina, Schmuki Patrik
Department of Materials Science WW-4, LKO, University of Erlangen-Nuremberg, Martensstrasse 7, 91058, Erlangen, Germany.
Department of Chemistry and Center for NanoScience (CeNS), Ludwig-Maximilians-Universität München, Butenandtstr. 5-11, 81377, Munich, Germany.
ChemSusChem. 2017 Jan 10;10(1):62-67. doi: 10.1002/cssc.201601264. Epub 2016 Dec 9.
'Black' TiO -in the widest sense, TiO reduced by various treatments-has attracted tremendous scientific interest in recent years because of some outstanding properties; most remarkably in photocatalysis. While the material effects visible light absorption (the blacker, the better), black titania produced by high pressure hydrogenation was recently reported to show another highly interesting feature; noble-metal-free photocatalytic H generation. In a systematic investigation of high-temperature hydrogen treatments of anatase nanoparticles, TEM, XRD, EPR, XPS, and photoelectrochemistry are used to characterize different degrees of surface hydrogenation, surface termination, electrical conductivity, and structural defects in the differently treated materials. The materials' intrinsic activity for photocatalytic hydrogen evolution is coupled neither with their visible light absorption behavior nor the formation of amorphous material, but rather must be ascribed to optimized and specific defect formation (gray is better than black). This finding is further confirmed by using a mesoporous anatase matrix as a hydrogenation precursor, which, after conversion to the gray state, even further enhances the overall photocatalytic hydrogen evolution activity.
“黑色”二氧化钛（从最广泛的意义上讲，是通过各种处理还原得到的二氧化钛）近年来因其一些突出特性而引起了极大的科学关注；最显著的是在光催化方面。虽然这种材料能吸收可见光（颜色越黑，吸收效果越好），但最近有报道称，通过高压氢化制备的黑色二氧化钛展现出另一个极具吸引力的特性；即无贵金属光催化产氢。在对锐钛矿纳米颗粒进行高温氢处理的系统研究中，利用透射电子显微镜（TEM）、X射线衍射（XRD）、电子顺磁共振（EPR）、X射线光电子能谱（XPS）和光电化学来表征不同处理材料的表面氢化程度、表面终止情况、电导率和结构缺陷。材料光催化析氢的固有活性既不与其可见光吸收行为相关，也不与非晶材料的形成相关，而是必须归因于优化的特定缺陷形成（灰色比黑色更好）。使用介孔锐钛矿基质作为氢化前驱体进一步证实了这一发现，该前驱体在转化为灰色状态后，甚至进一步提高了整体光催化析氢活性。
