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Undoped and Ni-Doped CoOx Surface Modification of Porous BiVO4 Photoelectrodes for Water Oxidation
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2016-10-06 00:00:00 , DOI: 10.1021/acs.jpcc.6b08654 Ya Liu 1 , Youhong Guo 2 , Laura T. Schelhas 3 , Mingtao Li 1 , Joel W. Ager
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2016-10-06 00:00:00 , DOI: 10.1021/acs.jpcc.6b08654 Ya Liu 1 , Youhong Guo 2 , Laura T. Schelhas 3 , Mingtao Li 1 , Joel W. Ager
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Surface modification of photoanodes with oxygen evolution reaction (OER) catalysts is an effective approach to enhance water oxidation kinetics, to reduce external bias, and to improve the energy harvesting efficiency of photoelectrochemical (PEC) water oxidation. Here, the surface of porous BiVO4 photoanodes was modified by the deposition of undoped and Ni-doped CoOx via nitrogen flow assisted electrostatic spray pyrolysis. This newly developed atmospheric pressure deposition technique allows for surface coverage throughout the porous structure with thickness and composition control. PEC testing of modified BiVO4 photoanodes shows that after deposition of an undoped CoOx surface layer, the onset potential shifts negatively by ca. 420 mV and the photocurrent density reaches 2.01 mA cm–2 at 1.23 vs VRHE under AM 1.5G illumination. Modification with Ni-doped CoOx produces even more effective OER catalysis and yields a photocurrent density of 2.62 mA cm–2 at 1.23 VRHE under AM 1.5G illumination. The valence band X-ray photoelectron spectroscopy and synchrotron-based X-ray absorption spectroscopy results show the Ni doping reduces the Fermi level of the CoOx layer; the increased surface band bending produced by this effect is partially responsible for the superior PEC performance.
中文翻译：
用于水氧化的多孔BiVO 4光电电极的未掺杂和Ni掺杂的CoO x表面修饰
用氧气析出反应（OER）催化剂对光阳极进行表面改性是增强水氧化动力学，减少外部偏压并提高光电化学（PEC）水氧化的能量收集效率的有效方法。在此，多孔BiVO 4光电阳极的表面通过氮气流辅助静电喷雾热解沉积未掺杂和掺Ni的CoO x进行了改性。这种新开发的大气压沉积技术可以控制厚度和成分，从而覆盖整个多孔结构。改性的BiVO 4光电阳极的PEC测试表明，在沉积未掺杂的CoO x之后表面层，开始电势负移约。420 mV，在AM 1.5G光照下，相对于V RHE，光电流密度在1.23 vs. V RHE时达到2.01 mA cm –2。掺Ni的CoO x的改性可产生更有效的OER催化，并在AM 1.5G光照下在1.23 V RHE时产生2.62 mA cm –2的光电流密度。价带X射线光电子能谱和基于同步加速器的X射线吸收能谱结果表明，Ni掺杂降低了CoO x层的费米能级。由于这种作用而产生的增加的表面带弯曲，部分归因于优异的PEC性能。
更新日期：2016-10-06
中文翻译：
用于水氧化的多孔BiVO 4光电电极的未掺杂和Ni掺杂的CoO x表面修饰
用氧气析出反应（OER）催化剂对光阳极进行表面改性是增强水氧化动力学，减少外部偏压并提高光电化学（PEC）水氧化的能量收集效率的有效方法。在此，多孔BiVO 4光电阳极的表面通过氮气流辅助静电喷雾热解沉积未掺杂和掺Ni的CoO x进行了改性。这种新开发的大气压沉积技术可以控制厚度和成分，从而覆盖整个多孔结构。改性的BiVO 4光电阳极的PEC测试表明，在沉积未掺杂的CoO x之后表面层，开始电势负移约。420 mV，在AM 1.5G光照下，相对于V RHE，光电流密度在1.23 vs. V RHE时达到2.01 mA cm –2。掺Ni的CoO x的改性可产生更有效的OER催化，并在AM 1.5G光照下在1.23 V RHE时产生2.62 mA cm –2的光电流密度。价带X射线光电子能谱和基于同步加速器的X射线吸收能谱结果表明，Ni掺杂降低了CoO x层的费米能级。由于这种作用而产生的增加的表面带弯曲，部分归因于优异的PEC性能。
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