The oxo-Co/phosphate based material (CoPi) developed by Kanan and Nocera in 2008 is among the most outstanding catalysts for water oxidation at neutral pH. The remarkable performance and striking properties of CoPi reside on its intriguing and unique structure. In the present contribution, TEM, SAED, UV-vis-NIR absorption and Raman spectroscopy were performed at 77 K, complemented by room temperature experiments, to unprecedentedly reveal that CoPi is composed by short-range ordered β-NaCoPO₄ (a solid ionic conductor) and expanded-lattice Co₃O₄ clusters with electronic structures, vibrational responses and catalytic properties quite deviated from those of their bulk counterparts. Internal morphological features of CoPi are also disclosed. Consequently, some aspects of the previously proposed structure and operating mechanisms are revised. This study derived in a deposition route which yields CoPi layers that outperforms, as water oxidation catalyst, the traditionally electrodeposited CoPi.

Kanan和Nocera于2008年开发的含氧-Co /磷酸盐基材料（CoPi）是在中性pH下水氧化的最杰出催化剂之一。CoPi出色的性能和引人注目的特性在于其引人入胜的独特结构。在本贡献，TEM，SAED，UV-VIS-NIR吸收和拉曼光谱在77K下进行，通过室温下的实验的补充，以前所未有的揭示COPI由通过短程有序β-NaCoPO ₄（固体离子导体）和扩展晶格Co ₃ O ₄具有电子结构，振动响应和催化特性的团簇，与它们的整体团簇完全不同。还公开了CoPi的内部形态特征。因此，对先前提出的结构和操作机制的某些方面进行了修订。这项研究以沉积路线为基础，该路线产生的CoPi层优于作为水氧化催化剂的传统电沉积CoPi。