Microenvironment Regulation of {Co₄^IIO₄} Cubane for Syngas Photosynthesis

It is a great challenging task for selectivity control of both CO₂ photoreduction and water splitting to produce syngas via precise microenvironment regulation. Herein, a series of UiO-type Eu-MOFs (Eu-bpdc, Eu-bpydc, Ru-Eu-bpdc, and Ru-Eu-bpydc) with different surrounding confined spaces were designed and synthesized. These photosensitizing Ru_x-Eu-MOFs were used as the molecular platform to encapsulate the [Co^II₄(dpy{OH}O)₄(OAc)₂(H₂O)₂]²⁺ (Co) cubane cluster for constructing Co₄@Ru-Eu-MOF (x = 0.1, 0.2, and 0.4) heterogeneous photocatalysts for efficient CO₂ photoreduction and water splitting. The H₂ and CO yields can reach 446.6 and 459.8 μmol·g^-1, respectively, in 10 h with Co₄@Ru-Eu-bpdc as the catalyst, and their total yield can be dramatically improved to 2500 μmol·g^-1 with the ratio of CO/H₂ ranging from 1:1 to 1:2 via changing the photosensitizer content in the confined space. By increasing the N content around the cubane, the photocatalytic performance drops sharply in Co₄@Ru-Eu-bpydc, but with an enhanced proportion of CO in the final products. In the homogeneous system, the Co cubane was surrounding with Ru photosensitizers via week interactions, which can drive water splitting into H₂ with >99% selectivity. Comprehensive structure-function analysis highlights the important role of microenvironment regulation in the selectivity control via constructing homogeneous and heterogeneous photocatalytic systems. This work provides a new insight for engineering a catalytic microenvironment of the cubane cluster for selectivity control of CO₂ photoreduction and water splitting.