Solar-driven carbonylation with CO2 replacing toxic CO as a C1 source is of considerable interest; however it remains a great challenge due to the inert CO2 molecule. Herein, we integrate cobalt single-site and ultrafine CuPd nanocluster catalysts into a porphyrin-based metal–organic framework to construct composite photocatalysts (Cu1Pd2) z @PCN-222­(Co) (z = 1.3, 2.0, and 3.0 nm). Upon visible light irradiation, excited porphyrin can concurrently transfer electrons to Co single sites and CuPd nanoclusters, providing the possibility for coupling CO2 photoreduction and Suzuki/Sonogashira reactions. This multicomponent synergy in (Cu1Pd2)1.3@PCN-222­(Co) can not only replace dangerous CO gas but also dramatically promote the photosynthesis of benzophenone in CO2 with over 90% yield and 97% selectivity under mild condition. Systematic investigations clearly decipher the function and collaboration among different components in these composite catalysts, highlighting a new insight into developing a sustainable protocol for carbonylation reactions by employing greenhouse gas CO2 as a C1 source.

Photosensitization associated with light absorption and energy/electron‐transfer represents the central processes for photosynthesis. However, it's still a challenge to develop a heavy‐atom‐free (HAF) strategy to improve the sensitizing ability of polymeric photosensitizers. Herein, we propose a new protocol to significantly improve the photosensitization by decorating mother conjugated microporous polymer (CMP‐1) with polycyclic aromatic hydrocarbons (PAHs), resulting in a series of CMPs (CMP‐2–4). Systematic study reveals that covalent modification with PAHs can transfer charge to Bodipy in CMP to further facilitate both intersystem crossing and electron‐hole separation, which can dramatically boost energy‐/electron‐transfer reactions. Remarkably, CMP‐2 as a representative CMP can efficiently drive the photosynthesis of methyl phenyl sulfoxide with 92 % yield, substantially higher than that of CMP‐1 (32 %). Experiments and theory calculations demonstrate the structure‐property‐activity relationship of these CMPs, opening a new horizon for developing HAF heterogeneous photosensitizers with highly efficient sensitizing activity by rational structure regulation at a molecular level.

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 x -Eu-bpdc, and Ru x -Eu-bpydc) with different surrounding confined spaces were designed and synthesized. These photosensitizing Rux-Eu-MOFs were used as the molecular platform to encapsulate the [CoII 4(dpy­{OH}­O)4(OAc)2(H2O)2]2+ (Co 4 ) cubane cluster for constructing Co4@Ru x -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 0.1 -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 0.1 -Eu-bpydc, but with an enhanced proportion of CO in the final products. In the homogeneous system, the Co 4 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.

A series of earth-abundant and efficient MOF catalysts were constructed by incorporating Cu(i) complexes with different steric functional groups for boosting photosynthesis.

Photosensitization associated with light absorption and energy/electron‐transfer represents the central processes for photosynthesis. However, it's still a challenge to develop a heavy‐atom‐free (HAF) strategy to improve the sensitizing ability of polymeric photosensitizers. Herein, we propose a new protocol to significantly improve the photosensitization by decorating mother conjugated microporous polymer (CMP‐1) with polycyclic aromatic hydrocarbons (PAHs), resulting in a series of CMPs (CMP‐2–4). Systematic study reveals that covalent modification with PAHs can transfer charge to Bodipy in CMP to further facilitate both intersystem crossing and electron‐hole separation, which can dramatically boost energy‐/electron‐transfer reactions. Remarkably, CMP‐2 as a representative CMP can efficiently drive the photosynthesis of methyl phenyl sulfoxide with 92 % yield, substantially higher than that of CMP‐1 (32 %). Experiments and theory calculations demonstrate the structure‐property‐activity relationship of these CMPs, opening a new horizon for developing HAF heterogeneous photosensitizers with highly efficient sensitizing activity by rational structure regulation at a molecular level.