Modulating the Microenvironments of Robust Metal Hydrogen‐Bonded Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution

Hydrogen-bonded organic frameworks (HOFs) are outstanding candidates for photocatalytic hydrogen evolution. However, most of reported HOFs suffer from poor stability and photocatalytic activity in the absence of Pt cocatalyst. Herein, a series of metal HOFs (Co₂-HOF-X, X=COOMe, Br, tBu and OMe) have been rationally constructed based on dinuclear cobalt complexes, which exhibit exceptional stability in the presence of strong acid (12 M HCl) and strong base (5 M NaOH) for at least 10 days. More impressively, by varying the -X groups of the dinuclear cobalt complexes, the microenvironment of Co₂-HOF-X can be modulated, giving rise to obviously different photocatalytic H₂ production rates, following the -X group sequence of -COOMe>-Br>-tBu>-OMe. The optimized Co₂-HOF-COOMe shows H₂ generation rate up to 12.8 mmol g^-1 h^-1 in the absence of any additional noble-metal photosensitizers and cocatalysts, which is superior to most reported Pt-assisted photocatalytic systems. Experiments and theoretical calculations reveal that the -X groups grafted on Co₂-HOF-X possess different electron-withdrawing ability, thus regulating the electronic structures of Co catalytic centres and proton activation barrier for H₂ production, and leading to the distinctly different photocatalytic activity.