Chuan-De Wu

The hydrogenation of CO ₂ to N , N ‐dimethylformamide (DMF) with dimethylamine requires the concerted transformation of three distinct substrates, a fundamental kinetic challenge that mononuclear catalysts can only address through high‐barrier, sequential steps. Herein, we demonstrate a ligand‐enabled proximity strategy in binuclear Cp*Ir(III) complexes, wherein the spatial confinement of two metal centers facilitates the concerted activation of multiple substrates. The optimized binuclear architecture, equipped with strategically positioned ‒OH pendants, transforms the rate‐limiting termolecular collision into a kinetically favorable, low‐barrier pathway. This electronic and spatial cooperativity culminates in a turnover number of 1 540 000, placing the catalyst among the most efficient molecular systems reported for DMF production with selectivity approaching quantitative (> 99%). Integrated computational and spectroscopic studies reveal that the dual‐Ir framework mitigates the entropic penalty inherent to termolecular processes, while the hydroxyl functionality polarizes the Ir‒H bond to promote H ₂ heterolysis and CO ₂ insertion. In situ NMR and infrared spectroscopy directly identify the key Ir–hydride and Ir–formate intermediates, providing experimental validation of the computationally predicted low‐barrier pathway. These findings establish for the first time how multimetallic cooperativity and secondary coordination sphere effects operate in concert to bypass the intrinsic kinetic limitations of single‐site catalysts.

The hydrogenation of CO ₂ to N , N ‐dimethylformamide (DMF) with dimethylamine requires the concerted transformation of three distinct substrates, a fundamental kinetic challenge that mononuclear catalysts can only address through high‐barrier, sequential steps. Herein, we demonstrate a ligand‐enabled proximity strategy in binuclear Cp*Ir(III) complexes, wherein the spatial confinement of two metal centers facilitates the concerted activation of multiple substrates. The optimized binuclear architecture, equipped with strategically positioned ‒OH pendants, transforms the rate‐limiting termolecular collision into a kinetically favorable, low‐barrier pathway. This electronic and spatial cooperativity culminates in a turnover number of 1 540 000, placing the catalyst among the most efficient molecular systems reported for DMF production with selectivity approaching quantitative (> 99%). Integrated computational and spectroscopic studies reveal that the dual‐Ir framework mitigates the entropic penalty inherent to termolecular processes, while the hydroxyl functionality polarizes the Ir‒H bond to promote H ₂ heterolysis and CO ₂ insertion. In situ NMR and infrared spectroscopy directly identify the key Ir–hydride and Ir–formate intermediates, providing experimental validation of the computationally predicted low‐barrier pathway. These findings establish for the first time how multimetallic cooperativity and secondary coordination sphere effects operate in concert to bypass the intrinsic kinetic limitations of single‐site catalysts.

Spatially confined donor–acceptor type polymeric microcavities featuring pyridazine sites for selective O ₂ activation enable synchronized proton–electron–oxygen transport, achieving efficient H ₂ O ₂ photosynthesis (8160 μmol g ⁻¹ h ⁻¹ ) in pure water.

Hydrocarbons derived from petroleum typically undergo energy‐intensive fractional distillations. Membrane separation technologies with high permeability and selectivity offer an energy‐efficient alternative. However, traditional membranes frequently encounter issues, such as swelling, deformation and diminished flux. Herein, quaternary ammonium salts are utilized to precisely control the interlayer spacing of graphene oxide (GO), facilitating the in situ growth of zeolitic imidazolate framework (ZIF‐8) to develop ZIF‐8‐GO membranes for shale oil separation. The ZIF‐8 nanoparticles serve to cross‐link the GO layers, effectively expanding the interlayer spacing and preventing swelling in organic solvents. The resultant ZIF‐8‐GO membrane achieves nearly complete rejection of n‐docosane in n‐hexane with a solvent permeance of 16.4 ± 0.8 L m ⁻² h ⁻¹ bar ⁻¹ , which is 71 times higher than that of commercial membranes such as the PuraMem ^® membrane (0.23 L m ⁻² h ⁻¹ bar ⁻¹ ), and surpasses previously reported membranes. The membrane is capable of concentrating hydrocarbons containing fewer than 20 carbon atoms and maintains its separation efficiency when transitioning from simple binary mixtures to more complex shale oil. This research opens a new avenue for the integration of MOF‐GO membranes into petroleum fractionation and provides a practical framework for the precise separation of shale oil.

This feature article summarizes the recent advances in constructing porous biomimetic catalyst platforms by using porous materials as the supporting matrices.

Three polyoxometalate-based hybrid coordination materials, [Co8(H2O)34(pz)2{Co4(H2O)2P4W30O112}]·16H2O (compound 1), [H3O]4[Co6(H2O)22(pz)2{Co4(H2O)2P

The synthesized p–d hybrid Ni–Al NC catalyst can withstand potential changes in electrocatalytic CO ₂ reduction to CO.

Reductive ring-opening of epoxides is a green pathway for synthesizing highly value-added alcohols. In this study, we present a practically applicable approach for the synthesis of anti-Markovnikov-type alcohols with high yields from aliphatic and aromatic epoxides under mild conditions by developing porous metal silicate (PMS) catalysts. A PMS material PMS-20 consists of cobalt and nickel bimetal redox-active sites, exhibiting exceptional catalytic activity and selectivity in the reductive ring-opening of terminal epoxides with >99% yield of primary alcohols. Comparing with the existing methods using noble metals, PMS-20 exhibits broad substrate scope and excellent functional group tolerance by synergistic work between cobalt and nickel species, which is clarified by dual chamber cell system characterization and theoretical calculation results.

The hydrodeoxygenation transformation of lignin-derived phenols provides an attractive pathway for the production of renewable biofuels; however, harsh process conditions strongly hinder its practical application. Herein, we report a porous metal silicate (PMS) material, PMS-36, which consists of metallic nickel and Lewis acid Al^III sites inside the pores, demonstrating high efficiency in catalyzing the hydrodeoxygenation transformation of guaiacol under mild conditions. PMS-36 also exhibits robust stability, which can be attributed to the strong interaction and charge transfer between metallic Ni and Al^III Lewis acid sites inside the confined pores. This study shows the importance of synergistic and confinement effects in developing high-performance and stable heterogeneous catalysts for the chemical transformation of biomass and its derivatives.