Acetylene-Linked Octupolar Conjugated Microporous Polymers for CO Photoreduction to Methanol: Effect of Acceptor and π-Bridge Modulation.

The development of efficient, metal-free photocatalysts for solar-driven CO reduction to methanol is promising for alleviating energy and environmental issues, but achieving high selectivity and conversion efficiency without sacrificial agents or co-catalysts remains a challenge. In this work, we report a series of acetylene-linked specialized donor-acceptor (D-A) type conjugated microporous polymers (CMPs) designed with tailored electronic structures to investigate their efficacy in photocatalytic CO reduction to methanol in an aqueous NaOH solution under visible light irradiation. Significantly, the optimized porous polymer TTT-DEBP, featuring a strong electron-accepting triazine ring and an extended π-conjugated diethynyl biphenyl (DEBP) system, achieved a higher CHOH production rate of 30.

Harnessing Bio-Inspired Axial Coordination to Boost Synergistic Effects for Enhanced Bifunctional Oxygen Electrocatalysis.

Strategic alteration of the chelating atoms around the metal center can modify the electronic band structure of the electrocatalyst, improving its performance in oxygen evolution and reduction reactions (OER/ORR). Advancements in the development of catalysts with heteroatoms and axial modifications in the coordination sphere are mostly limited to single-molecule electrocatalysts or elevated temperature-mediated pyrolysis approaches for oxygen electrocatalysis. Inspired by biological catalytic systems with axial coordination, a pyrolysis-free strategic methodology is adopted for the synthesis of an iron-metaled covalent organic polymer matrix axially laminated over cobalt-based metal-organic framework through an imidazole moiety.

Electrochemical energy storage enhanced by intermediate layer stacking of heteroatom-enriched covalent organic polymers in exfoliated graphene.

Covalent organic polymers (COPs) have garnered attention as potential materials for various applications, including catalysis, gas storage, and energy production. Owing to their highly conjugated structures, chemical stability, adjustable band gap, and tunable functionality, COPs have emerged as a versatile material. However, their inherent structural rigidity and poor conductivity pose challenges for energy storage applications.

Electrochemical oxygen activation driven by enamine-keto push-pull interactions in triazole-based covalent organic polymers.

We have developed two triazole-based covalent organic polymers (COPs) with donor-acceptor motifs. The keto-enriched COP demonstrated exceptional oxygen activation electrochemical stimuli, driven by strong push-pull interactions. studies and DFT calculations confirmed the critical role of enamine carbon positive charges in enhancing performance, setting new benchmarks in COP design.

Coordination Structure Modulation in Group-VIB Metal Doped AgPO Augments Active Site Density for Electrocatalytic Conversion of N to NH.

Doping is considered a promising material engineering strategy in electrochemical nitrogen reduction reaction (NRR), provided the role of the active site is rightly identified. This work concerns the doping of group VIB metal in AgPO to enhance the active site density, accompanied by d-p orbital mixing at the active site/N interface. Doping induces compressive strain in the AgPO lattice and inherently accompanies vacancy generation, the latter is quantified with positron annihilation lifetime studies (PALS).

Lewis Acid Mediated Alteration of Electron Density on a Copper Site via pπ-dπ Mixing Enhances the Electrochemical Nitrogen Reduction Reaction.

Strategic modulation of the electronic structure of the catalyst to foster the electrochemical nitrogen reduction reaction (eNRR) to the ammonia process significantly is still an area that needs to be explored. Herein, we report the incorporation of the Lewis acid into an electron-rich copper site regulating the electron density of the metal, which has been experimentally proved from the d-band center position to have a direct influence on the adsorption of N compared to the protons. The catalyst boron doped copper-cuprous oxide hybrid system (B-Cu/CuO) has shown promising Faradaic efficiency of 32% at -0.

Nickel Nanoparticles Immobilized over Mesoporous SBA-15 for Efficient Carbonylative Coupling Reactions Utilizing CO: A Spotlight.

Ecofriendly routes for the synthesis of carbamates and carbonylative coupling products such as benzyl formate derivatives are very demanding for both academia and industries. Foreseeing a sustainable green future, we systematically analyzed the synthesis history of both these chemicals, mentioning their pros and cons. As a step towards green chemistry, here we have optimized the reaction conditions for the synthesis of various benzyl formates from corresponding benzyl halides and carbamates from substituted anilines and alkyl halides catalyzed by Ni(0) nanoparticles (NPs) immobilized over amine-functionalized ordered mesoporous SBA-15 material in the presence of CO as C1 source.