Chuanqi Cheng

Electrocatalytic conversion of water‐soluble organics in aqueous media offers a sustainable route to high‐value chemicals, yet sluggish mass transport remains a critical bottleneck at industrially relevant current densities. Here, dimethyl sulfoxide (DMSO) is employed as the modifier to enhance mass transport by reconstructing hydrogen‐bond (H‐bond) networks. In the bulk electrolyte, DMSO inserts into the dense hydrogen bonds to expand the free‐volume distribution, releasing reactants from the solvation shell and accelerating their diffusion. Simultaneously, interfacial interactions between DMSO, reactants, and cations enrich local reactant concentrations, cooperatively facilitating the reaction kinetics. This dual‐enhancement mechanism achieves ∼60% Faradaic efficiency (FE) in electrocatalytic dehalogenative hydrogenolysis at 300 mA cm ⁻² . Our strategy demonstrates broad utility across the dehalogenative hydrogenation of other halogenated substrates and the hydrogenation of nitriles/nitro compounds, delivering >10% FE improvements. By coupling bulk diffusion acceleration with interfacial reactant enrichment, this work offers a promising strategy to overcome mass transport limitations in aqueous electrosynthesis.

Electrocatalytic conversion of water‐soluble organics in aqueous media offers a sustainable route to high‐value chemicals, yet sluggish mass transport remains a critical bottleneck at industrially relevant current densities. Here, dimethyl sulfoxide (DMSO) is employed as the modifier to enhance mass transport by reconstructing hydrogen‐bond (H‐bond) networks. In the bulk electrolyte, DMSO inserts into the dense hydrogen bonds to expand the free‐volume distribution, releasing reactants from the solvation shell and accelerating their diffusion. Simultaneously, interfacial interactions between DMSO, reactants, and cations enrich local reactant concentrations, cooperatively facilitating the reaction kinetics. This dual‐enhancement mechanism achieves ∼60% Faradaic efficiency (FE) in electrocatalytic dehalogenative hydrogenolysis at 300 mA cm ⁻² . Our strategy demonstrates broad utility across the dehalogenative hydrogenation of other halogenated substrates and the hydrogenation of nitriles/nitro compounds, delivering >10% FE improvements. By coupling bulk diffusion acceleration with interfacial reactant enrichment, this work offers a promising strategy to overcome mass transport limitations in aqueous electrosynthesis.

The intensified hydrogen evolution reaction (HER) competition is an elusive obstacle for the practical application of electrocatalytic acetylene (C ₂ H ₂ ) hydrogenation (EAH) for petroleum‐independent ethylene (C ₂ H ₄ ) formation. Fundamentally, ambiguous mechanistic insight severely hinders the rational design of efficient catalysts, leaving the identification of Eley–Rideal (E–R) or Langmuir–Hinshelwood (L–H) mechanisms as intrinsic challenges. Here, the L–H pathway is proven to be the predominant route, which is regarded as the principle for catalyst design. Consequently, a bimetallic AgPd alloy (AgPd NPs) is predicted and proven to be a promising catalyst. Accordingly, the AgPd NPs deliver a C ₂ H ₄ partial current density of 0.47 A cm ⁻² and a turnover frequency (TOF) of 8.27 s ⁻¹ (1.66‐fold vs. the Ag counterpart under equal conditions). In situ spectroscopic characterizations unveil that the Pd dopants could not only induce *H transfer to free sites to increase C ₂ H ₂ mass transfer, but also optimize the match degree of surface *H and *C ₂ H ₂ . *H migration‐enabled transport modulation could efficiently enhance the turnover process, simultaneously promoting C ₂ H ₄ formation while inhibiting HER competition.

The intensified hydrogen evolution reaction (HER) competition is an elusive obstacle for the practical application of electrocatalytic acetylene (C ₂ H ₂ ) hydrogenation (EAH) for petroleum‐independent ethylene (C ₂ H ₄ ) formation. Fundamentally, ambiguous mechanistic insight severely hinders the rational design of efficient catalysts, leaving the identification of Eley–Rideal (E–R) or Langmuir–Hinshelwood (L–H) mechanisms as intrinsic challenges. Here, the L–H pathway is proven to be the predominant route, which is regarded as the principle for catalyst design. Consequently, a bimetallic AgPd alloy (AgPd NPs) is predicted and proven to be a promising catalyst. Accordingly, the AgPd NPs deliver a C ₂ H ₄ partial current density of 0.47 A cm ⁻² and a turnover frequency (TOF) of 8.27 s ⁻¹ (1.66‐fold vs. the Ag counterpart under equal conditions). In situ spectroscopic characterizations unveil that the Pd dopants could not only induce *H transfer to free sites to increase C ₂ H ₂ mass transfer, but also optimize the match degree of surface *H and *C ₂ H ₂ . *H migration‐enabled transport modulation could efficiently enhance the turnover process, simultaneously promoting C ₂ H ₄ formation while inhibiting HER competition.

Although metal‒carbon bonds are prevalent in organometallics, integrating carbon donors alongside nitrogen, oxygen, and sulfur heteroatoms into the first coordination sphere of metal complexes poses a considerable challenge. Here, graphdiyne‐based sp‐carbon atoms are incorporated into the first coordination sphere of the metal complex, yielding an asymmetric sp‐C ₂ –M–O ₂ (M = Cu, Co, Ni) coordination geometry. During synthesis, hydrogen‐substituted graphdiyne (HsGDY) acts as a microporous polymeric ligand populated with periodically aligned diacetylene coordination sites, which spatially confine and arrange metal complexes within micropores featuring a dominant size of 1.5 nm. For the electrochemical NO reduction, the microporous framework of HsGDY, which is rich in sp‐carbons, accelerates NO mass transport, enabling elevated NO surface coverage even under diluted NO feeding streams. The electron‐donating sp‐carbons synergize with oxygen to tune the electronic structure of Cu ^δ+ (1 < δ < 2), reducing the formation barrier of *HNO and thus achieving a high NH ₃ Faradaic efficiency of 91.8% and a yield rate of 0.44 mg h ⁻¹ cm ² at 0.1 V versus a reversible hydrogen electrode (RHE). This work identifies graphdiyne‐based sp‐carbon atoms as viable constituents of the first coordination sphere of metal complexes, breaking the reliance on nitrogen, oxygen, and sulfur heteroatoms for constructing nonaxial asymmetric coordination geometries.

Although metal‒carbon bonds are prevalent in organometallics, integrating carbon donors alongside nitrogen, oxygen, and sulfur heteroatoms into the first coordination sphere of metal complexes poses a considerable challenge. Here, graphdiyne‐based sp‐carbon atoms are incorporated into the first coordination sphere of the metal complex, yielding an asymmetric sp‐C ₂ –M–O ₂ (M = Cu, Co, Ni) coordination geometry. During synthesis, hydrogen‐substituted graphdiyne (HsGDY) acts as a microporous polymeric ligand populated with periodically aligned diacetylene coordination sites, which spatially confine and arrange metal complexes within micropores featuring a dominant size of 1.5 nm. For the electrochemical NO reduction, the microporous framework of HsGDY, which is rich in sp‐carbons, accelerates NO mass transport, enabling elevated NO surface coverage even under diluted NO feeding streams. The electron‐donating sp‐carbons synergize with oxygen to tune the electronic structure of Cu ^δ+ (1 < δ < 2), reducing the formation barrier of *HNO and thus achieving a high NH ₃ Faradaic efficiency of 91.8% and a yield rate of 0.44 mg h ⁻¹ cm ² at 0.1 V versus a reversible hydrogen electrode (RHE). This work identifies graphdiyne‐based sp‐carbon atoms as viable constituents of the first coordination sphere of metal complexes, breaking the reliance on nitrogen, oxygen, and sulfur heteroatoms for constructing nonaxial asymmetric coordination geometries.

Electrosynthesis of epoxides from alkenes represents a safe and sustainable strategy to replace conventional synthetic methods that require harsh conditions. However, its practical industrial application is greatly restricted by low current density, competitive oxygen evolution reaction (OER), and poor electrocatalyst stability. Herein, we constructed a Co3O4/CeO2 heterojunction electrocatalyst with enhanced activity and stability toward chlorine (Cl)-involved anodic reactions. Spectroscopic and electrochemical characterizations combined with theoretical calculations reveal that strong electronic coupling at the heterointerface drives directional electron transfer from CeO2 to Co3O4, accelerating electron transport and facilitating Cl– activation. Moreover, the compressed Co–O bond of Co3O4/CeO2 enhances the stability and thus breaks the activity/stability tradeoff. Under practical conditions (100 mA cm–2), Co3O4/CeO2 not only realizes the gram-scale electrosynthesis of cyclohexene oxide with high Faradaic efficiency but also is suitable for other chlorination reactions. Our study provides a heterojunction-engineering strategy to promote the electrooxidation activity for Cl-involved anodic reactions.

Electrocatalytic hydrogenation offers a promising route to value‐added chemicals, yet mass transport limitations at industrial current densities remain a critical challenge. Here, we introduce a cyclodextrin‐regulated interfacial microenvironment that delivers a Faradaic efficiency (FE) of up to 88% for pyrazine hydrogenation at −100 mA cm ⁻² . The hydroxyl‐rich outer surface disrupts the ordered hydrogen‐bond network by inhibiting the reorientation of interfacial H ₂ O, facilitating the migration of the reactant to the electrode surface. Simultaneously, the hydrophobic cavities selectively recognize and bind substrates via host–guest interactions, creating oriented shuttle channel that lowers the transfer energy barrier and accelerates mass transport kinetics. This strategy can be extended to diverse hydrogenation reactions and to other deuteration reactions with improved FE at −100 mA cm ⁻² . Moreover, the synthesis of deuterated piperazines and their conversion into deuterium‐labeled drugs highlights their practical potential. This work provides a general interfacial engineering strategy to overcome mass transport bottlenecks in electrosynthesis, with broad implications for the production of high‐value chemicals and isotopically labeled compounds.