Zhen Liu

Efficient paired electrochemical synthesis requires precise synchronization between anodic intermediate generation and cathodic consumption. However, uncontrolled adsorption and mismatched reaction kinetics often result in intermediate accumulation and competing side reactions. Here, we address this challenge through interfacial regulation of both anodic and cathodic catalysts, enabling a synchronized electrocatalytic platform for α‐alkylation of nitriles using alcohols as sustainable alkyl sources. An Fe‐doped NiO anode and Pb/C cathode are rationally integrated to regulate alcohol oxidation, carbon–carbon coupling, and selective C═C hydrogenation. Fe incorporation tailors the electronic structure and adsorption behavior of Ni sites, accelerating alcohol activation while mitigating nitrile‐induced inhibition, whereas Pb/C selectively promotes alkene hydrogenation without affecting nitrile functionalities. The optimized paired system achieves 91.68% yield and >99% conversion for 2,3‐diphenylpropionitrile at 20 mA cm ⁻² , enabling continuous and efficient synthesis across a broad range of aromatic and aliphatic alcohols with excellent functional‐group tolerance and robust operational stability. This work provides a general catalyst design principle for paired electrochemical synthesis by coordinating interfacial reaction kinetics and intermediate flux between two electrodes.

Efficient paired electrochemical synthesis requires precise synchronization between anodic intermediate generation and cathodic consumption. However, uncontrolled adsorption and mismatched reaction kinetics often result in intermediate accumulation and competing side reactions. Here, we address this challenge through interfacial regulation of both anodic and cathodic catalysts, enabling a synchronized electrocatalytic platform for α‐alkylation of nitriles using alcohols as sustainable alkyl sources. An Fe‐doped NiO anode and Pb/C cathode are rationally integrated to regulate alcohol oxidation, carbon–carbon coupling, and selective C═C hydrogenation. Fe incorporation tailors the electronic structure and adsorption behavior of Ni sites, accelerating alcohol activation while mitigating nitrile‐induced inhibition, whereas Pb/C selectively promotes alkene hydrogenation without affecting nitrile functionalities. The optimized paired system achieves 91.68% yield and >99% conversion for 2,3‐diphenylpropionitrile at 20 mA cm ⁻² , enabling continuous and efficient synthesis across a broad range of aromatic and aliphatic alcohols with excellent functional‐group tolerance and robust operational stability. This work provides a general catalyst design principle for paired electrochemical synthesis by coordinating interfacial reaction kinetics and intermediate flux between two electrodes.

Selectively converting gaseous reactants via electrochemistry under industrially relevant lean feeds represents a green and sustainable pathway for gas upgrading and purification, yet achieving high selectivity remains challenging. Conventional catalysts are typically crystalline, with well-exposed active sites where competing reactions can readily occur, for example, parasitic hydrogen evolution and C–C coupling during electrochemical removal of trace acetylene from acetylene-lean streams. Here, we create an interface-confined reaction environment for selective acetylene semireduction into ethylene by introducing an amorphous corona onto crystalline Cu catalysts using electron-withdrawing ligands. The corona, with tunable chemistry and thickness, enriches acetylene near the catalyst surface while stabilizing active sites and key intermediates, thereby regulating reaction pathways. The optimized system achieves near-unity ethylene selectivity with strongly suppressed parasitic reactions, enabling efficient acetylene removal to below 5 ppm for 310 h. These findings establish the amorphous organic corona as a functional catalytic phase rather than merely a molecular ligand modification, and demonstrate its promise as an interface-confined design concept for selective gas electrocatalysis, with broader implications for gas upgrading and purification.

Removal of trace acetylene from ethylene is essential for polymer‐grade olefin production, yet current thermocatalytic purification requires elevated temperatures and hydrogen input. Here we report an electrified route for acetylene removal from ethylene streams using facet‐engineered Cu–TiO ₂ interfaces. By tuning the exposed facets of anatase TiO ₂ , we regulate the interfacial electronic interaction with supported Cu nanoclusters and thereby the balance among acetylene hydrogenation, hydrogen evolution, and carbon–carbon coupling. Among the catalysts examined, Cu–TiO ₂ {001} provides the most effective interfacial environment for selective acetylene‐to‐ethylene conversion, delivering an ethylene Faradaic efficiency (FE) of 95.4% under acetylene‐rich feed. Under purification‐relevant acetylene‐lean conditions, a 25 cm ² flow electrode suppresses residual acetylene to below 5 ppm while maintaining H ₂ FE below 5% during prolonged operation. Combined spectroscopy and theory indicate that the {001} facet strengthens Cu–TiO ₂ electronic coupling, stabilizes the Cu electronic structure and key hydrogenation intermediates under operating conditions, and disfavors competing pathways. Techno‐economic analysis supports the process potential of this electrified purification strategy.

Removal of trace acetylene from ethylene is essential for polymer‐grade olefin production, yet current thermocatalytic purification requires elevated temperatures and hydrogen input. Here we report an electrified route for acetylene removal from ethylene streams using facet‐engineered Cu–TiO ₂ interfaces. By tuning the exposed facets of anatase TiO ₂ , we regulate the interfacial electronic interaction with supported Cu nanoclusters and thereby the balance among acetylene hydrogenation, hydrogen evolution, and carbon–carbon coupling. Among the catalysts examined, Cu–TiO ₂ {001} provides the most effective interfacial environment for selective acetylene‐to‐ethylene conversion, delivering an ethylene Faradaic efficiency (FE) of 95.4% under acetylene‐rich feed. Under purification‐relevant acetylene‐lean conditions, a 25 cm ² flow electrode suppresses residual acetylene to below 5 ppm while maintaining H ₂ FE below 5% during prolonged operation. Combined spectroscopy and theory indicate that the {001} facet strengthens Cu–TiO ₂ electronic coupling, stabilizes the Cu electronic structure and key hydrogenation intermediates under operating conditions, and disfavors competing pathways. Techno‐economic analysis supports the process potential of this electrified purification strategy.

Electrocatalytic hydrogen peroxide (H ₂ O ₂ ) production through the two‐electron oxygen reduction reaction (2e ⁻ ORR) offers a promising route for sustainable H ₂ O ₂ synthesis under ambient conditions. However, the development of electrocatalysts that simultaneously exhibit high activity, selectivity, and stability remains challenging. Specifically, achieving precise control over catalytic centers remains challenging. Herein, an electron‐deficient linker engineering approach based on π‐conjugation tuning is proposed to tailor the electronic structure of nickel phthalocyanine (Ni−N ₄ ) active sites in covalent organic frameworks (COFs). Three dianhydride derivatives (i.e., benzene‐1,2,4,5‐tetracarboxylic dianhydride (PMDA), 1,4,5,8‐naphthalenetetracarboxylic dianhydride (NTDA), and perylene‐3,4,9,10‐tetracarboxylic dianhydride (PTDA)) were utilized to synthesize NiPc‐PMDA, NiPc‐NTDA, and NiPc‐PTDA COFs. Benefiting from the π‐conjugation‐tuned linker electronic properties, NiPc‐PTDA demonstrates an outstanding 2e ⁻ ORR selectivity of 92% and a high H ₂ O ₂ production rate of 34.8 mol g _cat ⁻¹ h ⁻¹ in a two‐electrode flow cell. Combined theoretical and experimental results support a correlation between linker electronic properties, the electronic state of the Ni centers, Ni–*OOH interaction, and the thermodynamic branching between H ₂ O ₂ release and further *OOH reduction. This work highlights the role of linker electronic properties in regulating catalytic centers and provides a π‐conjugation‐guided linker‐design approach for selective H ₂ O ₂ electrosynthesis in NiPc‐based COFs.

Oxygen activation is a cornerstone of sustainable electrosynthesis, yet controlling reactive intermediates without metallic centers remains challenging at industrial current densities. Here we establish nitrogen speciation as a molecular descriptor for governing oxygen activation in metal‐free macrocycles. Guided by density functional theory, we designed a tetra‐aza macrocycle with nearly exclusive pyridinic nitrogen, distinct from the mixed‐nitrogen environments of conventional porphyrins and phthalocyanines. This configuration uniquely stabilizes the key *OOH intermediate while strengthening interfacial electronic coupling with carbon supports. When integrated into a flow‐cell electrolyzer, the catalyst achieves ∼95% H ₂ O ₂ Faradaic efficiency and stability for over 800 h at 300 mA cm ⁻² , continuously generating >3 wt.% H ₂ O ₂ . Furthermore, in situ generated reactive oxygen species enable selective ambient upgrading of furfural to oxime (>90% yield). Techno‐economic analysis supports the economic viability of the process. By linking well‐defined nitrogen coordination to scalable device performance, this work provides a blueprint for translating molecular precision into practical electrocatalytic manufacturing.

Oxygen activation is a cornerstone of sustainable electrosynthesis, yet controlling reactive intermediates without metallic centers remains challenging at industrial current densities. Here we establish nitrogen speciation as a molecular descriptor for governing oxygen activation in metal‐free macrocycles. Guided by density functional theory, we designed a tetra‐aza macrocycle with nearly exclusive pyridinic nitrogen, distinct from the mixed‐nitrogen environments of conventional porphyrins and phthalocyanines. This configuration uniquely stabilizes the key *OOH intermediate while strengthening interfacial electronic coupling with carbon supports. When integrated into a flow‐cell electrolyzer, the catalyst achieves ∼95% H ₂ O ₂ Faradaic efficiency and stability for over 800 h at 300 mA cm ⁻² , continuously generating >3 wt.% H ₂ O ₂ . Furthermore, in situ generated reactive oxygen species enable selective ambient upgrading of furfural to oxime (>90% yield). Techno‐economic analysis supports the economic viability of the process. By linking well‐defined nitrogen coordination to scalable device performance, this work provides a blueprint for translating molecular precision into practical electrocatalytic manufacturing.

The spin-forbidden nature of triplet O ₂ activation poses a fundamental challenge for selective aerobic oxidative esterification of alcohols under mild conditions. Herein, we address this bottleneck via a coordination-number engineering strategy, precisely tailoring three-coordinate (Co _SA -N ₃ ) and four-coordinate (Co _SA -N ₄ ) cobalt single-atom catalysts. Reducing the coordination number triggers a high-spin Co(II) state with an upshifted d -band center, switching the O ₂ adsorption from a weak end-on ( η ¹ ) mode to a highly activated side-on ( η ² ) peroxo-like configuration on Co _SA -N ₃ . This electronic modulation substantially lowers the rate-determining hydrogen transfer barrier, enabling a near-quantitative ester yield of 98% under mild conditions. Furthermore, Aspen Plus simulations and techno-economic analysis validate the industrial feasibility and scalable profitability of this catalytic platform.

Proton exchange membrane (PEM) water electrolysis is vital for green hydrogen production, but its acidic oxygen evolution reaction (OER) is hindered by sluggish kinetics and catalyst delamination. To address this, a self-supported electrode was fabricated by anchoring Ru-deficient layered double hydroxides on a natural camphorwood substrate (NiRuv-LDH). Camphorwood's 3D hierarchical porous architecture provides structural integrity and hydrophilic microchannels that accelerate mass transport and gas release, eliminating polymeric binders. A chemical etching strategy successfully introduced atomic-scale Ru vacancies, reconfiguring the local electronic structure, reducing the rate-determining step barrier to 1.52 eV, and lowering the OER overpotential to 215 mV at 10 mA cm-2. In a PEM electrolyzer, the catalyst required only 1.75 V at 1.0 A cm-2 and demonstrated over 2,000 h of industrial-grade stability. Techno-economic analysis confirms its exceptional commercial viability, achieving a hydrogen production cost of ~US$ 0.3 per kg.