Feng Peng

Photoassisted aqueous zinc batteries provide a compact route to couple light input with electrochemical energy storage, but the ionic origin of light-enhanced capacity remains difficult to quantify because proton and zinc-ion storage pathways are strongly intertwined. Here, a self-supported Cu/Cu₂S nanoarray is used as a light-responsive conversion interface to resolve illumination-regulated H⁺/Zn²⁺ partitioning. By tuning proton accessibility through dimethylformamide, H₂O/dimethylformamide, and H₂O electrolyte matrices, the dominant charge carrier shifts from Zn²⁺-favored storage to nearly balanced H⁺/Zn²⁺ storage and then to H⁺-dominated storage. Illumination enlarges the cyclic voltammetry response by 110.2%, reduces polarization, and enables nearly 50% capacity enhancement at 5 A g^-1. State-resolved Raman spectroscopy, X-ray photoelectron spectroscopy, and ex situ X-ray diffraction reveal light-regulated ZnS/basic-zinc-salt evolution and improved Cu/S interfacial reversibility. These findings identify nanoscale Cu-S conversion interfaces as light-tunable platforms for directing proton-cation competition, offering a carrier-resolved design principle for photoassisted aqueous batteries.

The electrooxidation of liquid alcohols is conventionally characterized by peak-shaped voltammograms that conflate kinetic and mass-transport effects, precluding rigorous catalyst evaluation. This ambiguity stems from an unresolved competition: the hydroxide ion (OH−) is essential for reaction kinetics but, in excess, poisons the surface via rapid oxidation. Here, deliberate control of mass transport resolves this conflict, enabling the first engineering of well-defined limiting-current plateaus for methanol and ethanol oxidation. This plateau explicitly reveals an OH−-diffusion-limited regime, exposing a universal flux-activity trade-off. We leverage this insight to establish a transport-aware benchmarking framework, quantifying intrinsic activity, stability, and a new metric of flux-induced kinetic poisoning sensitivity. By balancing reactant fluxes to circumvent kinetic poisoning, an unprecedented record of geometric current density exceeding 1 A cm−2 was achieved for methanol oxidation. Our work redefines the optimization paradigm for complex electrocatalytic reactions, shifting the focus from static activity metrics to mastering dynamic interfacial flux.

As a core concept of heterogeneous catalysis, metal‐support interactions are pivotal controlling activity, selectivity, and stability via electronic and geometric effects. Here, we report a reactant‑transporting form of metal support interaction (MSI), named as strong metal‐reactive support interaction (SMRSI) where Pt/H ₂ directly hydrogenates lattice carbonate in calcite to CH ₄ with ≤ 415 °C onset and ∼98% selectivity (390–510°C). Because lattice carbon in carbonate minerals constitutes Earth's largest carbon reservoir, enabling low‑temperature lattice–carbonate conversion offers a catalytic lever to accelerate the slow carbon cycle (ACC) complementary to fast carbon cycle (FCC)‑based CO ₂ management. Operando techniques show a permeable amorphous interphase that dynamically encapsulates Pt, transports CO ₃ ²⁻ to active sites, and crystallizes into Ca(OH) ₂ , thereby sustaining a mobile triple‑phase boundary, where carbonate‑derived *CO intermediate was hydrogenated to CH ₄ . It is resolved that a low‑temperature interfacial CO ₂ release is diagnostic of boundary decomposition. Kinetics separate a CO ₃ ²⁻ ‑diffusion‑limited solid‑state path at low temperatures from a high‑temperature route akin to gaseous‑CO ₂ hydrogenation. The hydrogenated solid is re‐carbonated by CO ₂ , regenerating CaCO ₃ and retaining selectivity over cycles. Conceptually, the SMRSI extends MSI from electronic/geometric tuning to reactant transport, illustrating how moving solid‐solid@gas interfaces mediate transformations of solid reactants.

As a core concept of heterogeneous catalysis, metal‐support interactions are pivotal controlling activity, selectivity, and stability via electronic and geometric effects. Here, we report a reactant‑transporting form of metal support interaction (MSI), named as strong metal‐reactive support interaction (SMRSI) where Pt/H ₂ directly hydrogenates lattice carbonate in calcite to CH ₄ with ≤ 415 °C onset and ∼98% selectivity (390–510°C). Because lattice carbon in carbonate minerals constitutes Earth's largest carbon reservoir, enabling low‑temperature lattice–carbonate conversion offers a catalytic lever to accelerate the slow carbon cycle (ACC) complementary to fast carbon cycle (FCC)‑based CO ₂ management. Operando techniques show a permeable amorphous interphase that dynamically encapsulates Pt, transports CO ₃ ²⁻ to active sites, and crystallizes into Ca(OH) ₂ , thereby sustaining a mobile triple‑phase boundary, where carbonate‑derived *CO intermediate was hydrogenated to CH ₄ . It is resolved that a low‑temperature interfacial CO ₂ release is diagnostic of boundary decomposition. Kinetics separate a CO ₃ ²⁻ ‑diffusion‑limited solid‑state path at low temperatures from a high‑temperature route akin to gaseous‑CO ₂ hydrogenation. The hydrogenated solid is re‐carbonated by CO ₂ , regenerating CaCO ₃ and retaining selectivity over cycles. Conceptually, the SMRSI extends MSI from electronic/geometric tuning to reactant transport, illustrating how moving solid‐solid@gas interfaces mediate transformations of solid reactants.

Electro-reforming of biomass into value-added chemicals offers a sustainable approach for future energy developments. However, noble metal catalysts toward glucose electrooxidation suffer from deactivation, poor selectivity, and limited power density. Here, we present Au ^δ− -Cu ^δ+ sites in AuCu alloy that serve as stable and efficient catalyst for selective glucose electrooxidation to potassium gluconate at high current density. AuCu alloy ensures the co-adsorption of OH ⁻ on electron-deficient Cu ^δ+ sites and glucose on electron-rich Au ^δ− sites, stimulating the formation of oxidative *OH and intermediates. Selective adsorption of OH species on Cu ^δ+ sites also restrains the Au-OH formation and its subsequent oxidation to AuO _x , thereby preventing catalyst deactivation. Especially, for glucose electrooxidation, Au ₄ Cu ₂ alloy delivers a high selectivity toward potassium gluconate (97.15%), along with a low potential of 0.74 V (versus reversible hydrogen electrode) to achieve industrial current density of 500 mA cm ⁻² . Furthermore, Au ₄ Cu ₂ alloy realizes a stable electrolysis with a potassium gluconate productivity of 9.46 mmol cm ^–2 h ^–1 and Faraday efficiency of 93.60% in the membrane-free flow electrolyzer.

The advancement of carbon dioxide electroreduction (CO ₂ RR) from fundamental research to industrial deployment represents a multifaceted systems engineering challenge, demanding integrated optimization beyond isolated catalyst performance. This review synthesizes progress and hurdles across five critical subsystems: (1) feedstock CO ₂ supply and purification, (2) coupled reaction and product separation, (3) energy input integration with renewable sources, (4) upgrading of anode reactions beyond oxygen evolution reaction, and (5) innovative reactor design and scale‐up. We argue that achieving techno‐economic viability and net environmental benefit requires a paradigm shift from single‐component optimization to system‐level integration and process synergy. In this endeavor, process simulation tools, exemplified by the Aspen suite, act as an indispensable virtual laboratory, enabling quantitative analysis of mass and energy balances, techno‐economic assessment, and life cycle evaluation to de‐risk scale‐up. Future development must prioritize enhanced model accuracy, dynamic control for renewable intermittency, advanced materials development, and scale‐up engineering to fully realize CO ₂ RR as a cornerstone technology for carbon neutrality, energy structure transformation, and a sustainable chemical industry.