Zhongjian Li

A hybrid system combining water electrolysis and H ₂ autotrophic microorganism enables sustainable CO ₂ valorization, but is hindered by low H ₂ bioavailability and sluggish hydrogenase kinetics. Here, we report an interface-engineered inorganic–biological biohybrid, constructed by covalently anchoring iron single-atom catalysts (ISA) onto Cupriavidus necator ( C.N @ISA) via click chemistry. The ISA anchored interface generates a localized H ₂ -rich microenvironment, accelerates H ₂ dissociation, while the synergy between ISA and polyethylene glycol-phenylboronate linker stabilizes the inorganic-biological hybrid interface and promotes electron/proton transfer across microbial membrane. These coupled effects boost reduced form of nicotinamide adenine dinucleotide (NADH) regeneration and adenosine triphosphate (ATP) synthesis. In addition, ISA exhibits nanozyme-like activity, scavenging reactive oxygen species to protect cell viability. As a result, C.N @ISA achieves CO ₂ -to-bioplastic poly- β -hydroxybutyrate production of 1058.8 mg L ⁻¹ with a Faradaic efficiency of 42.0%. Integrating theoretical calculations, electrochemical analysis, and transcriptomics confirms that ISA simultaneously enriches and activates H ₂ while reinforcing intracellular metabolism, offering a generalizable strategy for carbon-negative biomanufacturing.

Producing hydrogen from formaldehyde oxidation reaction (FOR) offers a promising low‐energy approach for generating clean fuel. However, the FOR involves continuous C─H bond cleavage of adsorbed intermediates to generate abundant surface H*. This necessitates rapid transfer and consumption of H* to sustain fast oxidation kinetics. Herein, we developed a hydrogen‐spillover strategy to redistribute these surface H* to accelerate FOR kinetics by constructing RhCu single‐atom alloy supported on a Cu single‐atom‐rich carbon matrix (RhCu@Cu _SA NC). In this design, Cu incorporation creates a favorable landscape for H* migration toward the Cu _SA NC support, which acts as efficient H* acceptors and H─H coupling centers. Verified through multiple analyses, this hydrogen‐spillover mechanism is demonstrated to enhance FOR activity by accelerating H* redistribution. Consequently, RhCu@Cu _SA NC shows outstanding FOR performance, achieving a current density of 800 mA cm ^{− 2} at 0.39 V with nearly 100% H ₂ selectivity and excellent durability. When integrated into a hybrid alkali‐acid cell, it provides an open circuit voltage of 1.72 V and peak power density of 152.6 mW cm ^{− 2} with stable H ₂ production for over 1200 h at 10 mA cm ^{− 2} . These results demonstrate that hydrogen spillover boosts oxidative electrocatalysis, providing a general design principle for multicomponent catalysts with coordinated hydrogen dynamics.

Producing hydrogen from formaldehyde oxidation reaction (FOR) offers a promising low‐energy approach for generating clean fuel. However, the FOR involves continuous C─H bond cleavage of adsorbed intermediates to generate abundant surface H*. This necessitates rapid transfer and consumption of H* to sustain fast oxidation kinetics. Herein, we developed a hydrogen‐spillover strategy to redistribute these surface H* to accelerate FOR kinetics by constructing RhCu single‐atom alloy supported on a Cu single‐atom‐rich carbon matrix (RhCu@Cu _SA NC). In this design, Cu incorporation creates a favorable landscape for H* migration toward the Cu _SA NC support, which acts as efficient H* acceptors and H─H coupling centers. Verified through multiple analyses, this hydrogen‐spillover mechanism is demonstrated to enhance FOR activity by accelerating H* redistribution. Consequently, RhCu@Cu _SA NC shows outstanding FOR performance, achieving a current density of 800 mA cm ^{− 2} at 0.39 V with nearly 100% H ₂ selectivity and excellent durability. When integrated into a hybrid alkali‐acid cell, it provides an open circuit voltage of 1.72 V and peak power density of 152.6 mW cm ^{− 2} with stable H ₂ production for over 1200 h at 10 mA cm ^{− 2} . These results demonstrate that hydrogen spillover boosts oxidative electrocatalysis, providing a general design principle for multicomponent catalysts with coordinated hydrogen dynamics.

Electrochemical CO ₂ reduction (eCO ₂ R) powered by renewable electricity offers a sustainable route for carbon cycling and value‐added chemical synthesis. Among possible products, methane (CH ₄ ) is particularly attractive due to its high energy density and direct compatibility with existing natural gas infrastructure. However, it remains challenging to selectively produce CH ₄ with conventional copper catalysts. Herein, we developed a copper–phenolic network catalyst featuring atomically dispersed Cu─O ₄ sites, where adjacent uncoordinated hydroxyl groups from tannic acid (TA) act as intrinsic hydrogen‐bond donors to stabilize the oxygen‐bound formate intermediate (*OCHO). This hydrogen‐bond‐enabled microenvironment redirects eCO ₂ R from the conventional *CO‐mediated pathway toward a formate‐derived route, while simultaneously suppressing the competing hydrogen evolution reaction. As a result, the optimized Cu‐PTA catalyst delivers a high CH ₄ Faradaic efficiency of 75.5% with a partial current density of 302.0 mA cm ⁻² in aqueous electrolyte. Notably, this pathway‐steering strategy is readily applicable to deuterated electrolytes, enabling efficient production of deuterated methane (CD ₄ ) with a record‐high Faradaic efficiency of 83.1% and a partial current density of 415.6 mA cm ⁻² . This work establishes hydrogen‐bond engineering as a general approach for manipulating reaction pathways through local stabilization of oxygen‐bound intermediates toward sustainable synthesis of high‐value chemicals.

Electrochemical CO ₂ reduction (eCO ₂ R) powered by renewable electricity offers a sustainable route for carbon cycling and value‐added chemical synthesis. Among possible products, methane (CH ₄ ) is particularly attractive due to its high energy density and direct compatibility with existing natural gas infrastructure. However, it remains challenging to selectively produce CH ₄ with conventional copper catalysts. Herein, we developed a copper–phenolic network catalyst featuring atomically dispersed Cu─O ₄ sites, where adjacent uncoordinated hydroxyl groups from tannic acid (TA) act as intrinsic hydrogen‐bond donors to stabilize the oxygen‐bound formate intermediate (*OCHO). This hydrogen‐bond‐enabled microenvironment redirects eCO ₂ R from the conventional *CO‐mediated pathway toward a formate‐derived route, while simultaneously suppressing the competing hydrogen evolution reaction. As a result, the optimized Cu‐PTA catalyst delivers a high CH ₄ Faradaic efficiency of 75.5% with a partial current density of 302.0 mA cm ⁻² in aqueous electrolyte. Notably, this pathway‐steering strategy is readily applicable to deuterated electrolytes, enabling efficient production of deuterated methane (CD ₄ ) with a record‐high Faradaic efficiency of 83.1% and a partial current density of 415.6 mA cm ⁻² . This work establishes hydrogen‐bond engineering as a general approach for manipulating reaction pathways through local stabilization of oxygen‐bound intermediates toward sustainable synthesis of high‐value chemicals.

Plasma–electrocatalytic cascade ammonia synthesis offers a promising route for decentralized nitrogen fixation, yet remains hindered by excessive NO3– formation and poor energy matching between the two stages. Here, we propose a strategy that breaks this bottleneck by selectively generating NO2– via spark-discharge plasma and efficiently reducing it over a CuRu0.5 nanoalloy. Systematic optimization of the plasma discharge and electrocatalytic interface enables synergistic energy matching, delivering a record-low specific energy consumption of 273.41 kWh/kg NH3. Mechanistic studies reveal that Ru modulates the electronic structure of Cu, enhancing NO2– adsorption and deoxygenation while suppressing the hydrogen evolution reaction. This work establishes a generalized paradigm for low-energy, high-selectivity ammonia synthesis from air and water.

Selective resource recovery from waste streams is essential for sustainable nitrogen management. However, conventional ammonia recovery from ammonium (NH₄⁺)-and volatile organic compound (VOC)-containing wastewater is highly energy-intensive, and VOC-NH₃ coevaporation further undermines product purity. Here we report an advanced oxidation processes-interfacial solar steam generation (AOPs-ISSG) platform based on a cobalt oxide-loaded nitrogen-doped carbon catalyst (Co-NC) that integrates photothermal conversion and catalytic oxidation. By exploiting the differing adsorption, electron-transfer, and reactive oxygen species (ROS) reactivity of VOCs and NH₃, the system achieves selective VOC oxidation while preserving ammonia. Combined with alkaline solar interfacial evaporation, this selectivity supports concurrent VOC removal and efficient NH₃ recovery. Under simulated wastewater conditions (pH = 9), the Co-NC/AOPs-ISSG system achieves 90.1% NH₃ recovery and 95.3% VOC removal. It also demonstrates broad operational resilience across pH 7–10 and solar intensities up to 1.4 kW m^–2, consistently yielding high-purity ammonia suitable for direct reuse, as validated by plant experiments in which recovered-ammonia irrigation promoted ∼40% greater pea seedling growth compared with untreated wastewater. Solar utilization and process integration reduce operating cost and carbon emissions by 23.2% and 27.7% compared with conventional NH₃ recovery. These results highlight a low-carbon, economically viable pathway for selective ammonia recovery and sustainable nitrogen management.

Photocatalytic biohybrid systems, which interface photosensitizers with whole‐cell biocatalysts, represent a platform for sustainable solar‐to‐chemical CO ₂ conversion. However, their efficiency is fundamentally constrained by kinetic mismatch between sluggish transmembrane electron injection and uncoupled proton flux required for bioenergetic transduction. This uncoupling restricts the regeneration of adenosine triphosphate (ATP) and reduced nicotinamide adenine dinucleotide (NADH), the dual cofactors essential for driving carbon fixation pathways. Here, we introduce a proton enrichment strategy utilizing protonated manganese‐doped carbon dots (HMnCDs) that function simultaneously as reversible proton buffers and photoelectron donors. HMnCDs localize to the periplasm of Cupriavidus necato r H16, where their labile protons reinforce the transmembrane proton gradient driving ATP synthase. Concurrently, cytoplasmic HMnCDs facilitate proton‐coupled electron transfer, accelerating NADH photoregeneration. The concerted management of proton and electron fluxes decouples ATP generation from respiratory NADH oxidation, creating a synergistic cofactor supply even under electron transport chain inhibition. Consequently, the biohybrid achieves light‐driven autotrophic growth and poly(3‐hydroxybutyrate) biosynthesis from CO ₂ , attaining a record quantum efficiency of 20.8%. Multi‐omics analyses reveal global metabolic reprogramming, including upregulated carbon fixation pathways and adaptive modulation of energy homeostasis under the proton‐enriched microenvironment. This work establishes proton enrichment as a generalizable design principle for coupling photochemistry with cellular bioenergetics.