Jie Zeng

Photothermal catalysis under mild conditions offers a promising approach for converting CO2 into value-added chemicals. Herein, we propose a strategy to achieve atomic dispersion of Ni on a low-valence metal oxide (MnO), enabling the Ni species to maintain a stable atomically dispersed state under reducing atmospheres (NiAD/MnO). In comparison, the Ni atoms anchored on high-valence MnO2 go through high-temperature reduction aggregation and sintering due to the crystal phase transformation of the support (NiNP/MnO). In the photothermal reverse water–gas shift (RWGS) reaction, NiAD/MnO achieved a CO production rate of 9.9 mmol g–1 h–1 with 99.9% CO selectivity (410 °C), far exceeding the performance of NiNP/MnO. Transient experiments and in situ spectroscopic characterization revealed that the photothermal RWGS reaction proceeds via a redox mechanism mediated by axial oxygen atoms coordinated with Ni. Theoretical calculations further demonstrated that light irradiation boosted the CO2 hydrogenation via effectively reducing the energy barrier for *CO desorption on NiAD/MnO.

Transition-metal-catalyzed C–N cross-coupling is fundamental to the synthesis of pharmaceuticals, agrochemicals, and functional materials. However, many copper-based catalytic systems rely on exogenous molecular ligands to establish and tune the coordination environment around copper centers, which can increase catalyst-design complexity and complicate catalyst recovery and reuse. We report a copper single-atom catalyst (Cu–N3/OMC) that enables ligand-free C–N and C–O cross-coupling of aryl electrophiles, with isolated Cu sites embedded in a nitrogen-doped carbon framework that provides an intrinsic coordination environment. This system enables ligand-free copper-catalyzed C–N coupling of synthetically relevant aryl bromides and further extends the reaction to less-activated aryl chlorides. A broad range of substituted aryl and heteroaryl bromides─including electron-rich, electron-deficient, ortho-substituted, and fused substrates─undergo efficient coupling with diverse amines and alcohols, affording the corresponding products in moderate to excellent yields (up to 96%). Selected aryl chlorides are also compatible under KI-promoted conditions, albeit with reduced efficiency in some cases. The methodology is applicable to late-stage functionalization of complex pharmaceutical molecules and can be conducted on a preparative scale (5–100 mmol), affording yields of 90–95% and TONs of up to 84,000 under air. TON values were calculated based on the total Cu loading. More broadly, this work suggests that support-engineered coordination environments can influence the reactivity of isolated Cu sites, providing a strategy for ligand-free heteroatom cross-coupling.

Proton-exchange membrane fuel cells (PEMFCs) require efficient and durable platinum-group-metal-free (PGM-free) cathode catalysts for the oxygen reduction reaction (ORR). Iron–nitrogen–carbon (Fe–N–C) materials are promising candidates, but their practical application is hindered by rapid demetalation of Fe sites under acidic operating conditions. Here, we show that introducing a p-block metal (Bi) adjacent to the FeN4 motif triggers a pseudo-Jahn–Teller (p-J-T) distortion. This distortion stabilizes a medium-spin Fe(III) configuration (S = 3/2) with an empty dx2–y2 orbital. This empty orbital accepts lone-pair electrons from the nitrogen ligands, strengthening the Fe–N bond and suppressing proton-induced demetalation. The resulting FeBi–N–C catalyst exhibits a dramatically strengthened Fe–N bond, as evidenced by a shortened bond length (from 1.99 Å to 1.96 Å) and a 3-fold higher Fe retention after 20,000 cycles (78.8% vs 26.7%). This structural stability translates into a peak power density of 720 mW cm–2 in H2–O2 PEMFCs and 90% current retention after 150 h at 0.60 V. Our findings establish the p-J-T effect as a new chemical strategy to stabilize metal–nitrogen bonds against acid-induced demetalation.

Pitch-derived hard carbon emerges as an anode material for sodium-ion batteries, but its performance still suffers from the trade-offs among plateau capacity, rate capability, and compaction density. Herein, a catalytic aerobic oxidation strategy that enables controllable oxidation of pitch is employed to fabricate spherical hard carbon with tunable pore structures, realizing simultaneous enhancement of these abovementioned metrics. The spherical hard carbon achieves charging of 126.5 mAh g–1 within about 50 s and sustains sodium storage over continuous 1000 cycles at 9 A g–1. Under an increased areal loading, the anode maintains an areal capacity of 1.65 mAh cm–2, a volumetric capacity up to 332.6 mAh cm–3 and endures 100 charge–discharge cycles at a current density of nearly 3 mA cm–2. This work provides a strategy to design hard carbon anodes with enhanced volumetric capacity and rate performance for space-constrained energy storage scenarios.

To support dual‐carbon goals and address the limitations of conventional CO ₂ valorization technologies, this review summarizes recent advances in electrochemical–biological coupling systems for high‐value CO ₂ utilization, with emphasis on catalytic fundamentals, system integration, and industrial prospects. We discuss catalyst and reactor design for CO ₂ electroreduction to C ₁ /C ₂ liquid platform molecules, particularly formate, acetate, and methanol, and their subsequent biological conversion. The review further examines metabolic and engineering strategies by which microbial cell factories assimilate electro‐generated substrates to produce high‐value compounds, including amino acids, organic acids, polysaccharides, and polyhydroxybutyrate (PHB). Key bottlenecks in electrocatalyst stability, gas diffusion electrodes, reactor operation, carbonate accumulation, cathode flooding, metabolic compatibility, flux matching, and system‐level coupling are analyzed. We also highlight the roles of artificial intelligence, multiscale modeling, smart control, techno‐economic analysis, and life‐cycle assessment in accelerating scale‐up and industrial translation. Overall, electrochemical–biological coupling provides a “capture‐convert‐valorize” route that integrates renewable‐electricity‐driven electrocatalysis with biomanufacturing, enabling CO ₂ conversion into multicarbon, value‐added products and offering a promising platform for sustainable carbon recycling and carbon‐negative manufacturing.

To support dual‐carbon goals and address the limitations of conventional CO ₂ valorization technologies, this review summarizes recent advances in electrochemical–biological coupling systems for high‐value CO ₂ utilization, with emphasis on catalytic fundamentals, system integration, and industrial prospects. We discuss catalyst and reactor design for CO ₂ electroreduction to C ₁ /C ₂ liquid platform molecules, particularly formate, acetate, and methanol, and their subsequent biological conversion. The review further examines metabolic and engineering strategies by which microbial cell factories assimilate electro‐generated substrates to produce high‐value compounds, including amino acids, organic acids, polysaccharides, and polyhydroxybutyrate (PHB). Key bottlenecks in electrocatalyst stability, gas diffusion electrodes, reactor operation, carbonate accumulation, cathode flooding, metabolic compatibility, flux matching, and system‐level coupling are analyzed. We also highlight the roles of artificial intelligence, multiscale modeling, smart control, techno‐economic analysis, and life‐cycle assessment in accelerating scale‐up and industrial translation. Overall, electrochemical–biological coupling provides a “capture‐convert‐valorize” route that integrates renewable‐electricity‐driven electrocatalysis with biomanufacturing, enabling CO ₂ conversion into multicarbon, value‐added products and offering a promising platform for sustainable carbon recycling and carbon‐negative manufacturing.

The development of robust catalysts for CO ₂ methanation under intermittent operating conditions is key to harnessing renewable energy sources such as wind and solar. However, this pursuit faces two major obstacles. The heating‐cooling cycles induce prolonged thermal stress, resulting in catalyst deactivation. Moreover, the temperature‐sensitive selectivity hampers the ability to maintain high methane yield, leading to undesired by‐products. Herein, we report cobalt nanoparticles confined within carbon matrices, which achieved 82.3% CO ₂ conversion and > 99% CH ₄ selectivity over multiple heating‐cooling cycles toward intermittent CO ₂ methanation. The catalyst robustness arises from the low coefficient of thermal expansion and high thermal conductivity of the carbon matrix, which effectively mitigates thermal stress during temperature fluctuations. Mechanistic studies confirm that the reaction proceeds via a formate pathway, which contributes to the high CH ₄ selectivity across a wide temperature range. These insights provide a design framework for developing robust catalysts, advancing CO ₂ methanation performance, and the efficient use of fluctuating renewable energy sources.

The development of robust catalysts for CO ₂ methanation under intermittent operating conditions is key to harnessing renewable energy sources such as wind and solar. However, this pursuit faces two major obstacles. The heating‐cooling cycles induce prolonged thermal stress, resulting in catalyst deactivation. Moreover, the temperature‐sensitive selectivity hampers the ability to maintain high methane yield, leading to undesired by‐products. Herein, we report cobalt nanoparticles confined within carbon matrices, which achieved 82.3% CO ₂ conversion and > 99% CH ₄ selectivity over multiple heating‐cooling cycles toward intermittent CO ₂ methanation. The catalyst robustness arises from the low coefficient of thermal expansion and high thermal conductivity of the carbon matrix, which effectively mitigates thermal stress during temperature fluctuations. Mechanistic studies confirm that the reaction proceeds via a formate pathway, which contributes to the high CH ₄ selectivity across a wide temperature range. These insights provide a design framework for developing robust catalysts, advancing CO ₂ methanation performance, and the efficient use of fluctuating renewable energy sources.