Electrochemical CO2 and nitrite co-reduction provides a sustainable urea synthesis route but remains limited by low selectivity and an undecided C–N coupling mechanism. Here, we report co-sputtered bimetallic Cu–Co catalysts that facilitate urea formation via a tandem relay mechanism. The optimal Cu:Co ratio of 1:1 achieves a urea yield rate of 61 ± 6 mmol h⁻1gcat⁻1 at –1.2 V vs. RHE under neutral pH, emphasizing the importance of proton balance in sustaining proton-coupled electron transfer. In situ synchrotron-based infrared and Raman spectroscopy monitor the dynamic evolution of *CO, *NH2, and C‒N intermediates. In situ X-ray absorption spectroscopy indicates the structural stability of metallic Cu and Co active sites. Density functional theory calculations suggest that *COOH + *NH2 coupling initiates urea pathway, with *NH2CO formation as the potential-determining step. This study integrates rational catalyst design and in situ spectroelectrochemical analysis to advance understanding of electrochemical C–N coupling for urea synthesis. Electrochemical conversion of CO2 and nitrite offers a green route to produce urea. Here, the authors report co-sputtered copper cobalt catalysts enable efficient C–N coupling through a tandem mechanism, yielding 61 mmol h⁻1gcat⁻1 urea at –1.2 V vs. RHE.

The sustainable electrochemical upcycling of plastic waste into value-added chemicals while co-generating clean hydrogen offers a compelling strategy toward circular energy and materials systems. Herein, we report the synthesis of ultrathin, structurally disordered palladium–nickel bimetallenes (PdNi-bm) via a one-step solvothermal method. The incorporation of Ni into the Pd lattice induces charge redistribution and form heterogeneous Pd–Ni interfaces that enhance electron transfer and modulate the d-band structure. As a result, PdNi-bm exhibits exceptional bifunctional electrocatalytic activity for both the hydrogen evolution reaction (HER) and ethylene glycol oxidation reaction (EGOR) in alkaline media. The optimized PdNi-bm delivers a low overpotential of 86 mV at 10 mA cm⁻² for HER outperforming monometallic Pd metallenes. For EGOR, PdNi-bm achieves a significantly reduced overpotential (1.38 V vs. RHE) at 10 mA cm⁻² and high Faradaic efficiency (> 87%) for formate production. When applied to real PET hydrolysate, PdNi-bm enables efficient electro-upcycling at substantially anodic potentials, simultaneously generating hydrogen and valuable oxidation products (mainly formate). Integrated into a zero-gap membrane-electrode assembly, the PdNi-bm-based system achieves industrially relevant current densities of 0.6 A cm⁻² at only 1.82 V and maintains excellent operational stability over 100 h. This work highlights structurally disordered PdNi-bm as a robust and scalable bifunctional catalysts for simultaneous hydrogen production and PET waste valorisation.

The application spectrum of liquid metals as solvents in crystal synthesis is fast expanding. Harnessing liquid metal-mediated crystal growth with high spatial resolution is essential for the precise micro/nanopatterning of functional crystals. However, crystal growth under boundary confinement and postgrowth crystal evolution driven by solid-phase diffusion remains underexplored. Here, we investigate the evolution of AuGa2 intermetallic crystals formed by touch transfer of a liquid Ga layer onto lithography-patterned Au thin films. We demonstrate postgrowth coarsening of the as-grown AuGa2 crystals via Ostwald ripening, sustained by mass transport through a solid Ga phase. Three-month observations reveal that this ripening is a long-term effect that progressively diminishes over time. Pattern width and edge features are found to modify the local Ga/Au thickness, shifting phase equilibrium and thereby tuning crystal size and spatial distribution. These findings provide mechanistic insight for the precise control of crystal growth and patterning in liquid metal synthesis systems.

Manganese Prussian blue analogues (Mn-PBAs) are widely investigated as cathodes for aqueous zinc-ion batteries (AZIBs) owing to their open framework and potential two-electron redox, yet their true electrochemical stability and charge-storage mechanism remain contentious. Here, we systematically disentangle the roles of electrolyte composition and compositional variations in Mn-PBAs using a combination of electrochemical analysis, operando X-ray diffraction, solution-phase analysis, microscopy, soft X-ray absorption spectroscopy, and density functional theory. It is revealed that, independent of composition and electrolyte formulation, Mn-PBAs do not operate as stable intercalation hosts with aqueous zinc-ion electrolytes. Initial Na+ deintercalation triggers a monoclinic-to-cubic transition, accompanied by Mn3+-driven disproportionation and manganese dissolution, followed by electrochemical deposition of manganese oxide that contributes capacity beyond one electron, reaching 136 mA h g-1 in the Na+-Zn2+ dual salt electrolyte compared to 111 mA h g-1 in the Zn2+ based single salt system after activation. Subsequent discharge induces irreversible conversion of the Mn-PBA framework to a rhombohedral Zn-PBA phase, with later cycling dominated by the solid-solution behavior of Zn-PBA alongside repeated manganese dissolution-redeposition. As a result, the capacity of Mn-PBA converges toward that of Zn-PBA and decays rapidly, with only 60% (dual-salt) and 43% (single-salt) retention after 100 cycles. While the dual-salt electrolyte delays manganese dissolution and enables partial (de)intercalation within Zn-PBA, it does not alter the fundamental reaction pathway. Across the compositions investigated, differences are reflected primarily in activation behavior and electrochemical kinetics. These findings reconcile reports of high-rate cycling stability at modest capacities and establish intrinsic limitations of Mn-PBAs in AZIBs, highlighting the need for interfacial and electrolyte strategies to suppress Mn3+ disproportionation.

Electrochemical reduction of NO2- to NH4+ offers a direct, energy-efficient pathway for sustainable ammonia production by circumventing the rate-determining NO3--to-NO2- conversion that constrains the traditional NO3- reduction reaction (NO3RR). Herein, we introduce an electrochemical reduction conditioning (ERC) strategy to control Fe2O3 at different reduction potentials, generating a series of catalysts with tunable Fe3+/Fe2+/Fe components and lattice strain. Comprehensive ex situ and in situ characterization studies reveal that more negative ERC potentials induce greater structural disorder (i.e., tuned Fe/FeO/Fe2O3 components and pronounced lattice strain), which collectively enhance NO2- adsorption, water dissociation and hydrogenation of intermediates, while suppressing competing H2 evolution. Theoretical calculations support that these defective catalyst surfaces lower the energy barriers for NO2- adsorption. As a result, the optimized ERC-treated Fe2O3 catalyst achieves a high NH4+ production rate of 153 nmol s-1 cm-2, a faradaic efficiency of 93% and a partial current density of similar to 96.5 mA cm-2 at -1.0 V vs. RHE. Integration with plasma-generated NO2--rich electrolytes further demonstrates stable, decentralized NH4+ production, yielding 32 nmol s-1 cm-2. This work clarifies the mechanistic role of ERC-induced structural disorders in the NO2RR and provides design principles for next-generation metal-oxide catalysts enabling sustainable nitrogen-cycle management.

Abstract Manganese dioxide (MnO 2 ) is a leading positive electrode candidate for aqueous zinc-ion batteries, combining safety, high voltage, low cost, and sustainability for grid-scale storage. However, its practical development remains restricted by poor reversibility, rooted in an unresolved mechanistic debate spanning over a decade. Here, we combine operando characterizations, multimodal spectroscopic analyses, and theory to establish a unified picture: proton-primed MnO 2 dissolution and subsequent redeposition as nanocrystalline and disordered MnO x nanosheets, coexisting with reversible proton intercalation in parent MnO 2 and predominantly in deposited MnO x , forming a dual redox mechanism. pH-driven insulating byproduct precipitation emerges as a significant kinetic barrier that limits deep dissolution and capacity utilization. Guided by these insights, we introduce surface activation and architectural design strategies toward mitigating kinetic barriers, enabling enhanced capacity and stability in both Swagelok and pouch-type cells. By reconciling mechanistic ambiguity and translating it into actionable design principles, this work demonstrates a framework for developing durable Mn-based positive electrodes for sustainable energy storage.

Phonon dispersion relations along the [0,0, q], [0, q, 1], [0, q, q], and [q, q, q] directions of face-centered cubic Pd₀․₉₅Rh₀․₀₅ have been studied within the framework of the pseudopotential method. Without phenomenological fitting in real space, a transition-metal pseudopotential that is directly derived from generalized pseudopotential theory (GPT) has been used. This potential has been used to compute bulk modulus (B), elastic constants (C₁₁, C₁₂, and C₄₄) and phonon dispersion curves along symmetry directions. Both solid and liquid metal properties can be effectively described by the selected pseudopotential. The calculated results show excellent agreement with existing experimental data, validating the reliability of the current methodology for Pd–Rh alloys. The study indicates that increasing Pd concentration in Pd–Rh alloys lead to a consistent improvement of elastic constants and bulk modulus, highlighting the stiffening effect of Pd on the alloy system.

Metal-catalyzed hydrothermal deuteration is a versatile approach for hydrogen-deuterium exchange (HDE) reactions, offering precise isotopic labeling of organic molecules. Here, we report the development of a scalable flow deuteration method that permits the tunable isotopic selectivity of saturated short-chain fatty acids over platinum group metal (PGM) catalysts. Benchmarking against conventional batch hydrothermal deuteration in pressurized vessels demonstrated that flow deuteration sustains high steady-state activity, improves single-pass yields, and provides mechanistic insights into isotopologue formation. Under optimized conditions, 10 wt % Pt/C achieved 93% D (deuterium incorporation) and 98% isolated yield of sodium butyrate-d(7) in 90 min time-on-stream (TOS) under H-2-free conditions (20 bar D2O, 220 degrees C) in a single pass. Notably, flow deuteration afforded high selectivity to -d(7) (60%) and -d(6) (32%) isotopologues and favored the formation of thermodynamically stable isotopologues at elevated temperatures, as confirmed by isotopologue analysis (MS) and isotopomer distribution (NMR). The intrinsic activity of Pt (TOF = 6 h(-1)) exceeds that of Pd metal (with similar loading) by an order of magnitude, determined at iso-conversion (<20% conversion under differential reactor conditions). In situ catalyst activation allowed for four consecutive reaction cycles without loss of activity, with the catalyst maintaining stability over 540 min of time-on-stream. Density functional theory calculations revealed a facile and preferential alpha-C-H activation of butyric acid via cooperative C- and O-metal interactions on Pt, effectively lowering activation barriers at other C-sites and thereby promoting perdeuteration compared to Pd. Process intensification under flow conditions resulted in a 4-fold increase in the production rate, underscoring the potential of this approach for the scalable, selective, and operationally efficient synthesis of deuterated short-chain fatty acids. This work presents a viable blueprint for platform-specific isotopic labeling using flow chemistry.

Artificial nanozymes, defined as nanomaterials that mimic enzyme-like catalytic activity, emerge as adaptable tools for biomedical applications by uniting catalytic activity with structural stability and chemical versatility. Here, we introduce liquid gallium (Ga) as a catalytic center for nitric oxide (NO) generation and demonstrate its translation into a multifunctional coating. Ga nanoparticles were stabilized with tannic acid (TA) and embedded into a TA-zirconium (TA-Zr4+) metal-phenolic network (MPN), producing robust, substrate-independent films. Ga catalyzed the decomposition of S-nitrosothiols (RSNOs) through electron transfer, enabling NO generation from both model donors such as S-nitrosoglutathione (GSNO) and endogenous precursors in human umbilical vein endothelial cells (HUVECs), with activity retained over multiple cycles. The TA-Zr4+ framework stabilized the coatings and contributed intrinsic antioxidant and anti-inflammatory activities, resulting in a platform that amplified therapeutic outcomes. Functionally, the coatings displayed tunable NO generation, enhanced intracellular NO levels in HUVECs by ∼48%, reduced pro-inflammatory cytokines TNF-α and IL-6 by ∼35% and ∼40%, respectively, under LPS stimulation, and supported endothelial biocompatibility. Together, these findings establish liquid Ga as an efficient catalyst for NO generation and present a design strategy that advances implant coatings from conventional NO donor-based systems toward active, regenerative, and multifunctional therapeutic interfaces.

The electrochemical upcycling of plastic waste into value-added chemicals, coupled hydrogen (H2) generation, provides an attractive route toward circular materials use and low-energy fuel production. Here, we report ultrathin, structurally disordered palladium–nickel bimetallenes (PdNi-bm) synthesized through a one-step solvothermal method as bifunctional electrocatalysts for polyethylene terephthalate (PET)-derived ethylene glycol oxidation and H2 evolution. Ni incorporation into the Pd lattice induces charge redistribution and creates heterogeneous PdNi interfaces, which promote interfacial electron transfer and modulate the electronic structure of Pd. The optimized PdNi-bm catalyst exhibits enhanced alkaline HER activity, requiring an overpotential of only 86 mV at 10 mA cm−2, outperforming monometallic Pd metallenes. For ethylene glycol oxidation, PdNi-bm achieves 10 mA cm−2 at 1.38 V vs RHE and delivers a Faradaic efficiency above 87% for formate production. When applied to real PET hydrolysate, PdNi-bm enables efficient electro-upcycling at substantially reduced potentials while simultaneously producing H2 at the cathode and formate-rich oxidation products at the anode. In a zero-gap membrane-electrode assembly, the PdNi-bm-based system reaches an industrially relevant current density of 0.6 A cm−2 at only 1.82 V and maintains stable operation for over 100 h. These results establish structurally disordered PdNi-bm as robust bifunctional catalysts for energy efficient H2 production coupled with PET waste valorization.

Anti-inflammatory colchicine therapy has emerged as a new era for atherosclerotic cardiovascular diseases. However, the therapeutic benefit of colchicine has not been clearly defined. Herein, we present a double coordination-driven approach to fabricate a stable metal-organic nano-assembly of colchicine (COL-TA-Zn) by uniting the tropolone ring of colchicine (COL), phenolic groups of tannic acid (TA), and Zn 2+ ions. This design leverages the antioxidant and anti-inflammatory properties of COL and TA to create a nanoscale platform capable of scavenging radicals and modulating inflammatory pathways. Through robust Zn 2+ coordination, the resulting COL-TA-Zn nanocomplexes exhibit enhanced stability under physiological conditions, ensuring efficient delivery and sustained bioactivity. In vitro assays confirm suppression of foam cell formation and multiple inflammatory mediators, suggesting significant potential for managing atherosclerosis by targeting both oxidative stress and inflammation. Intravenous administration of COL-TA-Zn in Apoe − / − mice significantly reduces atherosclerotic plaque area, MMP-9, TNF-α, and reactive oxygen species (ROS) levels, thereby illustrating its superior anti-atherosclerotic efficacy compared to COL alone. These findings highlight the promise of the dual coordination-driven nanoplatform in cardiovascular disease treatment.

Hybridization between plasmonic-metal nanoclusters and graphene oxide (GO) plays a prominent role in the biosensing and plasmon-induced photocatalytic properties of nanocomposites. In this study, the adsorption models of Rh, Pd, and Pt doped Ag20 nanoclusters (NCs) on GO were built. Binding energies and electronic structures were calculated with the density functional theory method. It was found that the interaction occurred primarily between the NCs and the epoxy/hydroxyl groups. The binding energies are larger than 2 eV for all three sorts of adsorption. Despite some fluctuations, the binding energies rise with the number of Rh, Pd, and Pt atoms as a whole. Especially, the Rh atoms exhibited the most significant binding energy effect. The partial density of states indicated that the Rh, Pd, and Pt atomic orbitals play prominent roles in the GO-NCs interaction. As the energy mounted from -2 eV to the Fermi level, the hybridization contribution rates (HCRs) of all three kinds of NCs increase with the increasing energy. Within this energy range, the HCRs also increase generally with the increasing number of Rh, Pd, and Pt atoms. As a result, the HCRs slightly below the Fermi level exceed 50%. Generally, the Pd atoms tend to induce higher average HCRs.

Electrocatalytic transformations of oxygen, i.e., the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), are key processes in renewable energy conversion, defining to a large extent, the efficiency of numerous energy conversion technologies, such as fuel cells, metal-air batteries or water electrolyzers. However, the development of highly effective, stable and inexpensive materials for such conversion processes is a bottleneck. Hence, establishing generic catalyst design principles by identifying structural features of catalysts that influence their performance would constitute a major step towards the rational engineering of advanced electrocatalysts. In this study, by investigating a series of metal-substituted manganese oxide (spinel), Mn3O4:M (M = Sr, Ca, Mg, Zn, Cu), nanoparticles as a model system, we demonstrate experimentally and rationalized the dependence of the activity of Mn3O4:M for ORR and the oxygen binding strength in Mn3O4:M oxides on the properties of the M substituent, viz. the enthalpy of formation of the binary MO oxide and the Lewis acidity of the M2+ substituent. Incorporation of elements M that have a low enthalpy of formation of MO (i.e., highly exothermic oxides featuring relatively strong M‒O bonding) enhances the oxygen binding strength in Mn3O4:M, which increases its activity in ORR due to the established correlation between ORR activity and the binding energy of *O/*OH/*OOH species on the catalyst surface. Our work provides a new perspective on the design of new compositions for oxygen electrocatalysis relying on the substitution by redox-inactive elements affecting the binding energy of oxygen to the surface of the complex metal oxide catalysts (ORR/OER activity descriptor). We speculate that this concept is general and transferrable to a broad selection of materials and processes involving oxygen adsorption and redox, beyond electrocatalysis.

Understanding the structure of Ru(V)-oxo species is crucial for designing novel catalysts for sustainable energy applications, such as water splitting for green hydrogen production. This study reports the EPR detection of a Ru(V)-oxo intermediate stabilized by terpyridine and phenanthroline carboxylate ligands. The interaction between the carboxylate group and the ruthenium center, along with PCET-dependent hemilability under oxidative conditions, plays a critical role in achieving the high-valent state. Subtle changes in the coordination environment around the central metal also proved to be essential. Low-temperature NMR, high-resolution mass spectrometry, UV-Vis spectroscopy, and density functional theory calculations support these findings.

A high-entropy liquid metal alloy (Ga-Fe-Zn-Sn-Bi-Ni) is developed to address the multi-step complexity of green ammonia electrosynthesis from nitrate. Guided by molecular dynamics, design of experiments, and density functional theory, this alloy exploits high configurational entropy to form diverse, atomically dispersed active sites. The liquid state eliminates endothermic barriers by enabling nitrogen intermediates to move freely to the most energetically favorable sites. Crucially, a hydrogen shuttling mechanism is uncovered where Fe acts as a proton hub while Sn, Ni, and Zn store and transfer hydrogen to Fe, enhancing reaction kinetics and preventing catalyst saturation. This synergy boosts ammonia production rates up to sevenfold while maintaining high Faradaic efficiency (FE). By integrating entropy-driven design, dynamic site reconfiguration, and hydrogen management, this work establishes a robust foundation for efficient, scalable ammonia electrosynthesis in pursuit of NetZero targets.

SACs are an important class of materials that mediate chemical reduction reactions, a key subset of which is Ni within a carbon support for the electrochemical CO2 reduction reaction (CO2RR). However, how the metal atom/clusters and carbon‐based support act in concert to catalyze CO2RR is not well understood, with most reports attributing activity solely to the Ni‐Nx/C moieties. To address this gap, we have undertaken a mechanistic investigation, employing in situ X‐ray absorption spectroscopy (XAS) coupled with electrochemical studies and DFT calculations to further understand how Ni single atoms work in conjunction with the nitrogen‐doped carbon matrix to promote CO2RR to CO, and how the presence of impurities such as those present in CO2‐containing waste flue gases (including NOx, and CN‐) changes the catalyst upon reduction. In contrast to previous works, we do not find strong evidence for a purely metal‐based reduction upon application of negative reductive potentials. Instead, we present evidence for an increase in the equatorial vs. axial splitting of Ni, consistent with electrons moving onto the reactants via the Ni single atom 3dz2 orbital. In addition, we demonstrate a transient poisoning mechanism of the Ni SAC by nitrite and thiocyanate, explaining the recovery of activity during CO2RR.

Ultra‐thin 2D materials have gain significant attention for making next‐generation optoelectronic devices. Here, a large‐area heterojunction photodetector is fabricated using a liquid metal‐printed 2D SnO 2 layer transferred onto CdTe thin films. The resulting device demonstrates efficient broadband light sensing from visible to near‐infrared wavelengths, with enhanced detectivity and faster photo response. Significantly, the device shows a ≈10 5 ‐fold increase in current than the dark current level when illuminated with a 780 nm laser and achieves a specific detectivity of ≈10 12 Jones, nearly two orders of magnitude higher than that of a standalone CdTe device. Additionally, temperature‐dependent optoelectronic testing shows that the device maintains a stable response up to 140 °C and generates distinctive photocurrent at temperatures up to 80 °C, demonstrating its thermal stability. Through band structure analysis, DFT calculations, and photocurrent mapping, the formation of a p‐n junction is confirmed, which enhances carrier separation via the built‐in potential, significantly boosting photoresponse. These results highlight the potential of liquid metal‐derived 2D materials in heterostructure integration, paving the way for advanced optoelectronic applications.

Presently, the most common high-entropy systems are formed from the mixing of immiscible transition metals under extreme conditions. Here, a new class of high-entropy-like nanoparticles is reported, based entirely on post-transition metals, Ga, In, Sn, Zn, and Bi, which undergo core-level nanoscale homogenization via low-temperature sonication. Starting from a bulk high-entropy-like melt, with clear phase segregation, including Ga-rich, Zn-rich, and Bi-rich domains, ultrasonic agitation is applied to disrupt their immiscibility. The resulting cavitation and shear forces promote rapid mixing and atomic-level diffusion, forming uniformly distributed high-entropy-like, compositionally complex nanoparticles with a core-shell structure. When applied for electrochemical carbon dioxide reduction, the nanoparticles exhibit high current densities with a selectivity toward formates. The finding demonstrates a scalable route to high-entropy-like nanoparticles derived from post-transition metals, circumventing the need for high-temperature or shock-based synthesis, while also expanding the compositional space into softer, low-melting-point systems.

The photovoltaic-alkaline water (PV-AW) electrolysis system offers an appealing approach for large-scale green hydrogen generation. However, current PV-AW systems suffer from low solar-to-hydrogen (STH) conversion efficiencies (e.g., <20%) at practical current densities (e.g., >100 mA cm(-2)), rendering the produced H-2 not economical. Here, we designed and developed a highly efficient PV-AW system that mainly consists of a customized, state-of-the-art AW electrolyzer and concentrator photovoltaic (CPV) receiver. The highly efficient anodic oxygen evolving catalyst, consisting of an iron oxide/nickel (oxy)hydroxide (Fe2O3-NiOxHy) composite, enables the customized AW electrolyzer with unprecedented catalytic performance (e.g., 1 A cm(-2) at 1.8 V and 0.37 kgH(2)/m(-2) hour(-1) at 48 kWh/kgH(2)). Benefiting from the superior water electrolysis performance, the integrated CPV-AW electrolyzer system reaches a very high STH efficiency of up to 29.1% (refer to 30.3% if the lead resistance losses are excluded) at large current densities, surpassing all previously reported PV-electrolysis systems.

Aqueous zinc-ion batteries are promising for a safe, inexpensive, and sustainable platform for stationary energy storage, but their reversibility remains limited by dendrite and corrosion-mediated failure of the zinc anode. While low-concentration electrolyte additives have emerged as scalable solutions, the mechanistic underpinnings of their interfacial dynamics that dictate whether they enable long-term rechargeability or trigger premature dendritic failure remain poorly understood. Here, we investigate a series of pi-interactive aromatic alcohols and a cycloaliphatic reference additive and uncover how additive-zinc and additive-additive interactions jointly govern the formation, spatial organization, packing density, and mobility of the additive film. These interfacial dynamics govern Zn2+ transport, corrosion suppression, and zinc deposition morphology. Phenol, which strikes a balance between adsorption strength and interfacial mobility, forms a thick yet dynamic layer that suppresses hydrogen evolution mediated corrosion while promoting uniform zinc deposition. This leads to excellent cycling stability with nearly 2 Ah cm-2 cumulative plated capacity in a practically relevant asymmetric configuration at 24% depth of discharge under demanding 4 mA cm-2-4 mAh cm-2, including a thin separator and low electrolyte-to-capacity ratio, with the coulombic efficiency reaching 99.89% under kinetic control compared to 95.94% for the additive-free electrolyte. Full cell and pouch-cell tests further validate phenol's efficacy, establishing adsorption layer dynamics as a new paradigm for rationalizing electrolyte additives' efficacy in regulating zinc anode reversibility in aqueous batteries.