Search Results (64)

Ammonia (NH₃) is a compelling carbon-free hydrogen carrier. Its catalytic decomposition to produce a hydrogen/nitrogen (H₂/N₂) gas stream is central to the “NH₃-H₂” clean energy cycle, provided that residual NH₃ is removed to fuel-cell-grade purity downstream. This review integrates advances from the past five years across four major catalytic NH₃ decomposition pathways, encompassing conventional thermocatalysis, plasma-catalytic, photo(thermal), and electrically driven catalysis, within a unified mechanistic and practical framework, distinguishing it from existing single-pathway reviews. Noble metal catalysts, particularly Ru-based systems, achieve superior low-temperature activity through support engineering, promoter effects, and active-site construction. However, our analysis reveals that non-noble metal (Fe, Co, Ni) catalysts and their alloys, nitrides, and carbides have made substantial progress, with certain Co-based and bimetallic systems approaching Ru-level performance via interfacial oxygen vacancy engineering and electronic structure modulation. Emerging non-thermal routes effectively overcome thermodynamic barriers, enabling operation at temperatures 200–300 °C below conventional thermal requirements, though each faces distinct challenges in energy efficiency, stability, and scalability. Key challenges remaining across all pathways to practical implementation, including residual NH₃ removal and H₂ purification, catalyst deactivation and stability, heat management and energy efficiency, start-up/shut-down dynamics, as well as system integration and economics, are critically assessed. This review provides theoretical guidance and practical recommendations for developing scalable, low-temperature NH₃ decomposition technologies. Full article

In this work, ternary Mo–Ni–X (X = Al, Co, Cr, Cu, Fe, W) thin films with nominal composition Mo₈₀Ni₁₀X₁₀ (at. %) were prepared by magnetron sputtering and evaluated as electrocatalysts for the hydrogen evolution reaction (HER) in alkaline media. The influence of alloy composition, substrate type, and deposition temperature on catalytic performance was systematically investigated. Electrochemical screening revealed a strong dependence of HER activity on both substrate conductivity and ternary alloying, with Al-, Cr-, and W-containing systems showing the best performance on glassy carbon substrates. This highlights the importance of interfacial charge-transfer efficiency in determining catalytic behavior. The Mo₈₀Ni₁₀Cr₁₀/GC system was selected for detailed analysis. Deposition temperatures ≥ 500 °C resulted in enhanced HER activity, reaching an overpotential of η₁₀ = −222 mV at j = −10 mA cm⁻². The improved performance is attributed to temperature-induced microstructural optimization and electrochemically driven surface reconstruction, leading to the formation of a Ni-enriched active interface. AFM analysis confirmed surface restructuring during operation, with roughness increasing from ~1 to ~3 nm, indicating the formation of additional electrochemically accessible active sites. XPS results suggest partial depletion of Mo during cycling, while Cr mainly contributes to structural stabilization of the evolving thin film. Overall, the results demonstrate that HER performance is governed by the coupled effects of alloy composition, substrate-dependent charge transport, and in situ surface reconstruction. This work highlights magnetron sputtering as a scalable approach for designing homogeneous noble-metal-free thin-film electrocatalysts with tunable activity. Full article

The development of sustainable, noble-metal-free photocatalytic systems for acceptorless dehydrogenation (ADH) of cyclic amines remains a significant challenge. Herein, we report a novel heterogeneous photocatalyst constructed by covalently grafting a cobaloxime-based proton reduction catalyst onto a photosensitive covalent organic framework (PT-COF). The tailored PT-COF scaffold, featuring a donor–acceptor architecture and uncondensed amino groups, serves as both an efficient visible-light harvester and a porous support for cobalt active sites. The resulting Co-PT-COF hybrid exhibits excellent photocatalytic activity for the ADH of a wide range of cyclic amines, affording the corresponding N-heteroarenes in 62–95% yields under an Ar atmosphere at 28 °C with blue LED irradiation for 12 h in water. Notably, the catalyst demonstrates outstanding recyclability over five consecutive cycles with minimal loss of activity or cobalt leaching. Comprehensive photoelectrochemical and spectroscopic studies reveal that enhanced charge separation and efficient electron transfer from the photoexcited COF to the cobalt centers underpin the superior performance. Mechanistic investigations, including in situ EPR spectroscopy, confirm the involvement of α-amino radical intermediates in the catalytic cycle. This work establishes a sustainable platform for solar-driven dehydrogenation chemistry and provides a versatile blueprint for integrating molecular catalysts with photoactive frameworks. Full article

The oxygen reduction reaction (ORR) is a key process in electrochemical energy conversion technologies such as fuel cells and metal–air batteries; however, its sluggish kinetics and reliance on precious metal catalysts limit large-scale application. This review provides a comprehensive overview of recent advances in non-precious nanoscale electrocatalysts for ORR in alkaline media. Particular emphasis is placed on reaction mechanisms, including dominant pathways, kinetics, and key intermediates, as well as the advantages of alkaline electrolytes over acidic systems. The performance of various catalyst classes is systematically discussed, including transition metal-based materials (Fe, Co, Zn, Cu, and bimetallic systems) and metal-free carbon-based electrocatalysts. Special attention is given to heteroatom-doped carbon materials, carbon nanostructures, and emerging hybrid systems such as MXene-based composites. Comparative analysis highlights the relationship between catalyst composition, structure, and electrochemical performance metrics, including half-wave potential, onset potential, Tafel slope, number of electron transfer, and operational stability. Overall, non-precious catalysts demonstrate promising activity and durability, approaching that of noble metals under alkaline conditions. The insights summarized in this review guide the rational design of efficient, cost-effective ORR electrocatalysts and support the development of sustainable energy technologies. Full article

The rational configuration of electronic band structures through deep-seated structural disorder remains a formidable challenge in sustainable solar-to-fuel conversion. Herein, we report a transformative kinetic strategy to “freeze” an extraordinary density of non-equilibrium structural defects within an integrated Cu₄MgO₅/ZnO nanocomposite. Synthesized via a chitosan-assisted coordination-combustion route followed by rapid thermal quenching, the material preserves a record crystallographic dislocation density of 1.09 × 1015 m⁻² and significant lattice microstrain (1.04 × 10⁻³). This engineered structural disorder induces a profound reconfiguration of the electronic landscape, generating a continuous manifold of sub-bandgap “tail states” that narrow the optical bandgap to a remarkable 1.34 eV. Consequently, the defect-rich architecture facilitates unprecedented dual-channel photocatalytic performance under simulated solar irradiation in an aqueous solution containing 5 vol% triethanolamine (TEOA) as a sacrificial electron donor; the catalyst achieved a hydrogen evolution rate of 17,700.0 µmol g⁻¹ h⁻¹ and a methane production rate of 172.50 µmol g⁻¹ h⁻¹—representing a 36.3-fold and 43.1-fold enhancement over commercial ZnO, respectively. With an apparent quantum yield of 8.42% at 420 nm and robust photostability—maintaining 95.3% of its activity over five consecutive cycles (25 h total)—this noble-metal-free ternary system bypasses the limitations of traditional heterojunctions. Our findings establish a new benchmark for defect-engineered catalysts, providing a scalable blueprint for high-efficiency carbon neutrality and solar fuel production. Full article

Electrocatalytic water splitting powered by renewable energy is a promising route for sustainable hydrogen production. Rather than developing separate catalysts for HER and OER, recent efforts focus on multifunctional electrocatalysts that can efficiently drive both reactions, simplifying system design and improving efficiency. A major limitation of conventional water splitting is the high overpotential and low-value oxygen production in OER. To overcome this, hybrid water splitting replaces OER with more valuable oxidation reactions, such as pollutant degradation or organic upgrading, enhancing overall energy and economic efficiency. This review covers the fundamentals of water splitting and highlights key physicochemical techniques for probing electrocatalyst activity, particularly structural reconstruction under operating conditions. It evaluates noble-metal, nonprecious-metal, and metal-free nanocarbon catalysts in both acidic and alkaline media, with emphasis on their roles in alternative anodic reactions. Finally, it outlines current challenges and future directions for developing efficient, durable, and sustainable electrocatalysts for advanced hydrogen production systems. Full article

Water electrolysis has emerged as a strategically appealing route for the sustainable production of green hydrogen (H₂) via the hydrogen evolution reaction (HER), though the sluggish kinetics of the oxygen evolution reaction (OER) remains a bottleneck hindering large-scale practical applications. In this regard, an attractive solution is offered by the integration of the ethanol oxidation reaction (EOR) into hybrid water-splitting systems, favorably reducing anodic overpotentials. Nonetheless, an open challenge is related to the fabrication of eco-friendly and economically viable catalysts free from noble metals, combining efficiency and stability. Herein, we explore nickel-oxide-based nanostructures grown onto porous Ni foam scaffolds by a scalable hydrothermal (HT) approach as EOR electrocatalysts. Material properties arising from modulation of the sole HT growth time are investigated by complementary structural, microscopic, and spectroscopic techniques. Electrochemical tests demonstrate good durability and very attractive EOR performances, mainly influenced by the morphology and the NiOOH surface content of the target systems. Overall, the present work advances an attractive route to transition-metal-based electrocatalysts for efficient alcohol-oxidation-assisted water electrolysis. Full article

The oxygen evolution reaction (OER), a key half-reaction in electrochemical water splitting, is limited by sluggish multi-electron transfer kinetics, starting extensive research into efficient, low-cost nanoscale electrocatalysts, particularly those based on nickel, cobalt, and iron, as well as mixed-metal, hybrid, and heteroatom-doped carbon-based metal-free systems, as presented here. Ni- and Co-based electrocatalysts show high efficiency for alkaline OER due to optimized nanostructures, surface modifications, heterostructure design, and multi-metal doping, which enhance activity, stability, and electronic properties. Their performance relies on precise atomic-level control of structure and synergistic interactions, enabling them to approach or rival noble-metal catalysts. Iron-based electrocatalysts are also promising due to their abundance, low cost, and flexible redox chemistry, forming active iron oxyhydroxide species during operation; however, their low conductivity requires structural and electronic optimization. Beyond Fe, Ni, and Co, copper-based compounds, zeolitic imidazolate framework-derived structures, and manganese phosphide–cerium oxide composites offer enhanced oxygen vacancies, tunable structures, and strong interfacial synergy. Furthermore, heteroatom-doped carbon materials incorporating nitrogen, phosphorus, or sulfur improve catalytic activity by modifying electronic structure, creating active sites, and enhancing charge transfer. Overall, careful control of composition, structure, and electronic properties enables the development of efficient, durable, and scalable noble-metal-free catalysts for OER. Full article

Water electrolysis is a key technology for sustainable hydrogen production and a cornerstone of future low-carbon energy systems. However, large-scale deployment is constrained not only by efficiency and cost, but increasingly by the sustainability and availability of materials used in electrocatalysts and membranes. This review provides a materials-centric assessment of state-of-the-art and emerging electrocatalysts for alkaline (AEL), proton exchange membrane (PEM), and solid oxide electrolysis (SOEC) technologies, emphasizing the interdependence of performance, durability, cost, and sustainability. Electrocatalyst activity and stability are linked to cell- and stack-level efficiency, energy demand, and the levelized cost of hydrogen. Life cycle assessment (LCA) and resource criticality analyses are integrated to quantify environmental impacts, supply risks, and recycling potential of key materials, including platinum group metals, nickel, rare earth elements, and ceramic oxides. Particular attention is given to recycling and circularity strategies, which are essential for mitigating material scarcity and reducing upstream emissions, especially in PEM electrolyzers. Emerging catalyst concepts such as single-atom catalysts, high-entropy alloys, and noble-metal-free systems are discussed as promising pathways to reduce critical material dependence. The review concludes by highlighting the need for integrated material–technology–system approaches to enable efficient, scalable, and truly sustainable hydrogen production. Full article

Ammonia borane (AB) is recognized as a highly promising material for hydrogen storage owing to its exceptional safety and high hydrogen density, enabling controllable hydrogen release at room temperature through catalytic hydrolysis. The development of efficient catalysts to accelerate this process remains a critical research challenge. In this work, carbon nanotube (CNT)-supported Co-MoO₃ nanoparticles were synthesized through reduction with sodium borohydride. The catalyst with a Co/MoO₃ molar ratio of 1.0:0.1 (denoted as Co₁Mo_0.1/CNTs) showed optimal performance in AB hydrolysis, with a turnover frequency (TOF) of 19.15 mol_H2 mol_cat⁻¹ min⁻¹ and an activation energy (E_a) of 26.41 kJ mol⁻¹. The superior performance of the Co₁Mo_0.1/CNTs catalyst can be ascribed to the efficient proton-transfer promotion by carboxylated carbon nanotubes and the synergistic catalytic effect between Co and Mo in the system. This study offers a viable pathway for constructing high-efficiency noble metal-free catalysts for hydrogen production from AB hydrolysis. Full article

With the rapid industrialization, excessive reliance on fossil fuels has resulted in energy crises and environmental pollution, driving the search for sustainable alternatives. Biomass-derived resources have emerged as promising candidates to replace fossil-based feedstocks. Among these, furfural (FF) serves as a key platform molecule that can be catalytically hydrogenated to various high-value chemicals, with furfuryl alcohol (FA) representing one of the most valuable products. Currently, Cr-based catalysts remain predominant for the selective hydrogenation of FF to FA. However, the severe environmental toxicity of Cr necessitates urgent development of alternative Cr-free catalytic systems. This study systematically reviews recent advances in FF hydrogenation to FA, providing an in-depth discussion of reaction mechanisms, including adsorption configurations, solvent effects, and side reactions, as well as a comprehensive analysis of structure–activity relationships, involving active metal, support, promoter, and preparation methods. Furthermore, we evaluate the application of the advanced characterization techniques for monitoring the reaction processes. Finally, we propose the future research directions: (1) designing efficient and stable non-noble metal catalysts and (2) elucidating reaction mechanisms via the combined in situ characterization and theoretical calculations. These efforts would facilitate the academic understanding and industrial implementation of the FF-to-FA conversion process. Full article

The escalating concerns about global warming and energy shortages have presented an urgent need for efficient and environmentally sustainable hydrogen production methods. This work presents an efficient Ni₃S₂/ZnIn₂S₄ (ZIS) composite photocatalyst synthesized via a hydrothermal process, demonstrating enhanced performance for hydrogen evolution and benzyl alcohol oxidation under visible-light irradiation. Specifically, the optimized 3.2% Ni₃S₂/ZIS composite achieves hydrogen and benzaldehyde production rates of 4.342 mmol g^–1 h^–1 and 4.213 mmol g^–1 h^–1, respectively, 1.79 and 1.76 times greater than those of pristine ZIS. The system exhibits excellent selectivity, producing benzaldehyde as the sole by-product, and maintains stability over multiple reaction cycles. Mechanistic studies reveal that Ni₃S₂ facilitates charge separation and accelerates reaction dynamics by providing conductive channels and enhancing catalytic activity at the ZIS interface. These findings highlight the potential of Ni₃S₂/ZIS composites as cost-effective, scalable, and noble-metal-free photocatalysts for hydrogen production and green chemical synthesis, offering a promising pathway toward energy sustainability. Full article

Against the backdrop of global energy transition and strict environmental regulations, supercritical carbon dioxide (scCO₂) fracturing and oil displacement technologies have emerged as pivotal green approaches in shale gas exploitation, offering the dual advantages of zero water consumption and carbon sequestration. However, the inherent low viscosity of scCO₂ severely restricts its sand-carrying capacity, fracture propagation efficiency, and oil recovery rate, necessitating the urgent development of high-performance thickeners. The current research on scCO₂ thickeners faces a critical trade-off: traditional fluorinated polymers exhibit excellent philicity CO₂, but suffer from high costs and environmental hazards, while non-fluorinated systems often struggle to balance solubility and thickening performance. The development of new thickeners primarily involves two directions. On one hand, efforts focus on modifying non-fluorinated polymers, driven by environmental protection needs—traditional fluorinated thickeners may cause environmental pollution, and improving non-fluorinated polymers can maintain good thickening performance while reducing environmental impacts. On the other hand, there is a commitment to developing non-noble metal-catalyzed siloxane modification and synthesis processes, aiming to enhance the technical and economic feasibility of scCO₂ thickeners. Compared with noble metal catalysts like platinum, non-noble metal catalysts can reduce production costs, making the synthesis process more economically viable for large-scale industrial applications. These studies are crucial for promoting the practical application of scCO₂ technology in unconventional oil and gas development, including improving fracturing efficiency and oil displacement efficiency, and providing new technical support for the sustainable development of the energy industry. This study innovatively designed an amphiphilic modified amino silicone oil polymer (MA-co-MPEGA-AS) by combining maleic anhydride (MA), methoxy polyethylene glycol acrylate (MPEGA), and amino silicone oil (AS) through a molecular bridge strategy. The synthesis process involved three key steps: radical polymerization of MA and MPEGA, amidation with AS, and in situ network formation. Fourier transform infrared spectroscopy (FT-IR) confirmed the successful introduction of ether-based CO₂-philic groups. Rheological tests conducted under scCO₂ conditions demonstrated a 114-fold increase in viscosity for MA-co-MPEGA-AS. Mechanistic studies revealed that the ether oxygen atoms (Lewis base) in MPEGA formed dipole–quadrupole interactions with CO₂ (Lewis acid), enhancing solubility by 47%. Simultaneously, the self-assembly of siloxane chains into a three-dimensional network suppressed interlayer sliding in scCO₂ and maintained over 90% viscosity retention at 80 °C. This fluorine-free design eliminates the need for platinum-based catalysts and reduces production costs compared to fluorinated polymers. The hierarchical interactions (coordination bonds and hydrogen bonds) within the system provide a novel synthetic paradigm for scCO₂ thickeners. This research lays the foundation for green CO₂-based energy extraction technologies. Full article

The electrocatalytic decomposition of ammonia represents a promising route for sustainable hydrogen production, yet current systems rely heavily on noble metal catalysts with prohibitive costs and limited durability. A critical challenge lies in developing non-noble electrocatalysts that simultaneously achieve high active site exposure, optimized electronic configurations, and robust structural stability. Addressing these requirements, this study strategically engineered Cu-doped ZIF-8 architectures via in situ growth on nickel foam (NF) substrates through a facile room-temperature hydrothermal synthesis approach. Systematic optimization of the Cu/Zn molar ratio revealed that Cu_0.7Zn_0.3-ZIF/NF achieved optimal performance, exhibiting a distinctive nanoflower-like architecture that substantially increased accessible active sites. The hybrid catalyst demonstrated superior electrocatalytic performance with a current density of 124 mA cm⁻² at 1.6 V vs. RHE and a notably low Tafel slope of 30.94 mV dec⁻¹, outperforming both Zn-ZIF/NF (39.45 mV dec⁻¹) and Cu-ZIF/NF (31.39 mV dec⁻¹). Combined XPS and EDS analyses unveiled a synergistic electronic structure modulation between Zn and Cu, which facilitated charge transfer and enhanced catalytic efficiency. A gas chromatography product analysis identified H₂ and N₂ as the primary gaseous products, confirming the predominant occurrence of the ammonia oxidation reaction (AOR). This study not only presents a noble metal-free electrocatalyst with exceptional efficiency and durability for ammonia decomposition but also demonstrates the significant potential of MOF-derived materials in sustainable hydrogen production technologies. Full article

The early and accurate detection of cancer remains a critical challenge in biomedical diagnostics. In this work, we propose and investigate a novel surface plasmon resonance (SPR) biosensor platform based on a multilayer configuration incorporating copper (Cu), silicon nitride (Si₃N₄), and molybdenum disulfide (MoS₂) for the optical detection of various cancer types. Four distinct sensor architectures (Sys₁–Sys₄) were optimized through the systematic tuning of Cu thickness, Si₃N₄ dielectric layer thickness, and the number of MoS₂ monolayers to enhance sensitivity, angular shift, and spectral sharpness. The optimized systems were evaluated using refractive index data corresponding to six cancer types (skin, cervical, blood, adrenal, breast T1, and breast T2), with performance metrics including sensitivity, detection accuracy, quality factor, figure of merit, limit of detection, and comprehensive sensitivity factor. Among the configurations, Sys₃ (BK7–Cu–Si₃N₄–MoS₂) demonstrated the highest sensitivity, reaching 254.64 °/RIU for adrenal cancer, while maintaining a low detection limit and competitive figures of merit. Comparative analysis revealed that the MoS₂-based designs, particularly Sys₃, outperform conventional noble-metal architectures in terms of sensitivity while using earth-abundant, scalable materials. These results confirm the potential of Cu/Si₃N₄/MoS₂-based SPR biosensors as practical and effective tools for label-free cancer diagnosis across multiple malignancy types. Full article