The aerobic oxidation of aliphatic diols to lactones, such as 1,4-butanediol (BDO) to γ-butyrolactone (GBL), is of great interest but challenging in terms of catalytic efficiency and selectivity. While Pd-Au-based catalysts have been extensively investigated, research to date has largely focused on enhancing catalytic activity by lowering the activation barrier for C-H bond cleavage and increasing the number of sites available for O2 activation. Herein, we report that a Pd-Au/TiO2 catalyst featuring Pd atomic layers supported on Au decahedra delivers 96.0% GBL selectivity at 98.7% BDO conversion in aerobic oxidation. The turnover frequency (TOF) over 30Pd-Au/TiO2 reaches 22038 h-1, a value markedly higher than those reported previously for either Pd or Au catalysts. An abnormal 18O2 KIE effect and the generation of singly 18O-labeled 2-hydroxytetrahydrofuran (2-HTHF, 53.4%) and GBL (58.0%) over Pd-Au/TiO2, combined with in situ FTIR and DFT simulations, point to a mechanism involving insertion of oxygen species into the α-C-H bond to generate a COO* intermediate. Subsequent cleavage of the C-O bond within the COO* to yield an absorbed carbonyl, followed by intramolecular cyclization, constitutes the rate-determining step.

ABSTRACT Sustainable hydrogen generation through water electrolysis is vital for mitigating climate deterioration and the energy crisis. Nevertheless, industrialization is greatly constrained by the low energy utilization, resulting in substantial energy loss within the electrocatalytic system. In this review, focused on the enhanced energy utilization, the up‐to‐date advancements in the novel hybrid electrocatalysis are systemically discussed. In light of a theoretical discussion of energy efficiency in hybrid electrolysis, efficient regulation strategies are expounded for the reduced energy consumption. Special attention is placed on the interplay among the distinctive catalytic behavior, underlying reaction mechanism, and enhanced energy utilization. Valorization systems are proposed for the additional economic benefits in industrial communities, including wastewater purification, high‐valued chemical production, and seawater electrolysis. Moreover, self‐powered and self‐catalyzed electrolysis systems are also discussed for reduced electricity expense through renewable energy sources and intrinsic generated electricity. A systematic economic assessment is provided to evaluate the environmental impact and economic viability of energy‐saving hydrogen production systems. Finally, the prevailing challenges and future prospects are outlined to inspire deep investigation into enhanced energy utilization in high‐efficiency, scalable, and sustainable hydrogen generation through hybrid water electrolysis.

Abstract Identifying metal anchoring sites and their role in dynamic evolution is an important fundamental problem for catalysis research. For industrially used Al2O3 supports, precisely identifying metal anchoring sites remains challenging due to the intricate, diverse nature of their surface structures. Here, we deposited Pt nanoparticles onto hydroxyl groups (–OH) and lattice oxygen sites on hydroxyl-rich and partially dehydrated alumina. Different from the prevailing report of AlV consumption, AlVI transforms to AlV during Pt deposition on lattice oxygen sites. Moreover, different anchoring sites alter catalytic performance by driving the structural evolution of Pt atoms during hydrogenation. Pt nanoparticles bonded to hydroxyl groups are stable, while those nucleated on lattice oxygen undergo atomic redistribution to form more active sites for aromatic hydrogenation. These insights establish a direct link between initial coordination environment and dynamic behavior, advancing molecular-level understanding of metal–support interactions.

The hydroformylation of high-carbon alpha-olefins is a pivotal industrial process. Still, heterogeneous Co-based catalysts suffer from low activity and Co leaching due to strong coordination of CO to Co atoms. Herein, we address the dynamic evolution and active structure of Co species by interacting Co nanoparticles or ultrahigh-dispersed clusters with beta-Mo2C nanoparticles (Co-30Mo(2)C(particle)/CNF) and nanofilms (Co-100Mo(2)C(film)/CNF) on carbon nanofibers. The specific activity in the formation of heptanal from 1-hexene hydroformylation increased by 10.7 times on Co-30Mo(2)C(particle)/CNF (21.4 mol(heptanal)/mol(Co)/h) and 2.4 times on Co-100Mo(2)C(film)/CNF (4.7 mol(heptanal)/mol(Co)/h) compared with Co/CNF (2.0 mol(heptanal)/mol(Co)/h). Moreover, Co-100Mo(2)C(film)/CNF exhibits enhanced stability with only 1.7% Co leaching. The Mo2C nanoparticles interact with Co nanoparticles, oxidizing them to form highly active Co-MoOx sites with a lower CO insertion barrier. The reaction environment influences the structural evolution of the Co-MoOx interaction. In contrast, Mo2C nanofilms form robust Co-C and Co-Mo bonds at the Co-Mo2C interface, stabilizing atomically distributed Co clusters against leaching. This work establishes a morphology-driven strategy to control the dynamic interaction of Co and additives, thereby decoupling activity and stability in heterogeneous catalysis for hydroformylation.

Small molecules-assisted water electrolysis emerges as an efficient strategy for hydrogen production within sustainable energy conversion and storage systems. The urea oxidation reaction (UOR) is particularly attractive for electrocatalyst development and application due to its favorable thermodynamic voltage and the wide availability of urea. In this work, a self-supported electrode composed of aluminum-doped nickel phosphide nanoflowers on nickel foam (Ni2P-Al/NF) is fabricated. This monolithic electrode exhibits superior bifunctional catalytic activity toward both the hydrogen evolution reaction (HER) and UOR. The performance enhancement is attributed to an optimized electronic structure, including a modulated d-band center, tailored charge distribution, and favorable adsorption energetics for key intermediates. As a result, the Ni2P-Al/NF electrode requires remarkably low potentials of -109 mV for HER and 1.36 V for UOR to achieve a current density of 100 mA cm- 2. When configured into a two-electrode urea electrolyzer, the system attains the same current density at a cell voltage of only 1.56 V. Furthermore, the utility of this catalyst is demonstrated in a novel zinc-urea battery, which concurrently enables electricity output, continuous hydrogen generation, and purification of ureacontaining wastewater. This integrated approach offers a promising and environmentally benign pathway for advancing multifunctional energy technologies.

Hydrazine oxidation reaction (HzOR) emerges as a superior alternative to the sluggish oxidation reaction (OER) due to the ultralow thermodynamic potential. Herein, abundant Co2P4O12/Co2P heterostructures were constructed in N-doped carbon (denoted Co2P4O12/Co2P@NC) derived from the waste cigarette butts through the carbonization and subsequent phosphorization process. Owing to the hierarchically wave-like architecture, well-defined electron transfer pathway, and strong interfacial coupling between Co2P4O12 and Co2P, Co2P4O12/Co2P@NC expressed outstanding electrocatalytic performance, requiring ultralow potentials of -207 and 91 mV at a large current density of 500 mA cm-2 for the hydrogen evolution reaction (HER) and HzOR, respectively. When integrated into a hydrazine-assisted water electrolysis as both electrodes, the device required only 0.79 V to drive 500 mA cm-2, significantly lower than that for traditional water electrolysis. Density functional theory (DFT) calculations revealed that the presence of Co2P4O12 optimized the energy barriers of crucial reaction intermediates and accelerated the reaction kinetics for HER and HzOR effectively. Furthermore, an innovative and economic parallel integrated system, entirely driven by solar energy, was proposed as a concept for successive energy-saving hydrogen. This work provides a promising and pragmatic path for energy-efficient hydrogen generation and high-value reutilization of cigarette butt simultaneously.

Electrocatalytic carbon dioxide reduction (CO2RR) represents an innovative technology for energy conversion by converting CO2 into value-added multi-carbon fuels and chemicals, with copper (Cu)-based catalysts playing a pivotal role as the only known metallic capable of driving such multi-carbon product formation. However, pure Cu catalysts suffer from intrinsic limitations, including suboptimal selectivity toward desired hydrocarbons due to unstable key intermediate, and rapid deactivation caused by catalyst surface reconstruction under operational conditions. Cu-based alloy catalysts address the challenges of low selectivity, poor stability, and high overpotential in the electrocatalytic reduction of CO2 by optimizing intermediate adsorption and enhancing reaction kinetics. This review systematically examines the catalytic mechanisms, design principles, and performance of Cu alloys in steering CO2RR pathways toward key products (CO, HCOOH, CH4, C2H4, and C2+ alcohols). By alloying Cu with secondary metals (e.g., Ag, Zn, Sn, or rare-earth elements), bimetallic electronic effects modulate intermediate adsorption energetics (*CO, *COOH, *OCHO) and enhance C–C coupling kinetics. We propose future directions integrating in situ characterization and machine learning-driven alloy design to bridge fundamental understanding with industrial application. This work provides a comprehensive roadmap for developing next-generation Cu alloy catalysts to enable efficient CO2 valorization in a carbon–neutral energy landscape.

Bicyclohexane is a hydrogen storage reagent with high hydrogen density and low boiling point. Compared with the hydrogenation of biphenyl, the alkylation of benzene and cyclohexene to cyclohexylbenzene and hydrogenation is a promising way to prepare cyclohexane on a large scale. The research and development of high-efficiency cyclohexyl benzene hydrogenation catalyst should be further developed based on mature alkylation technology. This paper used an acidified USY molecular sieve to catalyze the alkylation of benzene and cyclohexene to cyclohexylbenzene, which achieved 100% conversion and selectivity. Furthermore, Pt/TiO2/γ-Al2O3 catalyst is prepared by pre-deposition TiO2 film of different thicknesses on γ-Al2O3 surface and then supported with platinum particles by Atomic layer deposition (ALD). The role of TiO2 film in improving the cyclohexylbenzene hydrogenation performance of the catalyst is studied. TEM, CO pulse chemisorption, CO-DRIFTs, quasi-in situ XPS, H-D exchange, and H2-TPR characterization show that compared with Pt/γ-Al2O3, TiO2 thin films on Pt/TiO2/γ-Al2O3 do not change the dispersion of Pt particles, but can form new Pt-TiO2 interactions. The hydrogenation performance of cyclohexylbenzene was improved by increasing the electron density and the proportion of planar active sites on the surface of platinum and reducing the energy barrier of hydrogen spillover. The research provides theoretical support for further bicyclohexane organic liquid hydrogen storage reagent development. The relevant metal-support interaction regulation strategy can be applied to the development of efficient catalysts for other aromatic molecules hydrogenation.

It is crucial to attain a sufficient surface distribution density of metal nanoparticles to achieve high catalytic performance in oxide-supported metal catalysts. Atomic layer deposition (ALD) is a powerful technique for preparing supported nanocatalysts to precisely regulate the metal particle size, structure and distribution in nanoscale. Not only suitable ALD deposition parameters, but also supports with sufficient ALD nucleation sites on the surface are required when using ALD to synthesize supported metal particles with ultrafine size and ultrahigh density. How to regulate the surface nucleation sites to acquire metal nanoparticles with high surface density and elucidating the mechanism are of great importance. Herein, we present a simple thermal treatment approach to activate the surface of γ-Al2O3, significantly enhancing the Pt loading and the density of Pt nanoparticles compared to raw γ-Al2O3 under identical deposition conditions. Detailed mechanism investigations reveal that removing carbonates on the surface of γ-Al2O3 during thermal treatment induces the generation of isolated –OH groups, which are verified to be nucleation sites of Pt ALD. The increase in the number of isolated –OH and its high reactivity towards anchoring Pt precursor molecules in ALD reaction both contribute to a high density of Pt nanoparticles. This work provides a novel approach to promote Pt ALD nucleation on the surface of γ-Al2O3 and an in-depth understanding of the mechanism for the nucleation promotion, which can be applied to other oxide supports.

Bifunctional catalysts comprising metal and acid sites are commonly used for many reactions. Interfacial acid sites impact intermediate reactions more than other sites. However, controlling the type and amounts of interfacial acid sites by regulating metal-support interaction (MSI) via traditional methods is difficult. Thus, the influence of MSI on interfacial acid sites remains unclear. We prepared Pt-mTiO2/α-Al2O3 (m represents the cycle number of TiO2) catalysts via atomic layer deposition (ALD). New Brønsted acid sites were generated via Pt-TiO2 interaction, and the acidity was precisely regulated by regulating Pt-TiO2 interaction by changing the TiO2 nanolayer thickness. We chose levulinic acid (LA) hydrogenation as a model reaction. The catalytic activity varied with the TiO2 nanolayer thickness and was linearly correlated with the Ti-OH species (Brønsted acid) content. Pt-40TiO2/α-Al2O3, with the highest acid site content of 0.486 mmol/g, exhibited the best catalytic activity. Hydrogen spillover and water dissociation at the Pt-TiO2 interface promoted Ti-OH species generation.

Introducing heterometals into Pt/C catalyst to construct multi-metal catalyst for improving the intrinsic activity is a rational strategy which can optimize the over-strong *O adsorption of Pt nanoparticles for oxygen reduction reaction (ORR). However, the practical activity and stability of such carbon supported Pt-based bimetallic catalysts are simultaneously limited by the conductivity degradation and deactivation caused by the weaker interaction between Pt and carbon support. Herein, by taking advantage of the precise control and self-limiting reaction of atomic layer deposition, we construct a novel Pt-Fe-NG structure in which Fe atoms play the bridging role between Pt nanoparticles and the N-doped graphene by multistep deposition. Impressively, the obtained catalyst exhibits an outstanding ORR half-wave potential of 0.948 V, a total four-electron pathway and superior durability over 10,000 cycles. The mass activity of the catalyst at 0.9 V is 15 times higher than that of commercial Pt/C. Moreover, when used as the cathode catalyst of Zn-air battery, the Pt-Fe-NG performs a maximum density power of 230 mW cm-2 and excellent stability after 180 discharge-charge cycles. The experimental results and theoretical calculations indicate that Fe bridging atoms play the role of elevating the d-band center of Pt nanoparticles and enhancing the interaction between Pt nanoparticles and carbon support, which paves a pathway for constructing novel multi-metal catalysts.

Hydrazine oxidation reaction (HzOR) has been proposed to replace the sluggish oxygen evolution reaction (OER) for energy-saving hydrogen generation. However, the rational design of bifunctional electrocatalysts that can simultaneously accelerate HER/HzOR kinetics and the source of the hydrazine chemical substrate are still challenging. Herein, interfacial heterogeneous nickel hydroxide/nickel phosphide microstructures are in-situ grown on nickel foam (Ni(OH)(2)/Ni2P/NF) via a combined electrodeposition-phosphorization-electrodeposition strategy. After Ni(OH)(2) modification, a charge redistribution is triggered between Ni(OH)(2) and Ni2P, reducing the charge-transfer resistance and optimizing the adsorption energy of reaction intermediates. Ni(OH)(2)/Ni2P/NF thus yields an impressive bifunctional electrocatalytic activity for HER and HzOR with potentials of -72 and -14 mV at 10 mA cm(-2), respectively. When using Ni(OH)(2)/Ni2P/NF as both electrodes, decreased cell voltage of 0.357 V is required to drive a current density of 100 mA cm(-2) in 0.5 M hydrazine-containing alkaline electrolyte. Furthermore, an intermittent hydrazine-assisted water electrolysis system is proposed to make the combination of hydrazine sewage purification and energy-saving hydrogen production realistic.

The development of cold‐adapted enzymes with high efficiency and good stability is an advanced strategy to overcome the limitations of catalytic medicine in low and cryogenic temperatures. In this work, inspired by natural enzymes, a novel cold‐adapted nanozyme based on a manganese‐based nanosized metal–organic framework (nMnBTC) is designed and synthesized. The nMnBTC as an oxidase mimetic not only exhibits excellent activity at 0 °C, but also presents almost no observable activity loss as the temperature is increased to 45 °C. This breaks the traditional recognition that enzymes show maximum activity only under specific psychrophilic or thermophilic condition. The superior performance of nMnBTC as a cold‐adapted nanozyme can be attributed to its high‐catalytic efficiency at low temperature, good substrate affinity, and flexible conformation. Based on the robust performance of nMnBTC, a low‐temperature antiviral strategy is developed to inactivate influenza virus H1N1 even at −20 °C. These results not only provide an important guide for the rational design of highly efficient artificial cold‐adapted enzymes, but also pave a novel way for biomedical application in cryogenic fields.

Tailoring the microporosity of intrinsically microporous polymers at the atomic level is one of the biggest challenges in achieving high-performance polymeric gas separation membranes. In this study, for the first time, the Al2 O3 atomic layer deposition (ALD) technique was used to modify the microporosity of a typical polymer of intrinsic microporosity (PIM-1) at the atomic level. PIM-1 with six ALD cycles (PIM-1-Al2 O3 -6) exhibited simultaneous high thermal, mechanical, pure- and mixed-gas separation, and anti-aging properties. The O2 /N2 , H2 /N2 , and H2 /CH4 separation performances were adequate above the latest trade-off lines. PIM-1-Al2 O3 -6 showed CO2 and O2 permeabilities of 624 and 188 Barrer, combined with CO2 /CH4 and O2 /N2 selectivities of 56.2 and 8.8, respectively. This significantly enhanced performance was attributed to the strong size sieving effect induced by the Al2 O3 deposition.

Electrocatalysis is a promising approach to clean energy conversion due to its high efficiency and low environmental pollution. Noble metal materials have been studied to show high activity toward electrocatalyltic reactions, although such applications remain restricted by the high cost and poor durability of the noble metals. By precisely adjusting the catalyst composition, size, and structure, electrocatalysts with excellent performance can be obtained. Atomic layer deposition (ALD) is a technique used to produce ultrathin films and ultrafine nanoparticles at the atomic level. It possesses unique advantages for the controllable design and synthesis of electrocatalysts. Furthermore, the homogenous composition and structure of the electrocatalysts prepared by ALD favor the exploration of structure-reactivity relationships and catalytic mechanisms. In this review, the mechanism, characteristics, and advantages of ALD in fabricating nanostructures are introduced first. Subsequently, the problems associated with existing electrocatalysts and a series of recently developed ALD strategies to enhance the activity and durability of electrocatalysts are presented. For example, the deposition of ultrafine Pt nanoparticles to increase the utilization and activity of Pt, fabrication of core-shell, overcoat, nanotrap, and other novel structures to protect the noble-metal nanoparticles and enhance the catalyst stability. In addition, ALD developments in synthesizing non-noble metallic electrocatalysts are summarized and discussed. Finally, based on the current studies, an outlook for the ALD application in the design and synthesis of electrocatalysts is presented. (C) 2020, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

A Pt/CNTs catalyst coated with N-doped carbon (xNC-Pt/CNTs) is synthesized by atomic layer deposition (ALD) and applied in methanol electrooxidation reaction. Pt nanoparticles and polyimide (PI) are sequentially deposited on carbon nanotubes (CNTs) by ALD. After annealing at 600 °C in H2 atmosphere, the PI is carbonized to produce porous N-doped carbon. Upon coating with a moderately thick layer of N-doped carbon, the optimized 50NC-Pt/CNTs show higher activity, better long-term stability, and improved CO resistance towards methanol electrooxidation compared with Pt/CNTs and commercial Pt/C (20 wt%). X-ray photoelectron spectroscopy characterization result indicates that the Pt–CO bond is weakened after N-doped carbon coating and CO adsorption on the Pt surface is weakened, leading to superior electrocatalytic performance.

A Pt/HZSM-5 catalyst was prepared by atomic layer deposition (ALD) for aqueous-phase hydrogenation of levulinic acid (LA) to valeric acid (VA). 5Pt/HZSM-5 produced with 5 cycles of Pt ALD was identified as a highly active and stable bifunctional catalyst, and a high yield of VA (91.4%) was achieved in aqueous solution. A close interaction between Pt and acid sites of HZSM-5 is favor for the selective generation of VA. The microporous structure and the acid sites of HZSM-5 were not changed after Pt ALD, and some Pt nanoparticles were located in the micropore channel of HZSM-5. This reveals that the Pt ALD has the advantage to protect the structure of zeolite. The average particle size of Pt nanoparticles, electric state of surface Pt, and surface acid sites are nearly not changed with the increase of Pt ALD cycle number. However, the ratio of Pt in the pore channel to that out of the pore decreases with the increase of ALD cycle numbers, resulting in a decrease of TOF of VA yield. For comparison, Pt nanoparticles supported on HZSM-5 were also produced by impregnation. But the pore structure of HZSM-5 was damaged, and more micropore were formed by impregnation method for Pt loading. Moreover, it exhibited very low catalytic activity, selectivity of VA, and stability.

Ideal heterogeneous tandem catalysts necessitate the rational design and integration of collaborative active sites. Herein, we report on the synthesis of a new tandem catalyst with multiple metal-oxide interfaces based on a tube-in-tube nanostructure using template-assisted atomic layer deposition, in which Ni nanoparticles are supported on the outer surface of the inner Al2O3 nanotube (Ni/Al2O3 interface) and Pt nanoparticles are attached to the inner surface of the outer TiO2 nanotube (Pt/TiO2 interface). The tandem catalyst shows remarkably high catalytic efficiency in nitrobenzene hydrogenation over Pt/TiO2 interface with hydrogen formed in situ by the decomposition of hydrazine hydrate over Ni/Al2O3 interface. This can be ascribed to the synergy effect of the two interfaces and the confined nanospace favoring the instant transfer of intermediates. The tube-in-tube tandem catalyst with multiple metal-oxide interfaces represents a new concept for the design of highly efficient and multifunctional nanocatalysts.