ABSTRACT This review summarizes advances in electric‐, magnetic‐, and microwave‐field‐assisted catalysis for gaseous pollutant removal. Conventional thermally driven catalytic processes, typically relying on resistive heating, are limited by suboptimal energy efficiency, slow heating rates, and non‐uniform temperature distribution, which collectively constrain catalytic performance. In response to these limitations, externally applied physical fields have emerged as promising strategies to enhance catalytic efficiency. These fields enable rapid and volumetric energy transfer through mechanisms such as Joule heating, magnetothermal effects, and microwave irradiation, thereby reducing energy consumption and shortening startup times. Beyond thermal effects, externally applied fields also induce non‐thermal interactions that modify the electronic structure of catalysts, facilitating reactant adsorption and activation while lowering reaction energy barriers. As a result, these synergistic thermal and non‐thermal effects contribute to enhanced low‐temperature catalytic activity, a broader operating temperature window, and improved resistance to catalyst deactivation. Accordingly, this review systematically summarizes recent advances in field‐assisted catalysis, with particular emphasis on both mechanistic insights and practical applications in pollutant degradation. It also discusses the current challenges and future opportunities in this field, providing valuable perspectives for the development of energy‐efficient environmental remediation technologies and sustainable energy conversion systems.
ABSTRACT Pd was successfully encapsulated inside Silicalite‐1 (S‐1) using a ligand‐assisted one‐pot hydrothermal strategy. AC‐TEM and XAFS characterizations confirmed that Pd species were confined in S‐1 as highly dispersed metallic clusters with the size < 0.9 nm. The confinement effect of S‐1 not only enhances the activity and C═O selectivity in the chemoselective hydrogenation of acetophenone, but also effectively inhibits Pd agglomeration and leaching. With L‐proline serving as the chiral modifier in the enantioselective acetophenone hydrogenation, the Pd@S‐1 catalyst exhibited a reaction rate and turnover frequency (TOF) of 60.6 mmol·h −1 ·g Pd −1 and 14.4 h −1 , which are 36 and 29 times higher than those of the impregnated Pd/S‐1 counterpart, respectively. The confinement effect of S‐1 prevents excessive coverage of metal active sites by the chiral modifier, thereby enhancing both activity and enantioselectivity. A size‐sieving effect was further demonstrated using chiral modifiers and acetophenone derivatives of different sizes. To validate the critical role of confinement, Pd@S‐1@S‐1 sample (core‐shell) and hollow‐Pd@S‐1@S‐1 sample (hollow‐shell structure) were constructed by epitaxial growth of S‐1 shell on the newly prepared or reduced Pd@S‐1, respectively. As compared to Pd@S‐1@S‐1, the hollow‐Pd@S‐1@S‐1 suffered from severe Pd aggregation and a sharp loss of activity due to the lack of pore confinement.
ABSTRACT This communication features a simple methodology for building catalytic cycles for heterogenous catalysts. The methodology is illustrated by an analysis of the catalytic cycle for dry reforming of methane () building from a previous microkinetic analysis of the reaction made by our group (Sandoval et al. ACS Catalysis 2021, 11, 18, 11478–11493) and making use of the principles for constructing chemical reaction networks. The proposed catalytic cycle was conceived under the Occam's razor principle. It has the following merits: (1) It simplifies the interpretation of the reaction mechanisms studied under Langmuir–Hinshelwood rationale. (2) It establishes a mechanistic relationship between dry reforming and the so‐called reverse water–gas shift reaction (). And, (3) it provides a reasonable explanation on the origin of catalyst deactivation by the accumulation of carbonaceous deposits.
ABSTRACT Transition metal oxy‐hydroxide (Ni, Fe, Co, Mo, and V)‐decorated ITQ‐2 composites were synthesized in‐situ via controlled delamination of layered MCM‐22(P) under optimized pH, generating highly accessible active sites with minimal diffusion limitations for biomass ‐derived molecules. The in‐situ delamination strategy avoids multistep post‐synthetic incorporation, ensuring maximum metal loading, strong anchoring, and structural integrity. Structural characterization confirmed nanosheet formation through the disappearance of the (002) interlayer reflection and broadening of intralayer reflections (220), (310)) in the X‐ray diffraction (XRD) pattern and an increase in external surface area (90 to ∼300 m 2 /g) and mesopore volume (∼0.02 to 0.40 cm 3 /g) from N 2 sorption. Field emission scanning electron microscopy (FE‐SEM) revealed a morphological transformation from stacked layers to dispersed platelets. The TEM/HR‐TEM showed uniform slit like layers (∼2.5 nm) decorated with transition metal species (1.5–4 nm). XPS studies established the existence of Ni, Fe, and Co in +2 oxidation states, whereas V and Mo existed as V 5+ and Mo 6+ species, respectively. Catalytic studies demonstrated bifunctionality: ITQ‐2‐Ni‐4 enabled complete hydrogenation of levulinic acid to γ‐valerolactone (97% selectivity) via enhanced H 2 spillover and uniform Ni dispersion. ITQ‐2‐V‐8 and ITQ‐2‐Fe‐2 achieved > 85% conversion in iso ‐eugenol oxidation to vanillin through redox cycling and peroxo‐species formation (> 90% selectivity). Though promising in activity, performance could be improved under continuous‐flow vapor‐phase conditions to mitigate coke deposition.
ABSTRACT Plasma‐driven H 2 O 2 generation offers a potential sustainable route for biotransformations, but its application is hindered by challenges such as insufficient H 2 O 2 production and enzyme degradation. This study establishes plasma‐driven biocatalysis using a nanosecond pulsed microwave plasma torch (npMWPT), highlighting its unique advantages over previously applied sources. npMWPT‐driven biocatalysis addresses insufficient plasma‐generated H 2 O 2 production by enabling continuous H 2 O 2 supply while decoupling plasma treatment from enzymatic reactions. We investigated the effectiveness of npMWPT‐driven biocatalysis using both immobilized and free recombinant unspecific peroxygenase from Agrocybe aegerita (r Aae UPO) to convert ABTS and ethylbenzene. For ABTS, immobilized r Aae UPO demonstrated reusability across five reaction cycles (turnover number TON 44,637 µmol ABTS* µmoL −1 r Aae UPO ). The decoupling of npMWPT‐based H 2 O 2 production resulted in a TON of 66,495 µmol ( R )‐1‐PhOl µmoL −1 r Aae UPO with ethylbenzene for free r Aae UPO, outperforming the use of immobilized r Aae UPO for the first time in plasma‐driven biocatalysis (TTN 22,116). Mixing optimization improved conversion rates, while observed enzyme inactivation under continuous operation revealed that H 2 O 2 generation exceeded enzymatic consumption under the investigated conditions. The present study identifies supply‐demand matching as the key optimization target for npMWPT‐driven biocatalysis. This proof‐of‐principle work demonstrates the successful integration of spatially decoupled npMWPT H 2 O 2 generation with peroxygenase‐based biocatalysis and provides a basis for future process‐controlled plasma‐driven biocatalysis.
ABSTRACT The carbon dioxide dry reforming of methane (DRM) is a promising technology for achieving carbon neutrality via the simultaneous conversion of two greenhouse gases (CH 4 and CO 2 ) into high‐value syngas. However, its industrial implementation is severely hindered by its highly endothermic nature and the rapid catalyst deactivation originating from metal sintering and carbon deposition. This review provides a comprehensive analysis of DRM technology, linking fundamental surface steps to advanced catalyst design strategies. It begins by clarifying the inherent thermodynamic and kinetic constraints, detailing the reactant activation, and uncovering the essence of catalyst deactivation. The design strategies for synthesizing durable and cost‐effective DRM catalysts are categorized into two dimensions: active site engineering (e.g., particle downsizing, bimetallic alloying, and promoter incorporation) and functional support modulation (e.g., acidity–basicity adjustment, oxygen vacancy generation, and multi‐functional confinement). Finally, this review proposes a multi‐dimensional roadmap for future commercialization. We emphasize the integration of data‐driven machine learning (ML), energy‐assisted catalysis, macroscopic process intensification, and techno‐economic analyses. This holistic perspective aims to bridge the gap between laboratory‐scale concepts and industrial feasibility, positioning DRM as a cornerstone technology of the sustainable chemical industry.
ABSTRACT Carbamoyl fluorides have emerged as a versatile and strategic key intermediate at the interface of synthetic organic chemistry, medicinal chemistry, and chemical biology. Due to their distinct stability and selectivity compared to their chloride counterparts, carbamoyl fluorides allow precise access to amides, ureas, carbamates, and various nitrogen‐containing scaffolds and molecular probes. In recent years, there has been a major drive toward their synthesis, including Metal‐promoted formation of carbamoyl fluorides, radical and photoredox reactions, and metal‐free sustainable reactions. Similar developments have increased their use in peptide modification, late‐stage functionalization, and covalent enzyme inhibition, indicating their increasing importance in drug discovery and materials science. This review provides an extensive overview of current synthetic methods for carbamoyl fluorides, with a focus on mechanistic understanding, reaction scope, and limitations. In addition, recent uses in pharmaceuticals, bioconjugation, and functional materials are also critically discussed. To summarize, the use of carbamoyl fluorides as a next‐generation acylating agent, tunable, biocompatible electrophile for covalent binding in modern chemical and chemical biology studies has been discussed.
ABSTRACT Modulating the structure of interfacial electric double layer (EDL) represents a pivotal strategy for enhancing the oxygen reduction reaction activity (ORR) of PtC catalysts in acidic media. This work elucidates the mechanistic influence of imidazolium based ionic liquids (IL) with tailored alkyl chain lengths (C 2 , C 4 , C 6 ) on both the ORR performance and the nanoscale organization of the EDL at the Pt electrocatalyst interface. We demonstrate that the imidazolium ring coordinates selectively with Pt surfaces, enabling stable adsorption and creating a well ordered, nanoconfined environment. Increasing alkyl chain length enhances hydrophobic interactions, which systematically disrupt the interfacial water network and break hydrogen bond continuity. Remarkably, the [C 4 C 1 im] + cation exhibits an optimal balance for structuring hydrogen bonds across both confined and bulk like regions, facilitating dynamic water clusters that yield maximum ORR activity. Through combined in situ attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR‐SEIRAS) and electrochemical studies, we uncover how molecular level design of IL governs hydrogen bond dynamics and directs proton coupled electron transfer kinetics, offering profound insights into interfacial microengineering for advanced electrocatalysis.
ABSTRACT The development of efficient and durable catalysts for ammonia decomposition is critical to realizing a hydrogen economy, yet remains challenging due to the trade‐off between noble metal loading and catalytic stability. Here, we demonstrate that ceramic fiber (CF) supports enable exceptional ammonia decomposition performance with ultralow Ru loading (0.3 wt%). The optimized Ru‐CF catalyst achieves 99.47% NH 3 conversion at 525°C under a gas hourly space velocity of 9000 mL·g cat −1 ·h −1 , maintaining stable operation over 100 h—substantially outperforming its glass fiber (GF)‐supported counterpart. A systematic mechanistic investigation reveals that the CF architecture not only induces abundant oxygen vacancies and modulates the electronic structure of Ru via strong metal–support interactions, but also optimizes Ru dispersion and creates a favorable distribution of acid–base sites. These synergistic effects collectively facilitate N─H bond cleavage and accelerate N 2 recombinative desorption—the kinetically relevant step—fundamentally enhancing the overall reaction kinetics. This work establishes fiber‐based supports as a versatile platform for designing high‐performance, low‐loading precious metal catalysts, offering a viable pathway toward practical hydrogen production from ammonia.
ABSTRACT Electrochemical ammonia oxidation can enable sustainable, distributed synthesis of nitrite and nitrate powered by renewable energy, as an alternative to the centralized Ostwald process. However, the catalyst‐centered research struggles to produce ammonia electrooxidation systems delivering faradaic efficiency, yield rates, selectivity, and stability required for industrial implementation. This perspective aims to explore why current strategies fall short, revealing fundamental constraints that could not be resolved by the catalyst design alone so far. Practical nitrite/nitrate yield rates require potentials where oxygen evolution dominates, while harsh operational conditions inevitably cause corrosion of most materials. We suggest that further progress requires an integrated approach at the overall system level, rather than catalyst design under model conditions, and translating studies of the catalytic and degradation mechanisms into a practical operational environment. In turn, this requires electrolyser architectures suitable for robust high‐current operation. This article aims to propose future research directions that might address these limitations.
ABSTRACT In this study, a novel synergistic three‐layer architecture‐comprising a microwave‐reduced Ni/C base, an electrodeposited Ni interlayer, and a bimetallic Ni–Cu top coat (Ni 30 Cu 70 /Ni/M)‐was designed for the hydrogen evolution reaction (HER) in alkaline media. Structural characterization by X‐ray diffraction (XRD) confirmed the formation of a highly crystalline Ni–Cu alloy, while scanning electron microscopy (SEM) and energy‐dispersive X‐ray (EDX) spectroscopy revealed morphological evolution and surface oxidation. The catalyst initially exhibited a low Tafel slope of approximately 79.4 mV dec −1 , suggesting a mechanism under mixed Volmer–Heyrovsky control. However, chronoamperometric tests at −0.3 V (vs. RHE) over 60 h showed a gradual increase in catalytic activity, suggesting a surface reconstruction process. The integration of structural and electrochemical data indicates stable HER performance over the tested 60‐h period. The findings demonstrate that surface engineering enhances catalytic efficiency in alkaline water electrolysis, emphasizing its significance for optimizing catalysts in practical applications. The findings provide a promising basis for future catalyst development.
ABSTRACT Catalysts based on traditional metal‐supported oxide systems have garnered significant attention in catalytic CO X processes. However, achieving simultaneous high activity, selectivity, and stability remains a formidable challenge, plagued by the limitation of active sites and structural intimacy. Inverse catalysts, as a novel derivative of traditional supported catalysts, invert the spatial configuration of oxides and metals by dispersing nano‐oxide on a metallic substrate. This creates unique interfacial structures and electronic properties via interfacial synergy effects, resulting in excellent performance in various catalytic reactions, making them one of the current research hotspots in the scope of C1 chemistry. This paper systematically reviews the research progress on inverse catalysts, which are categorized into Cu‐based, Ni‐based, and other metals‐based types, mainly focusing on the structural features and catalytic performance in typical small‐molecule conversion such as CO oxidation and CO 2 hydrogenation. It elaborates structure–performance correlations from interfacial interaction, electronic effect, and defect engineering, illustrates performance optimization strategies, and generalizes mainstream synthetic routes. Finally, the paper identifies current challenges in inverse catalysts research. This review offers structure–activity relationship insights and design principles for inverse catalysts, contributing to future directions in design and synthesis.
ABSTRACT The catalytic selectivity of heterogeneous reaction can be effectively regulated by the design of the thickness of zeolite in zeolite‐supported noble metal catalysts. Herein, taking the industrially important hydrogenolysis of the biomass‐derived compound vanillin as an example, ZSM‐5 zeolite with a thinner b ‐axis (75 nm) loaded with platinum particles (denoted as Pt/ut‐ZSM‐5) exhibited 99% conversion and 97% selectivity toward the target product 2‐methoxy‐4‐methylphenol. In contrast, the ZSM‐5‐supported platinum catalyst with a longer b ‐axis (175 nm) showed only 63.4% conversion and 50% selectivity, respectively. Molecular dynamics simulations reveal that the translocation times for intermediate vanillyl alcohol through thinner ZSM‐5 is longer than vanillin, and the diffusion of 2‐methoxy‐4‐methylphenol in thinner ZSM‐5 is faster than that of vanillin. The dynamics of vanillin, vanillyl alcohol and 2‐methoxy‐4‐methylphenol exhibit discontinuous behavior, accompanied by intermittent kinetic restrictions arising from free energy barriers within the straight tunnel of ZSM‐5. The translocation times of vanillin and vanillyl alcohol through the thicker ZSM‐5 zeolite are typically longer than those through the thinner one; the movement of vanillyl alcohol is still slower than vanillin in thicker zeolite. The slower release of intermediate vanillyl alcohol in both thinner and thicker ZSM‐5 demonstrates the possible rate‐limiting step in the reaction‐diffusion process.
ABSTRACT Nitrate (NO 3 − ) pollution threatens aquatic ecosystems and drinking water safety, while electrocatalytic nitrate reduction to ammonia (NO 3 RR) offers a route for pollutant removal and nitrogen recovery. Here, density functional theory calculations were used to screen 100 graphene‐supported asymmetric M1N 3 ─M2N 4 dual‐atom catalysts (M1, M2 = 3 d transition metals) by considering stability, pristine‐site availability, reaction pathways, and ammonia desorption. Single‐H adsorption free energy alone was insufficient to describe competition with the hydrogen evolution reaction in dual‐site systems; *2H and *OH surface states should also be considered when determining catalyst‐specific electrochemical potential windows. NO 3 − mainly adopted side‐on@bridge and side‐on@M1 configurations, leading to site‐dependent pathway branching. Zero or near‐zero U L values often coincide with strong NH 3 binding. NiN 3 ─ZnN 4 ‐P1 and CuN 3 ─CoN 4 ‐P2 displayed balanced profiles, with limiting potentials of −0.29 and −0.23 V and NH 3 desorption free energies of 0.12 and 0.35 eV, respectively. These results provide theoretical guidance for evaluating and designing asymmetric dual‐site NO 3 RR catalysts by jointly considering site availability, pathway thermodynamics, and product release.
ABSTRACT Previously, computational studies have showed MAX phases can be stable with lattice hydride, and some residual amounts of lattice hydride have been observed when prepared from TiH 2 precursor. Separately, MXenes have also been predicted to have activity for N 2 activation. Here, through quantitative H 2 ‐TPD experiments, we show that the MAX phases Ti 2 AlC, Ti 2 AlN, Ti 2 ZnN, V 2 AlC, Cr 2 AlC, Nb 2 AlC, Ti 3 AlC 2 , Ti 3 SiC 2 , and Zr 2 InN can be hydrogenated at elevated temperatures/pressure. They can accommodate up to 0.2 mol of hydrogen per formula unit, although neutron diffraction was unable to clearly identify the coordination site. Despite their compositional similarity to known early transition metal hydride catalysts such as TiH 2 , VH x , NbH x , there is no ammonia synthesis activity on the bare surface. However, by depositing ruthenium metal and cesium as promoter, ammonia synthesis rates up to 17.5 mmol/g/h were attained at 400°C and 50 bar. Kinetic studies on the catalysts revealed no hydrogen poisoning of ruthenium nanoparticles, due to electronic effects from co‐adsorbed hydrogen. The confirmed hydrogen absorption by MAX phases also has implications for various other properties as these materials are used in hydrogen‐containing environments.
ABSTRACT Persulfate‐based advanced oxidation processes (PS‐AOPs) have shown great potential for degrading refractory organic pollutants. However, the widely used persulfates exhibit limited activity at room temperature without efficient activation. Imidazolate metal–organic framework (MOF)‐derived nitrogen‐doped carbon materials offer distinct advantages in catalysis on account of their porous structures and abundant active sites. In this study, a nitrogen‐doped carbon material (ZIF‐67‐NC) was successfully synthesized via pyrolysis of ZIF‐67 combined with melamine. The resulting catalyst exhibited a hierarchical porous structure and was enriched with metallic Co nanoparticles, Co─N x active sites, as well as pyridinic/graphitic nitrogen functionalities. The catalytic performance of these materials in activating peroxymonosulfate (PMS) for phenol degradation in wastewater was evaluated, and the effects of pH, PMS concentration, and catalyst dosage on the degradation efficiency were systematically investigated. Under optimal conditions (pH = 7, PMS mass = 0.8 g, and catalyst mass = 15 mg), the phenol removal efficiency reached 92.0%. This work presents a viable and efficient strategy for the treatment of phenol‐containing wastewater using MOF‐derived nitrogen‐doped carbon materials.
ABSTRACT The development of efficient and durable non‐precious metal electrocatalysts for the oxygen reduction reaction (ORR) is critical to advancing electrochemical energy devices. Herein, we report a porous, carbazole‐based N‐doped carbon framework catalyst embedded with Fe 2 O 3 nanoparticles and Fe‐N x sites. The catalyst was synthesized via pyrolysis of N‐rich hypercrosslinked polymers (NHCP), which were derived from the Friedel‐Crafts reaction, followed by incorporation of hemin (Fe 2 O 3 /NHCP‐2). The introduction of hemin not only preserved the pristine porous architecture but also facilitated the formation of Fe 2 O 3 nanoparticles and Fe‐N x sites, and their synergistic effect enhanced the ORR kinetics in alkaline media. The optimized Fe 2 O 3 /NHCP‐2 catalyst exhibited a high half‐wave potential of 0.87 V and demonstrated robust long‐term durability in a 0.1 M KOH solution. When employed as the cathode material in zinc‐air batteries (ZABs), it delivered a peak power density of 186.84 mW cm −2 and a specific capacity of 731.37 mAh g Zn −1 . This study presents a promising non‐precious metal ORR electrocatalyst for future renewable energy applications.
ABSTRACT Covalent organic frameworks (COFs) are promising organic semiconductors in solar‐driven green hydrogen production. Promoting separation and migration of charge carriers is pivotal to achieve high hydrogen evolution efficiency. Herein, a structural and electronic engineering strategy has been presented through integrating the ketoenamine‐linked COFs containing ‐CF 3 groups (TpPa‐ x CF 3 , x = 0, 0.5, and 1) with cupric oxide (CuO) to form CuO@TpPa‐ x CF 3 dyad. The ‐CF 3 introduction enhances the amount of charge transfer channels between donor and acceptor units in TpPa‐xCF 3 , thereby promoting electron‐hole separation and photogenerated electron migration from TpPa‐xCF 3 to CuO, resulting in improved photocatalytic hydrogen production kinetics. The hydrogen evolution rate of CuO/TpPa‐CF 3 reaches 7354 µmol g −1 h −1 , which significantly surpasses those of CuO/TpPa‐0.5CF 3 (3789 µmol g −1 h −1 ) and CuO/TpPa (1823 µmol g −1 h −1 ), and even Pt‐based counterpart (6115 µmol g −1 h −1 ). This work provides a new strategy to construct noble‐metal‐free COF‐based photocatalytic systems for hydrogen production.
ABSTRACT The boundaries of reductive dehalogenations are being pushed forward with the power of visible light. Flavin derivatives absorb in the blue region and offer unique redox properties that allowed us to collect two photons and two electrons from cheap sacrificial donors in order to form super‐reducing excited flavin species. This enabled the highly selective monodebromination of nonactivated chiral gem‐ dihalohydrins (Br, Cl, F) with no erosion in the enantiomeric purity and resulted readily tolerant with often sensitive functional groups. Moreover, the reaction is compatible with other catalysts such as enzymes, which permits the design of multistep synthetic routes for the construction of molecular scaffolds with more than one stereocenter.
