Catalytic oxidation of carbon monoxide (CO) serves as a pivotal technology for environmental remediation, extensively employed in the purification of automotive exhaust and industrial emissions. Nevertheless, the development of catalysts that maintain high activity at low temperatures while remaining independent of noble metals continues to pose a challenge. In this study, a CuO/TiO2 heterojunction catalyst (denoted as CuTi-MMO-T, T = 300, 400, and 500 °C) was successfully synthesized through controlled-temperature calcination of a CuTi-LDH precursor. The optimized CuTi-MMO-400 achieved complete CO conversion at 150 °C under 41,200 mL·g−1·h−1. The catalyst maintained 100% CO removal over a broad temperature range of 150–400 °C. The synergistic interfacial effects between CuO and TiO2 significantly promoted CO adsorption on CuO and facilitated lattice oxygen migration, thereby enabling efficient CO oxidation via the Mars-van Krevelen (MvK) mechanism. This work provides mechanistic insight into the activation of lattice oxygen in heterojunction systems, and further lays both a theoretical foundation and a practical design pathway for developing high-performance, noble-metal-free catalysts for low-temperature CO oxidation.

Efficient separation and migration of photogenerated carriers remains pivotal yet challenging for advancing photocatalytic performance. To address this bottleneck, we construct an intimately coupled hydrogen-bonded organic framework (HOF)-perovskite (MA3Bi2Br9, MABB) heterojunction, where augmented built-in electric field (IEF) intensity enables directed accelerated carrier transfer. Benefiting from the interfacial compressive strain induced by lattice distortion, reinforced interfacial coupling interactions achieved in the optimized HOFMABB-100. This system demonstrates exceptional performance in selective toluene photooxidation, with benzaldehyde production rate reaching 11,350 mu mol g-1 h-1 and selectivity up 84 %. Simultaneously, HOF passivates the surface defects of MABB and thereby enhancing its stability by retaining 93 % of its catalytic activity after 4 successive cycles. This work validates the immense potential of HOF as a coupling module for designing highperformance lead-free perovskite photocatalysts.

Photocatalytic reduction has been applied for the removal of TcO4-/ReO4- due to the green and eco-friendly advantages, but reports on photocatalytic reduction for TcO4-/ReO4- were few, owing to the limited availability of suitable photocatalytic materials. Herein, two different Conjugated Microporous Polymers (CMPs) were constructed between triazine and thienothiophene using vinyl (Vi-TMT-TT) and phenyl (Ph-TBT-TT) groups as linker and were firstly used for the removal of ReO4-, respectively. Vi-TMT-TT was rich in triazine units with higher density and greater electronegativity, which was more likely to generate more protonation sites and was conducive to the adsorption of ReO4-. After light exposure, the completely planar framework enhanced the photocatalytic activity of Vi-TMT-TT, achieving photo-enhanced rhenium recovery (92 +/- 1)% removal in 100 ppm solutions, pH = 3). By the characterizations such as XPS, pH-zeta, EPR, and combined with DFT calculations, the mechanism was that ReO4- was firstly adsorbed on the triazine unit and reduced to insoluble Re(IV) by photogenerated single electrons in nitrogen atmosphere. The findings provide new insights into the design of materials for TcO4-/ReO4- removal.

Abstract BiVO4 photoanodes are promising for solar-driven water oxidation, but their performance is often limited by inefficient interfacial hole utilization and inadequate operational stability. Herein, via Mo modification, a conventional passive Nb2O5 protective layer on FeOOH/BiVO4 is converted into a functional interfacial layer, simultaneously enhancing photoelectrochemical activity and stability. The resulting Mo:Nb2O5/FeOOH/BiVO4 photoanode delivers a photocurrent density of 6.27 mA/cm2 at 1.23 V vs. RHE under AM 1.5G illumination and maintains stable operation for over 100 h at 0.7 V. Electrochemical analyses reveal markedly suppressed charge recombination and improved interfacial hole utilization. Combined Kelvin probe force microscopy, in situ light-assisted X-ray photoelectron spectroscopy, surface photovoltage measurement and density functional theory calculation demonstrate that Mo incorporation modulates the light-induced interfacial potential redistribution, reconstructs near-Fermi-level electronic states, and promotes a more favorable oxygen evolution reaction pathway. These findings provide an effective strategy for constructing high-performance BiVO4 photoelectrodes by functionalizing a passive protective layer.

Oxygen vacancies (Ov) play a pivotal role in enhancing photocatalytic C-H bond oxidation, yet their susceptibility to depletion under oxidative conditions significantly compromises catalyst stability. To address this challenge, we developed a surface engineering strategy through in-situ growth of a Bi-MOF layer on oxygen vacancy-rich Bi2WO6 (Bi2WO6-x@Bi-MOF). This interfacial Bi-O interaction not only constructed a built-in charge transfer channel to boost electron migration from Bi2WO6-x to Bi-MOF, but also shifted the Bi p-band center closer to the Fermi level (Ef) to facilitate the adsorption of oxygen molecules and toluene. This surface engineering strategy preferentially adsorbs O2 on Bi-MOF and prevents its direct interaction with the Bi2WO6-x host, thereby mitigating oxygen vacancy depletion and enhancing catalyst stability. The optimized photocatalyst achieves 96% toluene conversion and 80% benzaldehyde selectivity within 2 h of light irradiation and maintains excellent structural stability and catalytic performance over ten consecutive cycles. This study offers a new design strategy for constructing robust and efficient Ov-based photocatalytic systems and expands the potential application of MOF materials in complex interfacial reactions. Published by Elsevier B.V. All rights reserved.

Breaking the trade-off between activity and selectivity has always been a long-standing challenge in the field of catalysis. In this study, we introduce an innovative universal pseudo-fluctuation strategy utilizing surface-uncoordinated In(OH)3-x-ZnIn2S4 heterojunctions (ZIO) to achieve local free radical confinement. Notably, the low-coordination and contraction of In-O bonds generate disordered and loosely hydrogen-bonded chains, which enhances the adsorption and activation of toluene. Meanwhile, the dynamic transformation of In-O bonds regulates the d-band center while restructuring a dense hydrogen bonding network. This process locally confines highly reactive oxygen species and facilitates the desorption of benzaldehyde, effectively inhibiting the over-oxidation of the product. Ultimately, after 48 h of irradiation, the photocatalytic toluene oxidation rate of ZIO-2 reached 100.59 mmol g-1 without generating excessive oxidation by-products. Our work delineates a clear surface reaction pathway and introduces a novel design paradigm for atomic-scale photocatalysis in multi-state interfaces, paving the way for advanced catalysts that harness interfacial microenvironments to achieve enhanced performance.

Electrocatalytic upgrading of renewable biomass-derived glycerol represents a sustainable method to produce value-added chemicals, but the complex reaction network of key intermediates during the glycerol oxidation poses challenges to product selectivity. Herein, we report a nickel-doped tungsten oxide catalyst grown on nickel foam (Ni-WOx/NF) for the highly selective electrooxidation of glycerol to formic acid (FA). This optimized catalyst achieves an FA Faraday efficiency (FE) of 95.1% and operates stably for over 18 h, outperforming conventional non-precious metal catalysts. Mechanistic understanding revealed that nickel doping effectively modulates the valence states of tungsten, increasing the proportion of low-valent W4+ species. This promotes the desorption of FA from the catalytic interface, thereby inhibiting its over-oxidation and enhancing selectivity. Taking a step forward, an integrated electrocatalytic system coupling the anodic glycerol oxidation reaction (GOR) with the cathodic nitrate reduction reaction (NO3-RR) is constructed. This system enables the simultaneous coproduction of FA and ammonia (NH3), achieving a high FE for FA of 96.9% along with sustained stability over 12 h, demonstrating significant potential for practical applications. This work demonstrates a sustainable catalytic system for selective glycerol oxidation by precisely regulating the reaction pathways of key intermediates.

Mild and efficient degradation of polyethylene terephthalate (PET) waste requires natural PET hydrolases. However, their inherent limitations, such as high cost, poor operational stability, and catalytic working temperatures below the glass transition temperature of PET, urgently necessitate the advancement of highly thermostable systems with thermophilic catalysis performance. Here, we develop a hydrolase-mimicking thermophilic nanozyme using MgAl layered double oxide with the “memory effect”, which exhibits remarkable catalytic activity and structural stability over multiple reuse cycles. Moreover, different from traditional nanozymes that usually require the ·OH radical-involving mechanism for microplastic degradation, the catalytic hydrolysis capability of thermophilic nanozyme originates from abundant Lewis basic sites that activate water molecules to release OH− ions, thereby facilitating the degradation of PET powders and films under mild conditions. By exemplifying the superior degrading performance toward various polyesters and commercial plastic bottle pellets, thermophilic nanozymes provide an effective method for eliminating polyester microplastics with a distinctive hydrolytic degradation process and may inspire future explorations into the structural mimicry of natural hydrolases.

Selective photocatalytic upgrading of glycerol to glycolaldehyde is intrinsically challenging because, under a conventional C-C cleavage scenario, the carbon-based selectivity of a C2 product is, in principle, capped at 66.67%. Here, a size-regulated Pd on TiO2 platform as an efficient photocatalyst realized selective oxidation of glycerol into glycolaldehyde with selectivity up to 87.54%. As the Pd size increases from single atoms to nanoparticles, both glycerol conversion and glycolaldehyde selectivity increase monotonically, reaching 36.52% conversion and a glycolaldehyde formation rate of 12.05 mmol g‒1 h‒1. Combined in situ spectroscopy, isotope-labeling experiments, and density functional theory calculations reveal that increasing Pd size switches glycerol adsorption from a symmetric terminal-terminal mode to an asymmetric terminal-secondary mode, thereby promoting C-C activation and enabling a radical-mediated cleavage-recoupling route toward glycolaldehyde. Isotopic liquid chromatography-mass spectrometry verifies C-C recombination after bond cleavage, which accounts for the glycolaldehyde selectivity exceeding the conventional 66.67% carbon limit, water as a direct contributor to •OH generation, and oxygen incorporation into the products. This work establishes a mechanistic framework in which metal size alters the interfacial adsorption geometry and reaction energy, thereby providing a general strategy for the selective photocatalytic valorization of polyol biomass molecules.

The selective photocatalytic oxidation of glycerol into high-value-added chemicals presents a promising yet challenging pathway for sustainable energy and environmental applications. In this work, we atomically dispersed Pd single-atoms (Pd1) on Ti-deficient TiO2 (Ti1-xO2) by integrating hydrothermal synthesis with controlled impregnation. Ti defect-site combined with Pd single atom enabled simultaneous adsorption of two adjacent-OH of glycerol, which weakened and promoted the cleavage of C-C bond. In addition, the defective Ti caused lattice distortion of TiO2, which shifted d-band center of Pd single atoms upward, thereby promoting the adsorption of H2O and glycerol molecules as well as reducing the activation barrier of H2O to reactive oxidation species (center dot OH). The glycolaldehyde generation rate reached 4806 mu mol g-1 h-1 with selectivity of 66.64 %, which outperformed Pd1/TiO2 without Ti vacancies (generation rate of 1525 mu mol g-1 h-1 and selectivity of 26.05 %) and the reported photocatalysts. The findings establish a foundational strategy for developing efficient and highly selective photocatalysts in glycerol oxidation, especially for selective C-C bond breakage.

CO oxidation represents a critical environmental strategy for purifying exhaust streams from automotive and industrial sources. However, developing high-performance, cost-effective non-precious metal catalysts with low-temperature activity remains a major challenge. In this work, we synthesize CuO/Cu1.5Mn1.5O4 (CuMn-MMO-T) heterojunction catalysts via temperature-controlled calcination of CuMn-LDH precursors. The optimized CuMn-MMO-400 catalyst remarkably achieves complete CO oxidation at 170 degrees C under a high gas hourly space velocity of 41,200 mL g(-1) h(-1). It maintains 100 % CO removal across a broad temperature window (170 -400 degrees C) and demonstrates exceptional stability over 60 h of continuous operation at 400 degrees C. In situ analysis reveals the synergistic interface between CuO and Cu1.5Mn1.5O4 promotes reactant adsorption and lattice oxygen migration, enabling efficient oxidation of CO to CO2 through a Mars-van Krevelen (MvK) mechanism. Density functional theory (DFT) calculations confirm CuO adsorbs CO, while Cu1.5Mn1.5O4 provides lattice oxygen to achieve the oxidation of CO. This work provides fundamental insights into lattice oxygen activation mechanisms in heterostructured oxides and paves the way for rational design of transition metal catalysts for energy-efficient CO emission control.

Ammonia decomposition is a promising route for on-demand hydrogen production. Herein, we report the synthesis of a compressive-strained Ru/Y2O3-MgO catalyst that exhibits exceptional low-temperature activity for ammonia decomposition. Comprehensive characterizations reveal an ultrathin nanosheet morphology with strong metal-support interactions, which induce lattice mismatch and generate a compressive strain of approximately 4.9%. Kinetic modeling and density functional theory calculations both identify recombination desorption of N2 as the rate-determining step. The compressive strain modulates the electronic structure by shifting its center downward, thereby reducing the activation energy for N-N bond recombination and enhancing catalytic performance. Remarkably, the optimized catalyst with ultralow Ru loading (0.91 wt%) achieves an unprecedented hydrogen production rate of 2479.9 mmolgRu -1min-1 at 450 degrees C, the highest reported value under comparable conditions. This work provides both kinetic and mechanistic insights into the role of strain engineering in promoting ammonia decomposition, offering a promising avenue for efficient hydrogen production.

Residual-stress engineering in two-dimensional (2D) metallic nanostructures presents a promising yet underexplored strategy for tailoring catalytic functionalities. Herein, we demonstrate a breakthrough residual-stressdriven electronic reconstruction in ultrathin PdCu bimetallenes (PdCuene), which dramatically enhances photocatalytic nitrogen fixation performance. The introduction of 0.22 % residual tensile strain, triggers electronic reconfiguration at the atomic-level. This sophisticated strain engineering approach optimizes orbital hybridization states, thereby facilitating N equivalent to N bond activation through a dual synergistic mechanism: i) strain driven stretching of N equivalent to N bond, and ii) enhanced it-electrons feedback from Pd-Cu sites to N2. The optimized photocatalyst exhibits exceptional performance, achieving NH3 production rate of 243.8 mu mol g-1 h-1 under visible light irradiation with apparent quantum efficiency reaching 0.64 % at 350 nm, representing a remarkable 23-fold enhancement compared to pristine CN (10.6 mu mol h-1 g- 1). This work not only establishes residual stress as an intrinsic parameter for precisely manipulating the electronic structure of metallic catalysts but also provides fundamental insights into strain-mediated photocatalysis mechanisms, while simultaneously advancing sustainable paradigms for ammonia synthesis.

Photocatalytic reduction has been applied for the removal of TcO 4 − /ReO 4 − due to the green and eco-friendly advantages, but reports on photocatalytic reduction for TcO 4 − /ReO 4 − were few, owing to the limited availability of suitable photocatalytic materials. Herein, two different Conjugated Microporous Polymers (CMPs) were constructed between triazine and thienothiophene using vinyl (Vi-TMT-TT) and phenyl (Ph-TBT-TT) groups as linker and were firstly used for the removal of ReO 4 − , respectively. Vi-TMT-TT was rich in triazine units with higher density and greater electronegativity, which was more likely to generate more protonation sites and was conducive to the adsorption of ReO 4 − . After light exposure, the completely planar framework enhanced the photocatalytic activity of Vi-TMT-TT, achieving photo-enhanced rhenium recovery (92 ± 1) 4 − was firstly adsorbed on the triazine unit and reduced to insoluble Re(IV) by photogenerated single electrons in nitrogen atmosphere. The findings provide new insights into the design of materials for TcO 4 − /ReO 4 − removal.

Perovskite halides, a promising class of photocatalysts for the selective oxidation of C(sp3)H bonds, face critical challenges for practical implementation. Their inherent chemical instability under illumination and humid conditions, primarily driven by halide ion migration, remains a major obstacle to real-world application. In this work, dodecylphosphonic acid (DDPA)-grafted Cs3SbBiBr9 (CSBB) photocatalysts were achieved as an efficient and stable aerobic oxidation photocatalyst. The formation of strong MOP bonds between DDPA and CSBB directs charge transfer and suppress Br- migration. Concurrently, the long alkyl chain (C12) creates a hydrophobic surface, enhancing toluene adsorption while effectively repelling water and preventing perovskite hydrolysis. Remarkable toluene conversion rate of 21.648 mmol g-1 and 85% selectivity towards benzaldehyde is realized, which is 3.8 times that of pristine CSBB. Moreover, the stability of CSBB was significantly enhanced after DDPA modification.

Photosynthesis of H2O2 has been considered an eco-friendly strategy. However, the concentration of H2O2 reported in earlier studies is far from the industrial requirement. Herein, we present a strategy of employing phenolic hydroxyl-modified imine-based covalent organic frameworks (COFs) as catalysts for enhancing the photosynthesis of H2O2 in a benzyl alcohol (BA)/water system. H2O2 production rate was 19 times that by unmodified imine-based COFs, and the H2O2 concentration reached 380 mM with a record rate of 61.3 M h-1 under simulated solar irradiation. In addition, the selective oxidation of BA into benzaldehyde was achieved, indicating the potential for industrial applications. The phenolic hydroxylic group played an important role, as indicated by the result of experiments and DFT calculations. First, intermolecular hydrogen bonding between the phenolic hydroxyl group and BA facilitated electron transfer, thereby lowering the energy barrier for H2O2 generation. Second, intramolecular hydrogen bonding between the phenolic hydroxyl group and imine increased the energy barriers of H2O2 decomposition and ensured catalyst stability. Overall, our research highlights the critical role of hydrogen bonding in the H atom of C 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 NH in imine-based COFs in augmenting the photocatalytic activity.

Incorporating Fe into the metal-oxo clusters of Zr-based metal-organic frameworks (MOFs) via metal-to-cluster charge transfer (MCCT) is an effective strategy to enhance light absorption and redox activity, thereby improving photocatalytic performance. However, precise control over Fe active sites, particularly the number of Fe atoms, their oxidation states, and coordination environments, remains challenging. This difficulty arises from the dynamic nature of terminal and bridging -OH/H2O ligands on MOF nodes. In this study, three atomically defined Fe configurations (Fe1, Fe2, Fe3) is constructed in a 2D triazine-based zirconium carboxylate MOF (ZrTATB) via postsynthetic modification. A distinct non-linear structure-performance relationship is revealed for photocatalytic toluene oxidation, with Fe2 exhibiting optimal performance. Mechanistic studies reveal that Fe2 achieves a balanced coordination environment. This balance enables efficient water activation (generating •OH) and selective C─H bond cleavage concurrently. Specifically, Fe1 features four uncoordinated hydroxyls, adsorbs toluene too strongly. Fe3, fully saturates its coordination sphere, binds substrates weakly. In contrast, Fe2 preserves two free hydroxyls, achieving moderate adsorption strength and efficient •OH generation. Finally, water availability is found to govern product selectivity between benzaldehyde and benzoic acid, and reaction mechanism is accordingly proposed.

Photocatalytic selective benzene hydroxylation via activation of C(sp2)-H under visible light remains a challenging reaction. Copper-incorporated mixed metal oxide photocatalysts have shown promise in addressing this difficulty by enabling visible light harvesting, controlled reactive oxygen species (ROS) generation, effective ROS utilization, and reactant adsorption. However, copper incorporated metal oxide catalysts were suffered from poor catalytic activity and selectivity due to leaching of Cu species. To solve this problem, herein, a novel stable mixed metal oxide (CuZnSbO) was prepared for the first time by applying a facile method. Copper introduction brought about the suitable band gap energy for a wide range of visible light harvesting of the CuZnSbO catalyst. The copper species play a key role in activating H2O2 to produce hydroxyl radicals (center dot OH) for benzene oxidation by controlling charge recombination. The mixed metal oxide of zinc and antimony supports the included copper strongly enabling copper stability. The CuZnSbO not only generates available hydroxyl radicals but also facilitates efficient hydroxyl radical consumption to initiate C(sp2)-H activation, forming benzene radical intermediates en route to phenol. That is ever reported. CuZnSbO delivered 31.51 % benzene conversion and 100 % phenol selectivity. This work demonstrates the promise of engineered mixed metal oxide that boosts Cu species utilization for H2O2 and benzene activation. The photocatalyst showed good activity in selective oxidative hydroxylation reactions through harnessing visible light and controlled ROS generation. Importantly, Cu cations govern the photocatalytic center dot OH generation mechanisms as shown by XPS and active site deactivation analysis.

Degradation of microplastics represents a significant global environmental challenge, necessitating the development of bio-inspired catalysts with superior activity and stability, capable of mimicking natural plastic-degrading enzymes. Although nanozymes possess advantages such as low cost, ready availability, and multienzymatic activities, issues of self-consumption often hinder their practical application. Here, motivated by the acceleration of Li+ migration for improving the electrochemical reactivity and cycling stability of lithium iron phosphate (LFP), we engineered LFP by introducing Mn2+ to expand the lattice structure, resulting in Mn-doped LFP (LFMP) that modulates ion migration in nanozymes. Density functional theory (DFT) calculations reveal that Mn2+ doping expands the lattice structure of LFP while narrowing its bandgap, thereby significantly enhancing Li+ migration rates. Leveraging this design, LFMP exhibits enhanced peroxidase-like activity (3 times higher than that of LFP) and cycling stability (80% activity retention after 5 cycles versus 45% for LFP), enabling efficient degradation of microplastics made from polyamide 6, high-density polyethylene, and polypropylene. By exemplifying that the degradation efficiency achieved using LFMP nanozymes significantly exceeds that of traditional methods, we affirm that lattice expansion-driven ion migration may inspire future strategies to circumvent the self-consumption issue while maintaining high catalytic activity in nanozymes.