Solar-driven photocatalytic synthesis of hydrogen peroxide (H2O2) represents a highly promising green chemistry route, yet its efficiency is severely constrained by the rapid recombination of photogenerated carriers in traditional photocatalysts. In this study, a Cu doped CdSe-diethylenetriamine/benzoxazinebased 3-aminophenol-formaldehyde (Cu-CdSe-D/APF) photocatalyst integrating strain modulation effects and S-scheme heterojunction characteristics was successfully constructed via a Cu2+ modification strategy. Photocatalytic performance tests revealed that the as-synthesized 0.7%Cu-CdSe-D/APF exhibited superior H2O2 evolution activity under visible light irradiation (lambda >= 420 nm), achieving a yield of up to 5324.2 mu mol g(-1) h(-1), which is 5.3 times higher than that of pristine CdSe-D. Combined analyses using geometric phase analysis, high-resolution transmission electron microscopy, and density functional theory calculations confirmed that the introduction of Cu2+ induces a non-uniform compressive strain field within the 0.7%Cu-CdSe-D/APF. This strain field acts synergistically with the built-in electric field at the S-scheme heterojunction interface, which not only significantly suppresses the recombination of photo-generated electron-hole pairs but also accelerates the directional migration of carriers and the kinetics of surface catalytic reactions. This study provides a new paradigm for designing highly efficient photocatalysts for H2O2 synthesis through a "strain engineering-heterojunction construction" synergistic strategy. (c) 2026 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science & Technology.

Water dissociation is the kinetic bottleneck of the alkaline hydrogen evolution reaction (HER) and is strongly governed by the interfacial electric field. However, its precise and quantitative modulation remains challenging. Here, we report a molecular modification strategy to tune the interfacial electric field using the potential of zero charge (PZC) as a key descriptor. Pyridine sulfonic acid anchors onto CoS2via pyridinic nitrogen, inducing interfacial charge redistribution, while the hydrophilic sulfonate group modulates the local electrostatic environment through interactions with interfacial water. Potential-dependent surface charge analysis reveals a positive PZC shift of 40 mV, indicating an enhanced interfacial electric field under working potentials. In situ Raman spectroscopy shows pronounced changes in water vibrational modes, suggesting a reorganized hydrogen-bond network that facilitates water transport and dissociation. Density functional theory calculations correlate the PZC shift with a reduced water dissociation barrier (from 0.73 to 0.51 eV). As a result, the modified CoS2 exhibits an ultralow overpotential of 23.3 mV at 10 mA cm-2 and a Tafel slope reduced from 151.3 to 54.6 mV dec-1. This work establishes PZC as an effective descriptor for regulating interfacial electric fields and enhancing alkaline HER.

Catalytic hydrolysis is an effective strategy for decomposing tetrafluoromethane (CF4), one of the most chemically inert per- and polyfluoroalkyl substances (PFAS). A key challenge in this process lies in enhancing proton availability to facilitate efficient and stable C–F bond activation while ensuring long-term catalyst stability. Here we present an SO2-driven approach to significantly enhance H2O dissociation and proton-supplying through the in situ formation of Al–HSO4 and Ga–HS species. Combined experimental and theoretical investigations reveal that these species not only lower the energy barrier for C–F bond activation but also promote active site regeneration by facilitating defluorination, thus effectively overcoming catalyst deactivation. As a result, the optimized catalyst enables complete CF4 decomposition at a low temperature of 550°C, with stable operation for over 2500 hours. This work establishes a new paradigm for regulating proton transfer and offers a viable route for the efficient, durable degradation of gaseous PFAS. Catalytic breakdown of highly persistent fluorinated pollutants is hindered by limited proton availability and catalyst degradation. This study shows that in situ proton-supplying sites enable low-temperature, long-lasting decomposition of stubborn PFAS gas.

On-chip electrocatalytic microdevices (OCEMs) are versatile platforms for probing the intrinsic kinetics of individual nanomaterials. However, their applications in evaluating 2D van der Waals materials often suffer from substantial interfacial contact resistance at the electrode/catalyst junction and sluggish catalytic reaction kinetics at the catalyst/electrolyte interface. Herein, we develop an yttrium-doping strategy for monolayer MoS2 (Y-MoS2) that simultaneously optimizes charge injection across the solid-solid (electrode/catalyst) interface and hydrogen binding on the basal plane of MoS2. The Y doping downshifts the conduction band minimum of MoS2, lowering the Schottky barrier from 0.47 to 0.23 eV and enhancing electron injection across the electrode/catalyst interface. The matching spatial orbital symmetry of Y and Mo 4dxz/yz induces strong d-d electronic coupling, driving the formation of a favorable bridge hydrogen intermediate ( H bridge ∗ ) with an optimized binding energy of 0.36 eV for hydrogen evolution reaction (HER) at the catalyst/electrolyte interface. Benefiting from this synergistic optimization of band alignment and hydrogen binding, Y-MoS2 exhibits superior HER performance, delivering an overpotential of 187 mV at 10 mA cm-2, competitive with recent 2D MoS2-based electrocatalysts. This work establishes an optimized OCEM platform for decoupled mechanistic analysis and an orbital-level tuning strategy for efficient electrocatalyst design.

Photosynthesis is regarded as an eco-friendly route for synthesizing hydrogen peroxide (H2O2), a highly active compound with numerous industrial applications. Nevertheless, the rapid recombination of photogenerated carriers within the single-component catalyst severely restricts the productivity of H2O2. Herein, WO3 and CdS-diethylenetriamine (WO3/CdS-D) were applied to fabricate a S-scheme heterojunction comprising interfacial Cd−O bonds with the objective of enhancing performance and conducting a mechanistic investigation. It is evident that, under visible light irradiation, this composite material exhibits remarkable photocatalytic H2O2 production activity within pure water. The optimal 10 % WO3/CdS-D delivered an exceptional H2O2 production rate of 3311 μmol g-1 h-1, clearly superior to those of pristine CdS-D (2254 μmol g-1 h-1) and bare WO3 (7.9 μmol g-1 h-1). The enhancement in performance could be attributed to the interfacial coupling induced by the interfacial Cd−O bonds between WO3 and CdS-D, which facilitated directional charge migration. This study provides experimental and theoretical insight into the charge-transfer mechanism of S-scheme heterojunctions, aiding the design of efficient, green photocatalytic synthesis systems.

Aluminum (Al)-based catalysts are the most widely used materials for CF4 catalytic hydrolysis, where three-coordinated Al (AlIII) active sites play a pivotal role in C-F bond activation. The limited proportion of AlIII active sites in conventional Al-based catalysts suppresses their catalytic activity, thereby requiring high temperatures to achieve complete CF4 decomposition. In this work, we developed a Co-modified strategy to enhance CF4 hydrolysis performance by increasing the proportion of AlIII active sites. Structure characterization revealed that Co modification significantly raised the proportion of AlIII sites from 2% (pure Al2O3) to 13%. Temperature-programmed desorption (TPD) analysis showed that the 0.1Co/Al2O3 catalyst exhibits a CF4 adsorption capacity that is 2.0 times higher than that of unmodified Al2O3. Furthermore, in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) detected a 2 cm-1 red shift in the characteristic C-F bond peaks on the 0.1Co/Al2O3 catalyst, indicating enhanced C-F bond activation. As a result, the 0.1Co/Al2O3 catalyst achieved 100% CF4 decomposition at 580 degrees C for over 170 hours, significantly outperforming pure Al2O3 (58% and 20 hours). This work opens up a new approach for developing highly efficient catalysts for CF4 hydrolysis at low temperatures.

Thermocatalytic hydrolysis of perfluorocarbons (PFCs) is a promising way to reduce their emission and environmental hazards. However, hydrolysis of PFCs, such as CF4, usually suffers from a drastic activity decline during the induction period, which seriously hinders its conversion performances and practical applications. In this work, we found that the carbonaceous (*COO) species account for the activity decline during the induction period, and their detoxification could promote PFC hydrolysis at low temperature. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) shows that the poisoning signals belong to *COO species on the surface of γ-Al2O3 during CF4 catalytic hydrolysis. The adsorption configuration of *CFOH intermediate is the key to the formation of poisoned *COO species. By introducing Ni sites with strong *CFOH adsorption capacity into γ-Al2O3, the *CFOH at the Al active site can transfer to the adjacent Ni site to avoid the formation of poisoned *COO species, which was proved by DRIFTS and density functional theory. As a result, the optimal 0.1Ni/γ-Al2O3 (10% Ni loaded γ-Al2O3) catalyst achieved 100% CF4 conversion without any activity decline at 570 °C for over 300 h, much higher than that of ∼55% CF4 conversion on pure γ-Al2O3 at the same temperature. This work provides new insights into the detoxification of thermocatalytic PFC hydrolysis at low temperatures.

Gas diffusion electrode (GDE)-based flow cells are promising platforms for CO2 electrolysis, yet their practical application is hindered by critical challenges related to GDE stability at high current densities. While hydrophobic expanded polytetrafluoroethylene (PTFE)-based GDEs demonstrate inherent flooding resistance, their poor electrical conductivity necessitates the addition of conductive layers. However, the structure reconstruction of these conductive layers induces surface micro-crack formation and propagation, ultimately compromising electrode stability through serious flooding and hydrogen evolution reaction. In this work, a hydrophobic carbon layer is intercalated between the conductive layer and the catalyst layer as interlayer current collector to optimize the surface micro-cracks and enhance GDE stability for CO2 electrolysis. Scanning electron microscopy images showed fewer surface micro-cracks in the intercalated GDE, leading to lower Ohmic loss and more integrated conductive layer. Real-time electrode surface monitoring showed that the intercalated GDE effectively suppressed surface flooding. COMSOL simulations explained that surface micro-cracks cause uneven local current distribution of catalysts, contributing to device instability. As a result, the Cu deposited PTFE-based GDE with the intercalated carbon current collector operated stably for more than 40 h with a FE(C2+) of similar to 72% at current density of 600 mA cm(-2). This stability is 8 times longer than that of the GDE without intercalation. This work provides an effective approach for designing GDE structures to improve the stability of flow-cell devices in CO2 electrolysis applications.

Hydrogen peroxide (H2O2) is an attractive green oxidant and energy carrier, but its industrial production remains energy- and resource-intensive. Photocatalytic synthesis from O2 and H2O offers a safer and more sustainable alternative, yet its efficiency is hampered by sluggish formation and rapid decomposition pathways. Here, we demonstrate a plasmon-engineered strategy to overcome both challenges using Au@TiO2 core-shell nanostructures. The nanocubic Au@TiO2 (NC@TiO2) achieves a remarkable H2O2 production rate of 350.5 mM h-1g-1 under full-spectrum irradiation -1.6 times higher formation and 47% lower decomposition compared to bare TiO2. Spectroscopic analysis and simulations reveal that localized surface plasmon resonance (LSPR) in the Au core orchestrates photocarrier dynamics: electrons generated in TiO2 are funneled to Au sites to drive O2 reduction, while plasmonic hot electrons neutralize TiO2 holes that would otherwise decompose H2O2. The morphology dependence of this effect is evident: NC@TiO2 with stronger LSPR outperforms rhombic dodecahedral Au@TiO2. These results establish plasmon-mediated charge steering as a powerful tool to enhance both efficiency and selectivity in solar-to-chemical conversion, providing a design principle for next-generation photocatalysts.

Achieving efficient carrier separation in transition-metal-oxide semiconductors is crucial for their applications in optoelectronic and catalytic devices. However, the substantial disparity in mobility between holes and electrons heavily limits device performance. Here we develop a general strategy for enhancing hole mobility via reducing their effective mass through metal vacancy (VM) management. The introduction of VM yields remarkable improvements in hole mobility: 430 Efficient charge carrier separation is a substantial roadblock to achieving high performance in photoelectrochemical systems based on transition-metal oxides. Here a metal vacancy strategy is used to enhance hole mobility, resulting in general enhancement of photocurrent density in WO3, TiO2 and Bi2O3 photoanodes.

Electrocatalysis enables the conversion of CO2 into value-added fuels and chemicals, offering a sustainable solution for greenhouse gas mitigation. However, achieving high selectivity for C2 products like ethylene (C2H4) remains challenging due to competing C1 pathways and complex multielectron processes. Here, we demonstrate that plasmon resonances can selectively enhance the electroreduction of CO2 to C2H4 by 27.0% on a CuPd catalyst under LED illumination (625 nm) at -1.3 VRHE. Photocurrent response, in situ FTIR spectroscopy, and COMSOL simulations reveal that plasmon-derived hot electrons and heating greatly facilitate *CO formation at the CuPd interface, which diffuses to the Cu surface for subsequent C-C coupling. DFT calculations show that the increased *CO coverage on the Cu sites reduces the energy barrier for C-C coupling, ultimately enhancing C2H4 generation. This work offers valuable mechanistic insights into plasmon-mediated electrocatalysis, guiding the development of more efficient plasmonic tandem electrocatalysts for future carbon recycling technologies.

The intensifying global energy crisis,coupled with environmental degradation from fossil fuels,highlights that photocatalytic hydrogen evolution technology offers a promising solution due to its efficiency and sustainability.In this study,we synthesized CeO2/Cd7.23Zn2.77S10-DETA(diethylenetriamine is abbreviated as DETA,and subsequently CeO2 is referred to as EO,Cd7.23Zn2.77S10-DETA is abbreviated as ZCS,and the composite with EO comprising 30%is abbreviated as EO/ZCS)nanocomposites with S-scheme heterojunctions.Under conditions without external co-catalysts and utilizing only visible light as the excitation source,EO/ZCS nanocomposites exhibited outstanding photocatalytic hydrogen evolution activity and remarkable stability,presenting significant advantages over conventional methods that rely on co-catalysts and ultraviolet light.The photocatalytic hydrogen evolution rate of EO/ZCS nanocomposites reached 4.11 mmol/(g·h),significantly surpassing that of EO(trace)and ZCS(2.78 mmol/(g·h)).This substantial enhancement is attributed to the S-scheme charge transfer mechanism at the heterojunctions in EO/ZCS nanocomposites,which effectively facilitates the efficient separation and transfer of photogenerated electron-hole pairs,thereby substantially enhancing photocatalytic hydrogen evolution activity.Through techniques such as X-ray photoelectron spectroscopy(XPS)and theoretical calculations,we confirmed the formation of S-scheme heterojunctions and elucidated their photocatalytic hydrogen evolution mechanism.The results underscore the potential of EO/ZCS nanocomposites as highly efficient and stable photocatalysts for hydrogen production under environmentally benign conditions.

Single-atom Fe-N-C catalysts have attracted significant attention in the NO x reduction reaction (NO x RR). However, the origin of their selectivity in the NO x RR remains unclear, impeding further advancements in application. Herein, we investigate the potential-driven competitive mechanism for NH3 and NH2OH production in the NO x RR over single-atom pyridinic-FeN4 and pyrrolic-FeN4 sites using constant-potential density functional theory calculations. The origin of selectivity in the NO x RR is linked to the switching of Fe 3d orbitals as they interact with intermediates. The selectivity between NH3 and NH2OH is determined by the applied potentials. The pyridinic-FeN4 predominantly generates NH3 at higher reduction potentials (-0.6 to -1.2 V, vs SHE), while NH2OH is favored at lower reduction potentials (0.6 to -0.6 V). The pyrrolic-FeN4 shows a similar potential-dependent product distribution, with a crossover potential of -1.0 V. The selectivity-determining intermediates (SDIs) in the NO x RR are *NH2OH and *NH2 + *OH. The potential-dependent selectivity is governed by the switching of Fe 3d orbitals interacting with SDIs, from dumbbell-shaped Fe 3dz 2 to four-leaf clover-like Fe 3dxz, 3dyz, and 3dx 2 -y 2, which plays a crucial role in controlling product distribution based on applied potentials. These findings offer new insights into the product selectivity of single-atom catalysts for the NO x RR.

Due to the issue of energy depletion, photocatalytic hydrogen evolution has gained significant attention in recent years as a sustainable energy conversion technology. However, traditional single photocatalytic materials often face problems of low catalytic activity and stability. To address this challenge, this study proposes novel BiOBr/Cd0.805Zn0.195S (BO/CZS) nanocomposite materials, which effectively enhance photocatalytic hydrogen evolution efficiency through an S-scheme heterojunction design. Under visible light without the use of a co-catalyst, pure BO shows almost no photocatalytic hydrogen evolution activity, while CZS exhibits a hydrogen evolution rate of 4.0 mmol·g‒1·h‒1. The hydrogen evolution rate of the 2

Acidic CO2 electroreduction to multi-carbon (C2+) products using Cu-based catalyst has attracted considerable attention for CO2 recycling due to high single-pass CO2 utilization. However, its development is drastically limited by the poor stability, especially at high current density, caused by Cu dissolution/reconstruction during the reaction. Herein, we find the trace dissolved oxygen in the electrolyte accounts for the Cu dissolution/reconstruction and report an in-situ passivation strategy to prevent oxygen adsorption for inhibiting Cu dissolution/reconstruction for high stability CO2-to-C2+ conversion. Theoretical and in situ spectroscopy demonstrate that aluminum citrate (AC) passivation layer decreases the adsorption of oxygen on Cu surface to effectively prevent the Cu oxidation, which is beneficial for the formation and adsorption of linearly bonded *CO toward C-C coupling. As the result, the Cu catalysts with AC layer achieve over 60% Faradaic efficiency C2H4 and 38.7% energy efficiency to C2+ for over 150 h stability at 500 mA cm-2 in strong acidic electrolyte.

CO2 electroreduction to produce fuels and chemicals is of great significance. Molecular catalysts offer valuable advantages in light of their well-defined active sites and tunable structural and electronic properties. However, their stability is often compromised by rigid conjugated structures. Herein, we proposed a hydrogen-bond regulation strategy that enables reversible structural deformation of metal phthalocyanines (MPcs) by incorporating methoxy groups into the phthalocyanine framework, thereby improving the flexibility and stability of MPcs. Calculations suggested that intermediate absorption induced structural deformation in MPcs. Moreover, hydrogen-bond interactions and conformational changes enriched with substituted methoxy groups in MPcs enhance structural flexibility. Operando Raman studies revealed that these hydrogen bonds correlated with the reversible structural deformation of NiPc. The optimized catalysts, facilitated by hydrogen bonds, achieved stable operation for over 500 h at 100 mA cm-2 with >98% Faradaic efficiency in CO2-to-CO electrocatalytic reduction, significantly outperforming molecular catalysts lacking appropriate hydrogen-bond interactions.

Acidic CO 2 electroreduction reaction (CO 2 RR) garners significant attention as a promising approach for cutting carbon density, as it effectively mitigates CO 2 loss by suppressing carbonate species formation. Unfortunately, achieving efficient multi‐carbon products (C 2+ ) production in acidic media remains challenging due to two main limitations: weak CO adsorption on Cu sites and competitive H* adsorption caused by the high concentration protons (H + ). To overcome these challenges, a cation‐anion‐modification strategy is proposed using an ionic liquid layer—1‐Propyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([PMIM][NTf 2 ])—on Cu surface. Density functional theory calculations predict that PMIM + cation strengthens *CO adsorption through quasi‐hydrogen bonding, while NTf 2 − anion creates a hydrophobic environment, effectively reducing H* coverage and promoting *CO adsorption. Resistance tests demonstrate that [PMIM][NTf 2 ] modification effectively reduced proton diffusion. Attenuated total reflection infrared spectroscopy (ATR‐IR) confirmed the reinforcement of *CO adsorption on the modified Cu surface. As a result, the [PMIM][NTf 2 ] modified Cu catalyst achieved a remarkable partial current density of ≈640 mA cm −2 for C 2+ products, with exceptional faradaic efficiency of 80.1% and durability of ≈20 h at a partial current density exceeding 500 mA cm −2 in a flow cell. This study highlights the potential of cation‐anion modification strategies for significantly enhancing CO 2 RR in acidic media.

Abstract Perfluorinated compounds (PFCs) are emerging environmental pollutants characterized by their extreme stability and resistance to degradation. Among them, tetrafluoromethane (CF4) is the simplest and most abundant PFC in the atmosphere. However, the highest C─F bond energy and its highly symmetrical structure make it particularly challenging to decompose. In this work, a yolk–shell Al2O3 micro‐reactor is developed to enhance the catalytic hydrolysis performance of CF4 by creating a local autothermic environment. Finite element simulations predict that the yolk–shell Al2O3 micro‐reactor captures the heat released during the catalytic hydrolysis of CF4, resulting in a local autothermic environment within the yolk–shell structure that is 50 °C higher than the set temperature. The effectiveness of this local autothermic environment is experimentally confirmed by in situ Raman spectroscopy. As a result, the obtained yolk–shell Al2O3 micro‐reactor achieves 100% CF4 conversion at a considerably low temperature of 580 °C for over 150 h, while hollow and solid Al2O3 structures required higher temperatures of 610 and 630 °C, respectively, to achieve the same conversion rate, demonstrating the potential of yolk–shell Al2O3 micro‐reactor to significantly reduce the energy requirements for PFCs degradation and contribute to more sustainable and effective environmental remediation strategies.