Strong Oxidation Research Articles

DBD plasma induced SMOSI and encapsulation for regulation of Brønsted-Lewis acid sites of Cr-MOFs@ZrO2

Dielectric barrier discharge (DBD) plasma for the synthesis of Zr-MOFs followed by the calcination and combination with Cr-MOFs was presented to prepare a Brønsted-Lewis bifunctional catalyst for the conversion of glucose to 5-hydroxymethylfurfural (HMF). The strong electric field on the catalyst surface formed by DBD plasma induced the enhancement of strong metal oxide support interaction (SMOSI), which could be indicated by XPS. SMOSI could change the embedding degree of metal micro-particles. SMOSI accompanied with the encapsulation of Zr metal nanoparticles could regulate the acid sites of the catalysts. Lewis acid played an important role in the isomerization of glucose to fructose, while Brønsted acid played a key role in the further conversion of glucose. The strong Brønsted acid sites determined the conversion of glucose to HMF. Cr-MOFs@ZrO2-D with the DBD plasma method afforded a higher Brønsted to Lewis acid ratio, compared with Cr-MOFs@ZrO2-S with the hydrothermal method. Glucose conversion of 97.9 % and HMF yield of 38 % were obtained with DMF solvent system and Cr-MOFs@ZrO2-D at 150 °C for 2h. This research provided a new method for preparing Zr-MOFs by DBD plasma and a new idea to comprehensively understand the role of Brønsted and Lewis acid sites in glucose conversion.

Electrocatalysts for the Formation of Hydrogen Peroxide by Oxygen Reduction Reaction.

Hydrogen peroxide (H2O2) is a widely used strong oxidant, and its traditional preparation methods, anthraquinone method, and direct synthesis method, have many drawbacks. The method of producing H2O2 by two-electron oxygen reduction reaction (2e- ORR) is considered an alternative strategy for the traditional anthraquinone method due to its high efficiency, energy saving, and environmental friendliness, but it remains a big challenge. In this review, we have described the mechanism of ORR and the principle of electrocatalytic performance testing, and have summarized the standard performance evaluation techniques for electrocatalysts to produce H2O2. Secondly, according to the theoretical calculation and experimental results, several kinds of efficient electrocatalysts are introduced. It is concluded that noble metal-based materials, carbon-based materials, non-noble metal composites, and single-atom catalysts are the preferred catalyst materials for the preparation of H2O2 by 2e- ORR. Finally, the advantages and novelty of 2e- ORR compared with traditional methods for H2O2 production, as well as the advantages and disadvantages of the above-mentioned high-efficiency catalysts, are summarized. The application prospect and development direction of high-efficiency catalysts for H2O2 production by 2e- ORR has been prospected, which is of great significance for promoting the electrochemical yield of H2O2 and developing green chemical production.

Enabling Efficient Oxygen Evolution via Anchoring Carbon-Layer-Confined RuOx on a Well-Matched Substrate.

Oxygen evolution reaction (OER) is a multistep proton-coupled four-electron process with sluggish kinetics, which seriously limits the hydrogen production efficiency, thus it is of great importance to develop an efficient and stable OER catalyst. In this study, a two-step differential pyrolysis strategy is employed to design a three-dimensional porous microstructured material consisting of RuOx nanoparticles coated by a thin-layer carbon, where the active particles were isolated in separate chambers and the RuOx nanoparticles mainly existed in the form of a heterogeneous interface between RuO2 and partial metallic Ru. The preparation parameters of the catalysts are optimized via combining transient and steady-state polarization properties, and the target catalyst Cat-500-1.5t shows the best OER catalytic performance after ca. 60 h of a chronopotentiometry test in an acidic medium with a much smaller performance change than other samples. The unique design of adopting a carbon layer to form separate reaction chambers largely mitigates the excessive oxidation loss of the active components under strong oxidation potential. The suitability of the catalyst with the loaded substrate and test media is explored, and in an acidic medium, the carbon paper is much better than the titanium fiber, while in an alkaline medium, the titanium fiber is obviously superior to the carbon paper. On both carbon paper and titanium fiber, the performance in an alkaline medium outperforms that in an acidic medium, and the possible reasons for the performance difference are analyzed. Herein, to obtain the actual electrocatalytic performance, the optimal design of the catalyst structure and matching suitable conductive substrate in a specific medium are quite necessary, which provides a feasible strategy for the acquisition of efficient and stable electrocatalysts and the desirable presentation of performance.

Modified Si Oxidation Behavior by Ultrathin Ni Catalyst Enabling Oxidant-Less Metal-Assisted Chemical Etching.

Metal-assisted chemical etching (MACE), a wet-based anisotropic etching process for semiconductors, has emerged as an alternative to plasma-based etching. However, using noble metal catalysts in MACE limits the implementation of complementary metal-oxide-semiconductor (CMOS) processes. This study explores Si etching using an ultrathin Ni catalyst as a novel approach for MACE. The thickness of the Ni catalyst emerges as a critical parameter, with 1 nm of Ni proving to be the optimal thickness to achieve smooth and deep etching. Unlike conventional MACE methods, the ultrathin Ni catalyst enables Si etching without strong oxidants. Wafer-scale Si etching demonstrates the versatility of the ultrathin Ni catalyst in producing various microstructures. It is found that the ultrathin Ni/Si interfacial state plays a crucial role in influencing the Si reactivity, lowering the barrier for Si oxidation. CMOS-compatible and cost-efficient ultrathin Ni makes MACE a promising alternative for semiconductor nanofabrication. This study pioneers MACE using an ultrathin non-noble metal catalyst, offering valuable insights for researchers in this field.

A three-stage oxidation method improves sludge dewaterability by achieving sustained oxidation and phased enhanced coagulation: Ingeniously using H2O2 as a “converter”

Sludge reduction is essential for mitigating the environmental hazards associated with sludge. The use of ferric chloride (Fe(III)) catalyzed ferrate (Fe(VI)) can significantly enhance sludge dewaterability by increasing the Fe(VI) oxidation rate and maintaining in-situ enhanced coagulation. However, its weak oxidation ability at the sludge’s original pH limits its practical application. To address this, hydrogen peroxide (H2O2) strengthened Fe(VI)/Fe(III) was employed to efficiently improve sludge dewaterability without pH adjustment, thereby enhancing the environmental utilization capacity of sludge. Compared to raw sludge, the treatment of Fe(VI)/Fe(III)–H2O2 resulted in approximately the 95% reduction in specific resistance to filtration (SRF) and increased the bioavailable phosphorus (P) content in dewatered sludge. During the oxidation process, highly reactive species such as tetravalent iron (Fe(IV)) and hydroxyl radicals (OH) were generated, facilitating the release of tightly bound water in extracellular polymeric substances (EPS). Importantly, the oxidation process was divided into three stages (persistent moderate oxidation — fast strong oxidation — sustained weak oxidation) based on the predominant reactive species (Fe(IV) or OH). This division promoted more robust and more durable oxidation processes. Phased enhanced coagulation occurred during the oxidation process. The gradual increase in Fe(III) content led to the re-flocculation of damaged EPS, enlarging the size of sludge drainage pores/channels and improving water discharge efficiency. Additionally, the costs and carbon emissions of chemicals for the Fe(VI)/Fe(III)–H2O2 process were 18% and 52% lower than those of the traditional Fenton method. This study not only achieves the goals of sludge reduction and resource collection but also provides insights into selecting sludge conditioning methods that meet pollution reduction and carbon emission reduction requirements.

Redox ability dependent SO2 tolerance for low-temperature NH3-SCR of MnO2@MeOX (Me = Ti, Ce, Cu) catalysts

Elucidating the deposition behavior of sulfates on catalysts of low-temperature ammonia-assisted selective catalytic reduction (NH3-SCR) helps improve their SO2 tolerance and applicability. Therefore, this study aimed to explore the impact of the redox properties of low-temperature NH3-SCR catalysts on their catalytic activity and SO2 tolerance. Oxidizing Mn@Ce, neutral Mn@Ti, and reducing Mn@Cu catalysts were prepared, and their NH3-SCR activities and SO2 tolerances were evaluated. Subsequently, the characteristics of the catalyst poisoned by SO2 over time and the deposition behavior of sulfates on the catalyst were analyzed to determine the reaction pathway between SO2 and the NH3-SCR catalyst. The SO2 tolerance of the catalysts decreased in the following order: oxidizing Mn@Ce > neutral Mn@Ti > reducing Mn@Cu. Combined with the characteristic results, we found that the amount of shell-metal sulfate increased with SO2 poisoning time, indicating it was the dominant factor in catalyst deactivation. Specifically, the amount of shell-metal sulfate followed the order Mn@Cu-S12 (31.4 µmol) > Mn@Ti-S12 (24.9 µmol) > Mn@Ce-S12 (9.5 µmol). Additionally, the increasing SO42− ratio from Mn@Me-S4 to Mn@Me-S12 followed the order Mn@Cu (6.7 %) > Mn@Ti (4.4 %) > Mn@Ce (1.7 %), implying that the reduction of Mn@Cu favors chemical SO2 poisoning pathway and facilitates the deposition of copper sulfate. In contrast, Mn@Ce with its strong oxidation properties, is beneficial for inhibiting the chemical poisoning pathway of SO2 and alleviating the deposition of cerium sulfate. Consequently, this study demonstrates that the redox ability of catalyst regulates the SO2 poisoning pathways, aiding the development of low-temperature NH3-SCR catalysts with high SO2 tolerance.

Enhanced removal of phenolic pollutants over MnO2 initiated by peracetic acid: In situ generation of a heterogeneous Mn(III)-hydroperoxo complex

Widely distributed manganese oxides are among the strongest oxidants in nature and effectively enhance the water decontamination by peracetic acid (PAA) activation. However, the precise mechanism requires further investigation. In this work, the intrinsic mechanism of PAA activation by MnO2 was systematically studied. Through in situ diffuse-reflectance UV–vis spectra and resonance Raman spectra, the active species was identified as a non-radical heterogenous Mn(III)-hydroperoxo complex. During the process, PAA drastically converted Mn(IV) in MnO2 into homogeneous Mn(II), which subsequently generated the active Mn(III) species in the aid of PAA on the surface of MnO2. By interacting with pollutants, the peroxide bond in Mn(III)-hydroperoxo broke, accompanied by the regeneration of Mn(IV). Eight phenolic compounds having para-substituent of –CH3, −H, −Cl, –COCH3, –CHO, –COOH, –COOCH3, and –NO2 were selected for degradation. Due to the electrophilic character of Mn(III)-hydroperoxo, the removal rates were 100 %, 100 %, 98.8 %, 69.8 %, 49.6 %, 30.2 %, 28.1 %, and 3.0 % respectively at the 45 min of experiment. The MnO2/PAA system was also readily coupled with a filtration membrane for continuous treatment of phenol in nearly 100 % removal efficiency. This study not only offered an efficient non-radical PAA activation protocol for water decontamination, but also elucidated the catalytic mechanism and redox cycle of MnO2 in PAA solution in the selective oxidation process.

Halide Perovskite Induces Halogen/Hydrogen Atom Transfer (XAT/HAT) for Allylic C−H Amination

AbstractAllylic C−H amination has emerged as a powerful tool to construct allylamines, common motifs in molecular therapeutics. Such reaction implies an oxidative path for C−H activation but furnishes reductive amines, inferring mild oxidants’ inactivity for C−H oxidation but strong oxidants’ detriment to products. Herein we report a heterogeneous catalytic approach that manipulates halogen‐vacancies of perovskite photocatalyst and exploits halogenated‐solvents (i.e. CH2Cl2, CH2Br2) as mild oxidants for selective C−H allyl amination with 19,376 turnovers. CsPbBr3 nanocrystals induce cooperative hydrogen‐atom‐transfer (HAT, C−H oxidation, and halogen‐vacancy CsPbBr3−x formation) and halogen‐atom‐transfer (XAT, CsPbBr3−x‐induced solvent reduction) under a radical chain mechanism. Terminal/internal olefins are amenable to forge aromatic/aliphatic, cyclic/acyclic, secondary/tertiary allylamines (70 examples), including drugs or their derivatives.

Status and Enhancement Techniques of Plastic Waste Degradation in the Environment: A Review

Plastic waste has been gradually accumulating in the environment due to rapid population growth and increasing consumer demand, posing threats to both the environment and human health. In this overview, we provide a comprehensive understanding of the degradation of plastics in real environments, such as soil, aquatic environment, landfill, and compost. Both conventional and biodegradable plastics exhibit limited degradation in real environments, except for biodegradable plastics during industrial composting with high thermophilic temperatures. Meanwhile, we also review techniques for enhanced degradation of plastics such as physical technologies (e.g., photocatalysis, mechanical degradation, and pyrolysis), chemical technologies (e.g., hydrolysis, alcoholysis, ammonia, strong oxidation, and supercritical fluids), and biotechnologies (e.g., microorganisms, microfauna, and microalgae). The future research directions for the enhancement of plastic degradation are also discussed, such as the establishment of equivalency standards, adoption of internal control techniques, the control of precise recycling of plastic products, and the ecotoxicology of their degradation products. Therefore, this review comprehensively summarizes the state of plastic degradation in real environments and proposes methods to improve plastic degradation, providing a theoretical basis for the future control and disposal of plastics.

A Mini-Review on the Use of Chelating or Reducing Agents to Improve Fe(II)-Fe(III) Cycles in Persulfate/Fe(II) Systems

Persulfates (PSs) have recently gained recognition as strong oxidants notably for soil and groundwater remediation. Ferrous iron (Fe(II)) has been extensively employed in activating PS. However, the PS/Fe(II) system still suffers from some inherent drawbacks, including the fast accumulation of ferric ion (Fe(III)) or precipitation of Fe(III), sluggish conversion from Fe(III) to Fe(II), and the unwanted scavenging of SO4•− by excess Fe(II). To overcome these issues, the following two types of reagents are usually used: chelating agents and reducing agents. There are 11 chelating agents mentioned in this paper (EDTA, CA, etc.) and 3 reducing agents (HA, thiosulfate and A-Boron). This review extracted data from studies to give a data-based overview on how the added agents can improve the PS/Fe(II) system under varied conditions. The mechanisms of improvement by chelating agents could be classified into the following three categories: to control excess Fe(II), reduce Fe(III) to Fe(II), and inhibit Fe precipitation. The data analysis suggested an optimal working agent/Fe(II) ratio of 0–2 with acidic and neutral pH. The mechanism of using a reducing agent for PS/Fe(II) system improvement is simply reducing Fe(III) to Fe(II), using hydroxylamine, thiosulfate, etc. The improvement was significant at a hydroxylamine/Fe (II) molar ratio between 0 and 10, yet overdosed hydroxylamine can scavenge the reactive radicals, resulting in negative effects. The future research trend was also proposed in this review.

Electrochemical Ferrier Rearrangement of Glycals.

The Ferrier rearrangement (FR) is a well-documented reaction that relies on strong acids or oxidants to convert glycals into unsaturated glycosyl derivatives. In this work, we introduce an electrochemical variant of the FR, offering a broad substrate compatibility. Various nucleophiles and glycal derivatives afford 2,3-unsaturated glycosyl derivatives in high yields with excellent diastereoselectivities. This sustainable method promises to expand the electrochemistry applications in sugar chemistry.

Acid-Promoted Self-Photocatalyzed Regioselective Oxidation: A Novel Strategy for Accessing Quinoxaline-2,3-diones.

Disclosed here is an efficient approach for the preparation of quinoxaline-2,3-diones using air (O2) as a green oxidant via acid-promoted self-photocatalyzed regioselective oxidation of quinoxalin-2(1H)-ones at C-3 position. This protocol presents a novel synthetic route for the preparation of quinoxaline-2,3-dione derivatives, featuring mild reaction conditions, simple operation, and a wide range of substrates, without the need for external photocatalysts, metal reagents, and strong oxidants.

Tailoring the Heterointerfaces of Earth-Abundant Transition-Metal Nanoclusters on Nickel Oxide Nanosheets for Enhanced Overall Water Splitting through Electronic Structure Optimization.

Evolving highly competent and economical electrocatalysts for alkaline water electrolysis is crucial in renewable hydrogen energy technologies. The slow hydrogen evolution reaction (HER)/oxygen evolution reaction (OER) kinetics under alkaline electrolytes, still, has troubled developments in high-performance green hydrogen production systems. Herein, we demonstrate the tailoring of the interface of earth-abundant transition-metal nanoclusters (MNCs), including iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu) nanoclusters on nickel oxide nanosheets (M NCs|NiO NS) through metal-support interaction for enriched overall water splitting under an alkaline electrolyte. The strong metal-metal oxide interaction allows alteration of the binding capabilities of hydrogen ions (*H) and hydroxyl ions (*OH) on Ni electrodes. Specifically, the robust interaction between Fe and NiO reveals optimized binding of H* and OH* energies, facilitating the water-splitting reaction under an alkaline electrolyte. In addition, the improved HER/OER catalytic activity is attained with the Fe NCs|NiO NS with small overpotentials of ∼62.0 and ∼380.0 mV for the HER and OER, respectively, a high mass activity of ∼90.0 A g-1, a turnover frequency of ∼5.94 s-1, and long-lasting stability via offering abundant electrochemical active sites, three-dimensional (3D) morphologies, and high dispersion of nanoclusters that provide effective charge and mass transport processes. This study provides a promising strategy for the effective design of efficient bifunctional electrocatalysts based on earth-abundant materials for alkaline water electrolyzers.

Deep oxidation of NO via catalytic ozonation

ABSTRACT In addition to selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR) which are available to remove NOx from flue gas, oxidation method is receiving more and more attention because this method makes it possible to remove NOx and SO2 from flue gas simultaneously by wet scrubbing. O3 as a strong oxidant has a high oxidation capacity and it can oxide NO to N2O5 which has a higher water solubility compared with NO2. However, it needs a long reaction time and the escape of unreacted ozone may cause secondary pollution. In this study, FeMnCo/Al2O3 catalyst and FeMnCe/Al2O3 catalyst were prepared and applied to enhance the deep oxidation of NOx with ozone and reduce O3 slip. Effects of various operating parameters such as O3/NO ratio, gas residence time and operating temperature were evaluated and the results demonstrate that N2O5 began to generate when O3/NO ratio was higher than 1.0 and increased with increasing O3/NO ratio. Little residual O3 was formed in the presence of catalyst while 350 ppm O3 was measured at the outlet gas when O3/NO ratio was controlled at 2.0. The N2O5 conversion efficiency increased with increasing gas residence time, operating temperature and the highest N2O5 conversion efficiency was achieved at 100°C. Furthermore, the conversion efficiency remained around 90% during 20 h operation over FeMnCe/Al2O3 catalyst with an O3/NO ratio of 1.73, a gas residence time of 1.2 s, and a temperature of 100°C. On the other hand, the N2O5 conversion efficiency remained around 80% during 3 h operation over FeMnCo/Al2O3 catalyst. Overall, FeMnCe/Al2O3 catalyst reveals good potential for deep oxidation of NO by O3 and can be further developed as a viable catalyst for reducing NO emission from industries.

Palladium-Functionalized Nanostructured Nickel-Cobalt Oxide as Alternative Catalyst for Hydrogen Sensing Using Pellistors.

To meet today's requirements, new active catalysts with reduced noble metal content are needed for hydrogen sensing. A palladium-functionalized nanostructured Ni0.5Co2.5O4 catalyst with a total Pd content of 4.2 wt% was synthesized by coprecipitation to obtain catalysts with an advantageous sheet-like morphology and surface defects. Due to the synthesis method and the reducible nature of Ni0.5Co2.5O4 enabling strong metal-metal oxide interactions, the palladium was highly distributed over the metal oxide surface, as determined using scanning transmission electron microscopy and energy-dispersive X-ray investigations. The catalyst tested in planar pellistor sensors showed high sensitivity to hydrogen in the concentration range below the lower flammability limit (LFL). At 400 °C and in dry air, a sensor response of 109 mV/10,000 ppm hydrogen (25% of LFL) was achieved. The sensor signal was 4.6-times higher than the signal of pristine Ni0.5Co2.5O4 (24.6 mV/10,000 ppm). Under humid conditions, the sensor responses were reduced by ~10% for Pd-functionalized Ni0.5Co2.5O4 and by ~27% for Ni0.5Co2.5O4. The different cross-sensitivities of both catalysts to water are attributed to different activation mechanisms of hydrogen. The combination of high sensor sensitivity to hydrogen and high signal stability over time, as well as low cross-sensitivity to humidity, make the catalyst promising for further development steps.

Engineered biochars for simultaneous immobilization of as and Cd in soil: Field evidence

Agricultural soil contamination by potentially toxic elements (PTEs) such as arsenic (As) and cadmium (Cd) poses a serious threat to food security. Immobilization serves as a widely used approach for the remediation of PTEs contaminated soils, nevertheless, the long-term effectiveness for the simultaneous immobilization of both cations and oxyanions remains a challenge. In order to effectively enhance the synergistic immobilization effect of soil As and Cd contaminated by multiple elements and improve the ecological environment of farmland. In this study, a typical polluted tailings area farmland was selected for situ immobilization experiments, and biochar was prepared from cow manure (CMB), rice straw (RSB), and pine wood (PWB) as raw materials. On this basis, the pristine biochar was modified with ferric chloride (F), potassium permanganate (K), magnesium chloride (M), and aluminum chloride (A), respectively. Furthermore, the immobilization effect of modified biochar on As-Cd and the stress effect on soil respiration were investigated. The results showed that CMB and RSB reduced the bioavailability of heavy metals, potassium permanganate has strong oxidizing properties, and the strong oxidability of potassium permanganate stimulated the generation of more oxygen-containing functional groups on the surface of biochar, thereby enhancing the adsorption and complexation effect of modified materials on As and Cd. Among them, the extracted Cd concentration of Diethylenetriamine pentaacetic acid (DTPA) in KCMB and KRSB in 2020 decreased by 8.23–43.12% and 9.67–35.29% compared to other treatments, respectively. Meanwhile, the KCMB and KRSB treatments also reduced the enrichment of As and Cd in plant tissues. In addition, the dissolved organic carbon (DOC) content in KCMB treatment was relatively high, and the carbon stability of the material was weakened. Simultaneously, the soil respiration emission of KCMB treatment was increased by 5.63% and 11.93% compared to KRSB and KPWB treatments, respectively. In addition, the structural equation also shows that DOC has a large positive effect on soil respiration. In summary, the KRSB treatment effectively achieve synergistic immobilization of As-Cd and provide important guiding significance for green and low-carbon remediation of polluted farmland.

Quantitative Analysis of Ferrate(VI) and Its Degradation Products in Electrochemically Produced Potassium Ferrate for Waste Water Treatment

Potassium ferrate(VI) (K2FeO4) as a particularly strong oxidant represents an effective and environmentally friendly waste water treatment material. When produced by anodic oxidation in highly alkaline aqueous solution, the K2FeO4 product is separated and sealed in inert plastic bags with the retention of some liquid phase with high pH. This method proved to be excellent for long-term storage at moderately low temperature (5 °C) for industrial applications. It is still imperative to check the ferrate(VI) content of the product whenever it is to be used. Fe-57 Mössbauer spectroscopy is an excellent tool for checking the ratio of ferrate(VI) to the degradation product iron(III) in a sample. For this purpose, normally the spectral areas of the corresponding subspectra are considered; however, this approximation neglects the possible differences in the corresponding Mössbauer–Lamb factors. In this work, we have successfully determined the Mössbauer–Lamb factors for the ferrate(VI) and for the most common iron(III) degradation products observed. We have found superparamagnetic behavior and low-temperature phase transformation for another iron(III) degradation product that made the determination of the Mössbauer–Lamb factors impossible in that case. The identities of a total of three different iron(III) degradation products have been confirmed.

High-Efficiency Photo-Assisted Large Current-Density Water Splitting with Mott-Schottky Heterojunctions.

The development of bifunctional photogenerated carrier-assisted electrocatalytic (PCA-EC) electrodes that operate with stability at large current-density remains a significant challenge. Herein, we demonstrate a simple sputtering-deposition process to synthesize a novel MnWO4/FeCoNi Mott-Schottky heterojunction coating and deposit it on a pure Ti substrate to prepare high-performance PCA-EC electrodes, which exhibits enhanced light absorption range/intensity and rapidly separated photogenerated electron-hole pairs. This design allows photogenerated electrons to directly participate in the hydrogen evolution reaction (HER), while the strong oxidation of photogenerated holes significantly reduces the defect formation energy of active metals, thereby facilitating the rapid reconstruction of highly active Ni(FeCo)OOH/MnOOH species for the oxygen evolution reaction (OER). As expected, the as-prepared electrode demonstrates the overpotentials of 64 mV for the HER and 204 mV for the OER at 10 mA cm-2 under illumination. Benefiting from the stable interface with Fe/Co/Ni-O-Mn/W bonding units, the dual-electrode photoassisted electrolytic cell achieves long-term stability at current densities of 500 and 1000 mA cm-2. This work provides detailed insights into the enhancement mechanism of PCA-EC and contributes to the development of photo-assisted water splitting electrodes for large current-density applications.

High‐Efficiency Photo‐Assisted Large Current‐Density Water Splitting with Mott‐Schottky Heterojunctions

The development of bifunctional photogenerated carrier‐assisted electrocatalytic (PCA‐EC) electrodes that operate with stability at large current‐density remains a significant challenge. Herein, we demonstrate a simple sputtering‐deposition process to synthesize a novel MnWO4/FeCoNi Mott‐Schottky heterojunction coating and deposit it on a pure Ti substrate to prepare high‐performance PCA‐EC electrodes, which exhibits enhanced light absorption range/intensity and rapidly separated photogenerated electron‐hole pairs. This design allows photogenerated electrons to directly participate in the hydrogen evolution reaction (HER), while the strong oxidation of photogenerated holes significantly reduces the defect formation energy of active metals, thereby facilitating the rapid reconstruction of highly active Ni(FeCo)OOH/MnOOH species for the oxygen evolution reaction (OER). As expected, the as‐prepared electrode demonstrates the overpotentials of 64 mV for the HER and 204 mV for the OER at 10 mA cm−2 under illumination. Benefiting from the stable interface with Fe/Co/Ni‐O‐Mn/W bonding units, the dual‐electrode photoassisted electrolytic cell achieves long‐term stability at current densities of 500 and 1000 mA cm−2. This work provides detailed insights into the enhancement mechanism of PCA‐EC and contributes to the development of photo‐assisted water splitting electrodes for large current‐density applications.

Fabrication of CoTiO3/MgIn2S4 S–scheme heterojunctions with efficient charge separation to enhance the photocatalytic activities of hydrogen generation and formaldehyde removal

The efficient separation of photoinduced charge carriers is a primary factor in the catalytic performance of photocatalysts. Constructing S-scheme heterojunctions is a prospective strategy to efficiently and spatially separate photoinduced charges while retaining strong oxidation and reduction capacities of the catalyst system. Herein, CoTiO3/MgIn2S4 (abbreviated x% CTO/MIS, where x% represents the mass ratio of CTO-to-MIS; x = 5, 10, 15, 20, and 25) heterojunctions were successfully synthesized using a hydrothermal method. These heterojunctions exhibited highly efficient and reusable visible-light photocatalytic properties for hydrogen (H2) generation and formaldehyde (HCHO) degradation. Notably, the 15 % CTO/MIS demonstrated an admirable H2 evolution activity of 631.77 μmol·g−1·h−1, with AQE = 2.25 % at λ = 420 nm, and an HCHO degradation rate of 67.18 %. The intermediate products generated during HCHO removal were identified applying in situ diffuse reflectance infrared Fourier transform spectroscopy. The exceptional catalytic performance of the synthesized materials was attributed to the boosted light absorption and utilization, rapidly separation, and transfer of photoproduced charge carriers, which resulted from the internal electric field of the S-scheme mechanism. Moreover, the S-scheme electron transfer pathway for the CTO/MIS catalyst system during the photocatalytic process was confirmed using electron spin resonance spectroscopy, free-radical capturing tests, density functional theory calculations, in situ X-ray photoelectron spectroscopy, and semiconductor energy band theory. The study offers an innovative perspective for establishing S-scheme heterojunctions with highly efficient and stable photocatalytic activity for H2 generation and HCHO removal.