Oxidation Reaction Research Articles

Hydroxyl Radical Mediated Heterogeneous Photocatalytic Baeyer–Villiger Oxidation over Covalent Triazine/Heptazine‐Based Frameworks

AbstractThe Baeyer–Villiger (B–V) oxidation of ketones to the corresponding lactones/esters is a classic and essential reaction in the chemical industry. However, this oxidation process has not yet been achieved in ambient conditions with the aid of oxygen and heterogeneous photocatalysts. In this study, we developed an organic photocatalytic system using covalent triazine/heptazine‐based frameworks (CTF‐TB/CHF‐TB) to enable the B–V oxidation reaction under mild conditions through a cascade reaction pathway. Experimental data and theoretical calculations showed that heptazine/triazine units can “chelate” and decompose the in situ generated H2O2 into hydroxyl radicals (⋅OH). Compared to conventional methods that primarily involve metal‐activated benzaldehyde at elevated temperatures (e.g., 60 °C), the ⋅OH generated in our study can readily cleave the C−H bond of benzaldehyde, forming an active intermediate that drives subsequent sequential processes: O2→H2O2→⋅OH→Ph‐CO⋅→Ph‐COOO⋅. By employing this photocatalytic process, a yield of 91 % and a selectivity of over 99 % were obtained in the oxidation of cyclohexanone to caprolactone at room temperature. This performance is comparable to the state‐of‐the‐art catalysts, and our CHF‐TB catalyst demonstrates impressive reusability, maintaining a high yield after 5 consecutive runs. This work presents a straightforward approach for C−H cleavage by organocatalysts to produce ϵ‐caprolactone in a mild manner by B–V oxidation.

Breaking Activity‐Durability Inverse Relationship via Electrode Engineering by Utilizing β‐MnO2/RuO2 Heterostructures for Efficient Seawater Electrolysis

AbstractSignificant efforts are underway to enhance the efficiency of water electrolysis for sustainable hydrogen production. Approaches that were explored are the design of an efficient anode, engineering of electrolytes, and application of diffusion protective layer over the catalyst to protect it from corrosive reactions. Here we are exploring the engineering of electrode fabrication to enhance the efficacy of anode catalysts by ensuring that the materials are carefully selected. β‐MnO2 has been used to develop a cost‐effective method for electrode fabrication that establish a Schottky junction at heterostructure interface. This method transforms commercial RuO2, which is considered to be less active and stable, highly selective for chlorine oxidative reactions, into a highly active, stable, and OER‐selective in alkaline medium and surrogate seawater. With the help of thorough electrochemical techniques, we found that this engineering significantly improves the effective electrochemical surface area, and higher kinetics and conversion per unit site, profoundly affecting the charge transfer mechanism and optimizing the adsorption of OER intermediates, resulting in much‐increased mass activity. It is observed that the selectivity of the OER was enhanced due to the Lewis acid repercussions of β‐MnO2.

A Nitrogen- and Carbon-Present Tin Dioxide-Supported Palladium Composite Catalyst (Pd/N-C-SnO2)

For the first time, nitrogen- and carbon-present tin dioxide-supported palladium composite catalysts (denoted as Pd/N-C-SnO2) were prepared via an HCH method (HCH is the abbreviation for the hydrothermal process–calcination–hydrothermal process preparation process). In this work, firstly, three catalyst carriers (denoted as cc) were prepared using a hydrothermal-process-aided calcination method, and catalyst carriers prepared using ammonia monohydrate (NH3∙H2O), N,N-dimethylformamide (C3H7NO) and triethanolamine (C6H15NO3) as the nitrogen sources were nominated as cc1, cc2 and cc3, respectively. Secondly, these catalyst carriers were reacted with palladium oxide monohydrate (PdO·H2O) hydrothermally to generate catalysts c1, c2 and c3. As testified by XRD and XPS, besides carbon materials and the N-containing substances, the main substances of all prepared catalysts were SnO2 and metallic palladium (Pd). Above all things, all resultant catalysts, especially c2, showed a prominent electrocatalytic activity towards the ethanol oxidation reaction (EOR). As indicated by the CV (cyclic voltammetry) results, all fabricated catalysts presented a clear electrocatalytic activity towards the EOR. In the CA (chronoamperometry) measurement, the faradaic current density of EOR measured on c2 at −0.27 V vs. an SCE (saturated calomel electrode) after 7200 s was still maintained at about 5.6 mA cm−2. Preparing a novel catalyst carrier, N-C-SnO2, and preparing a new EOR catalyst, Pd/N-C-SnO2, were the principal dedications of this preliminary work, which was very beneficial to the development of Pd-based EOR catalysts.

How Ir‐Rh Alloys Improve Electrochemical Ammonia Oxidation Activity Studied by Density Functional Theory

The electrochemical ammonia oxidation reaction (AOR) has applications in hydrogen storage and ammonia waste remediation. Using density functional theory, we investigate the mechanism of AOR on Ir, Rh, and their alloys at varied atomic ratios (Ir75Rh25, Ir50Rh50, and Ir25Rh75) towards N2(g), NO2–(aq), and NO3–(aq) formation. This work introduces a method for computational alloy design by considering both electronic energy and configurational entropy. The structures considered are selective to N2(g) formation and all favoured *N‐N coupling. An Ir50Rh50 alloy was found to reduce the theoretical onset potential for N2(g) formation relative to pure Ir while not exhibiting a downhill coupling step corresponding to catalyst poisoning by *N as shown for pure Rh, consistent with previous experimental work. The formation of NO2–(aq) and NO3–(aq) demand significantly higher potentials, typically limited by the final hydroxylation step before desorption.

Interfacial Engineering‐Assisted Energy Level Modulation Enhances the Photoelectrochemical Water Oxidation Performance of Bismuth Vanadate Photoanodes

AbstractBiVO4 faces significant challenges for widespread application in photoelectrochemical (PEC) water oxidation due to its poor hole transport ability, high surface defect density, and sluggish water oxidation reaction kinetics. Employing interfacial engineering to assist in energy level modulation is an effective strategy to address these challenges. Herein, a CuCrO2 hole transport layer (HTL) is coupled and further grew NiCo‐MOF in situ to prepare a NiCo‐MOF‐CuCrO2‐BiVO4 composite photoanode. The novel composite photoanode not only achieves a photocurrent density of 5.75 mA cm−2 at 1.23 V versus a reversible hydrogen electrode (vs RHE) but also maintains stable operation for over 24 h. Comprehensive physicochemical characterization and density‐functional theory calculations confirm that the built‐in electric field generated by the p–n heterojunction formed between the CuCrO2 HTL and BiVO4 photoanode enhances the hole transport ability. Moreover, the NiCo‐MOF chelated on the photoanode surface not only passivates the surface defect states but also accelerates the kinetics of the water oxidation reaction. Under the synergistic effect of dual modification, the PEC water oxidation performance of the BiVO4 photoanode is dramatically improved. This pioneering work presents a MOF/HTL/BiVO4 configuration that provides a blueprint for the future development of integrated photoanodes for efficient solar energy conversion.

Engineering Topological and Chemical Disorder in Pd Sites for Record‐Breaking Formic Acid Electrocatalytic Oxidation

AbstractDesigning palladium‐based formic acid oxidation reaction (FAOR) catalysts to achieve significant breakthroughs in catalytic activity, pathway selectivity, and toxicity resistance is both urgent and challenging. Here, these challenges are addressed by pioneering a novel catalyst design that incorporates both topological and chemical disorder, developing a new class of PdCuLaYMnW high‐entropy amorphous alloys with a porous network (Net‐Pd‐HEAA) as a highly active, selective, and stable FAOR electrocatalyst. This novel Net‐Pd‐HEAA demonstrates record‐breaking FAOR performance, achieving the mass and specific activities of 5.94 A mgPd−1 and 8.94 mA cm−2, respectively, surpassing all previously reported Pd‐based catalysts and showing strong competitiveness against advanced Pt‐based catalysts. Simulataneously, Net‐Pd‐HEAA exhibits extraordinary stability in accelerated durability tests (ADT) and chronoamperometry (CA) tests. Advanced characterization and in situ, spectral analysis reveal that the extremely disordered atomic structure effectively regulates the geometric and electronic structure of the Pd sites, enhancing active intermediate coverage, facilitating dehydrogenation pathway, and inhibiting the production/adsorption of CO. Furthermore, when employed as the anode catalyst in proton exchange membrane water electrolysis (PEMWE), Net‐Pd‐HEAA only requires a potential of 1.28 V to obtain a current density of 1 A cm−2, and operates stably in a highly corrosive electrolyte for over 100 h.

Distinct Pathways Determined by Photocatalytic C─H or O─H Bond Activation for Hydroxyl Compounds Conversion Paired With Hydrogen Production

AbstractSelective control of C─H or O─H bond activation in photocatalytic conversion coupled with hydrogen production is a promising yet challenging goal. Here, an efficient photocatalytic system is reported that can produce high‐valued tartaric acid or formaldehyde and simultaneous producing hydrogen. At optimized conditions, the directional conversion of glycolic acid into tartaric acid is achieved with a selectivity of 76.24%, and the selectivity of methanol oxidation into formaldehyde reaches 88.21%. A high hydrogen production rate of 21.43 mmol·g−1·h−1 is obtained using glycolic acid as substrate. Mechanism studies reveal that α‐C─H bond is preferentially activated in glycolic acid adsorbed on the photocatalyst, while O─H bond is preferentially activated in methanol, forming carbon‐centered radical (•CH(OH)COOH) or oxygen‐centered radical (CH3O•) for subsequent coupling or oxidation reactions. This work demonstrates the selective control of the photocatalytic conversion process of different hydroxyl compounds, providing a new perspective for achieving organic compounds selective activation coupled with hydrogen production.

A novel pillar-layered MOF with urea linkers as a capable catalyst for synthesis of new 1,8-naphthyridines via the anomeric-based oxidation

AbstractMetal-based catalysts play an essential role in organic chemistry and the chemical industry. This research designed and successfully synthesized a pillar-layered metal–organic framework (MOF) with the urea linkers, namely Basu-HDI, as a novel and efficient heterogeneous catalyst. Various techniques such as FT-IR, EDX, elemental mapping, SEM, XRD, BET, and TGA/DTA studied its structure and morphology. Then, we investigated the synthesis of new 1,8-naphthyridines utilizing Basu-HDI in mild conditions via a one‐pot, three‐component tandem Knoevenagel/Michael/ cyclization/anomeric-based oxidation reaction. Final products were achieved by anomeric-based oxidation without employing an oxidation agent. Remarkably, this tandem process gave a good range of new 1,8-naphthyridines with high yields in a short reaction time. The pure products were confirmed by FT-IR, 1H NMR, 13C NMR, and mass spectrometry techniques. Moreover, the introduced catalyst showed good efficiency and stability and can be reused four times without significantly reducing efficiency.

C–H Trifluoromethylthiolation of aldehyde hydrazones

The selective C–H trifluoromethylthiolation of aldehyde hydrazones afforded interesting fluorinated building blocks, which could be used as a synthetic platform. Starting from readily available (hetero)aromatic and aliphatic hydrazones, the formation of a C–SCF3 bond was achieved under oxidative and mild reaction conditions in the presence of the readily available AgSCF3 salt via a one-pot sequential process (28 examples, up to 91% yield). Mechanistic investigations revealed that AgSCF3 was the active species in the transformation.

Syngas Production via Oxidative Reforming of Propane Using a CO2- and O2-Permeating Membrane

Recently, ceramic–carbonate membrane reactors have been proposed to selectively separate CO2 at elevated temperatures and to valorize this pollutant gas by coupling a catalyzed reaction. This work explores using a membrane reactor to perform the oxidative reforming of propane by taking advantage of the CO2- and O2-permeating properties of a LiAlO2/Ag–carbonate membrane. The fabricated membrane showed excellent permeation properties, such as CO2/N2 and O2/N2 selectivity, when operating in the 725–850 °C temperature range. The membrane exhibited remarkable stability during the long-term permeation test under operating conditions, exhibiting minor microstructural and permeation changes. Then, by packing a Ni/CeO2 catalyst, the membrane reactor arrangement showed efficient syngas production, especially at temperatures above 800 °C. A hydrogen-rich syngas mixture was obtained by the contributions of the oxidative reforming and cracking reactions. Specific issues observed regarding the membrane reactor’s performance are attributed to the catalyst that was used, which experienced significant poisoning by carbon deposition during the reaction, affecting syngas production during the long-term test. Thermodynamic calculations were performed to support the experimental results.

Electrochemical Upgrading of Waste Polylactic Acid Plastic for the Coproduction of C2 Chemicals and Green Hydrogen

Tandem alkali-catalyzed hydrolysis and alkaline electrolysis have gradually become appealing avenues for the reformation of polyester plastics into high-value-added chemicals and green hydrogen with remarkable environmental and economic benefits. In this study, an electrochemical upcycling strategy was developed for the electrocatalytic oxidation of polylactic acid (PLA) hydrolysate into valued C2 chemicals (i.e., acetate) and hydrogen fuel using N, P-doped CuOx nanowires (NW) supported on nickel foam (NF) as the electrocatalyst. This 3D well-integrated catalyst was easily prepared from a Cu(OH)2 NW/NF precursor with Saccharomycetes as a green and safe P and N source. The electrocatalyst can efficiently catalyze the lactate monomer derived from the hydrolysis of PLA waste to acetate with high selectivity and exhibits a lower onset potential for the lactate oxidation reaction (LOR) than for water oxidation, saving 224 mV to deliver a current density of 30 mA/cm2. The experimental results reveal that the plausible pathway of the LOR on these CuOx NW involves oxidation and subsequent decarboxylation. Divalent copper species have been verified to be active sites for LOR via in situ Raman spectroscopy.

Revealing Reaction Conditions to Drive the Oxidation Reaction of Hydroxyacetone to Lactic Acid on Cu/ZrO2 Catalyst

Revealing Reaction Conditions to Drive the Oxidation Reaction of Hydroxyacetone to Lactic Acid on Cu/ZrO2 Catalyst

Synergetic Modulation of Electronic Properties of Cobalt Oxide via “Tb” Single Atom for Uphill Urea and Water Electrolysis

AbstractExploring single‐atom (SA) catalysts in hybrid urea‐assisted water electrolysis offers a viable alternative to both Hydrogen (H2) generation and polluted water treatment. However, the unfavorable electronic stabilization, low SA content, intrinsically slow kinetics, and imbalanced adsorption‐desorption steps are the bottleneck for its scale‐up implementation. Herein, a rare‐earth Terbium single atom (TbSA) is topologically stabilized on defect‐rich Co3O4 (TbSA@d‐Co3O4) by Tb─O co‐ordination for urea oxidation reaction (UOR) and H2 evolution reaction (HER). Benefitting from the strong TbSA interaction with the d‐Co3O4, the TbSA@d‐Co3O4 achieves a 10 mA cm−2 current density at 1.27 V and −35 mV for UOR and HER, respectively. Remarkably, when TbSA@d‐Co3O4 is applied as a bi‐functional catalyst in a two‐electrode system, it merely requires 1.22 V to acquire 10 mA cm−2 with excellent operational stability for 100 h. The hybrid electrolyzer can be successfully empowered by the triboelectric nanogenerator, AA battery, and solar panel with a nominal potential of 1.5 V. The mechanistic investigation predicts “TbSA” insertion in d‐Co3O4 lowered the potential determining step, attributed to balanced reaction energetics for adsorption‐desorption of intermediates and favorable charge transfer characteristics for UOR. This work offers a new paradigm to explore the catalytic properties of rare‐earth “f‐block” elements to create advanced electrocatalysts via structural modulation.

Insights into Catalytic Oxidative Reaction Mechanisms of Pentane on the Ru(0001) Surface

Insights into Catalytic Oxidative Reaction Mechanisms of Pentane on the Ru(0001) Surface

Rapid oxidation of phenolic compounds by O3 and HO●: effects of the air–water interface and mineral dust in tropospheric chemical processes

Abstract. Environmental media affect the atmospheric oxidation processes of phenolic compounds (PhCs) released from biomass burning in the troposphere. To address the gaps in experimental research, phenol (Ph), 4-hydroxybenzaldehyde (4-HBA), and vanillin (VL) are chosen as model compounds to investigate their reaction mechanism and kinetics at the air–water (A–W) interface, on TiO2 mineral aerosols, in the gas phase, and in bulk water using a combination of molecular dynamics simulation and quantum chemical calculations. Of the compounds, Ph was the most reactive one. The occurrence percentages of Ph, 4-HBA, and VL staying at the A–W interface are ∼ 72 %, ∼ 68 %, and ∼ 73 %, respectively. As the size of (TiO2)n clusters increases, the adsorption capacity decreases until n > 4, and beyond this, the capacity remains stable. A–W interface and TiO2 clusters facilitate Ph and VL reactions initiated by the O3 and HO⚫, respectively. However, oxidation reactions of 4-HBA are little affected by environmental media because of its electron-withdrawing group. The O3- and HO⚫-initiated reaction rate constant (k) values follow the order of A–WPh > TiO2 VL > A–WVL > A–W4-HBA > TiO2 4-HBA > TiO2 Ph and TiO2 VL > A–WPh > A–WVL > TiO2 4-HBA > TiO2 Ph > A–W4-HBA, respectively. Some byproducts are more harmful than their parent compounds, so they should be given special attention. This work provides key evidence for the rapid oxidation observed in the O3/HO⚫ + PhC experiments at the A–W interface. More importantly, differences in the oxidation of PhCs by different environmental media due to the impact of substituent groups were also identified.

Ultra-fast synthesis of transition metal-MXene nanocomposite electrocatalyst for energy-saving seawater hydrogen production: Experiment and theory

Switching from the urea oxidation reaction (UOR) to the oxygen evolution reaction (OER) is a beneficial way to lower the amount of energy needed to make hydrogen gas during the hydrogen evolution reaction (HER). Due to the sluggish reaction kinetics of the six electrons reaction of UOR, designing a privileged bifunctional electrocatalyst for both HER and UOR necessitates. The 2D nano-sized non-noble metal electrocatalysts make it possible to speed up reactions and improve their electrocatalytic performance. We synthesized nickel-cobalt-MXene composite nanosheets (NiCoMXene) on the surface of copper foam using a one-pot, simple, and ultra-fast electrochemical method. This 2D electrocatalyst demonstrates high electrocatalytic performance towards HER (overpotential of 76 mV at −10 mA cm−2) with excellent durability in alkaline media. Furthermore, NiCoMXene nanocomposite served as a bifunctional electrocatalyst to investigate hydrogen gas production by a hybrid system HER coupled with UOR in seawater. The NiCoMXene requires a low overpotential for HER (81 mV) and UOR (1.38 V) to achieve a current density of 10 mA cm−2 in seawater, and the needed cell voltage to reach the same current density is 1.42 V in seawater. Our DFT analysis found a significant synergy between MXene and NiCo in the electrocatalyst. PDOS analysis showed remarkably that introducing Ni atoms to MXene shifts the d-band center to the left (lower energy), while Co atoms shifts it to the right (higher energy) and increased states near the Fermi level. This electronic structure makes the nanocomposite an ideal electrocatalyst, with MXene providing electrons and Co atoms serving as active sites for both HER and UOR.This research work can provide a useful directive to explore the electrocatalysts with outstanding catalytic activity.

Recent Advances in Rechargeable Zn-Air Batteries

Rechargeable Zn-air batteries are considered to be an effective energy storage device due to their high energy density, environmental friendliness, and long operating life. Further progress on rechargeable Zn-air batteries with high energy density/power density is greatly needed to satisfy the increasing energy conversion and storage demands. This review summarizes the strategies proposed so far to pursue high-efficiency Zn-air batteries, including the aspects of the electrocatalysts (from noble metals to non-noble metals), the electrode chemistry (from the oxygen evolution reaction to the organic oxidation reaction), electrode engineering (from powdery to free-standing), aqueous electrolytes (from alkaline to non-alkaline) and the battery configuration (from liquid to flexible). An essential evaluation of electrochemistry is highlighted to solve the challenges in boosting the efficiency of rechargeable metal-air batteries. In the end, the perspective on current challenges and future research directions to promote the industrial application of rechargeable Zn-air batteries is provided.

NH4Cl‐Assisted Electrosynthesis of P‐Doped Co(OH)2 Nanosheet on Cu2S Hollow Nanotube Arrays for Glycerol Electrooxidation

AbstractThe glycerol oxidation reaction (GOR) for producing high‐value‐added organic compounds is of great research interest due to its potential in alleviating the energy crisis. Herein, a facile NH4Cl‐assisted electrodeposition strategy is reported to fabricate 3D nano‐forest array‐like hollow nanostructures. The hierarchical heterojunction by combining phosphorus doping Co(OH)2 nanosheets with Cu2S nanotube arrays (P‐Co(OH)2@Cu2S NTs/CF) is developed to realize the optimization on GOR. The optimized P‐Co(OH)2@Cu2S NTs/CF catalyst exhibits an exceptional activity with a formate Faradaic efficiency (FE) of 97.40% at a potential of 1.30 V (vs RHE). The experimental results indicate that this unique hollow nano‐forest structure, grown on a conductive support, can expose more active sites and facilitate electron transfer, thereby demonstrating excellent GOR performance. This work provides new opportunities for the design of electrocatalysts of high‐activity and low‐cost hollow heterostructure electrocatalysts for glycerol electrooxidation.

Enhanced Adsorption Kinetics and Capacity of a Stable CeF3@Ni3N Heterostructure for Methanol Electro‐Reforming Coupled with Hydrogen Production

Alkaline methanol‐water electrolysis system is regarded as an appealing strategy for electro‐reforming methanol into formate and producing hydrogen with low energy‐consumption compared with alkaline water electrolysis. However, stability and selectivity under high current densities for practical application remain challenging. Herein, a CeF3@Ni3N nanosheets array anchored on carbon cloth (CeF3@Ni3N/CC) was fabricated. The gradual extrusion of F species from Ni(OH)2 lattices can stabilize hierarchical structure and construct abundant heterostructure interfaces. Moreover, CeF3 can modulate electron distribution of Ni3N, thus simultaneously enhancing the surface adsorption kinetics and capability of methanol and OH‐, which is conducive to enhanced methanol oxidation reaction (MOR) activity and selectivity. Therefore, bifunctional CeF3@Ni3N/CC exhibits low potential of 1.43 V at 500 mA cm‐2, along with high stability over 72 h and high faradaic efficiency (FEs) in MOR, as well as an overpotential of 76 mV to achieve 50 mA cm‐2 for hydrogen evolution reaction (HER). Furthermore, membrane‐free CeF3@Ni3N/CC||CeF3@Ni3N/CC cell for MOR||HER delivers high electrocatalytic activity, long‐term stability and FEs at high current density of 300 mA cm‐2. This study highlights the importance of optimizing surface adsorption behavior of active species, as well as rational design of highly efficient heterostructure electrocatalysts for methanol upgrading coupled with hydrogen production.

Enhanced Adsorption Kinetics and Capacity of a Stable CeF3@Ni3N Heterostructure for Methanol Electro‐Reforming Coupled with Hydrogen Production

Alkaline methanol‐water electrolysis system is regarded as an appealing strategy for electro‐reforming methanol into formate and producing hydrogen with low energy‐consumption compared with alkaline water electrolysis. However, stability and selectivity under high current densities for practical application remain challenging. Herein, a CeF3@Ni3N nanosheets array anchored on carbon cloth (CeF3@Ni3N/CC) was fabricated. The gradual extrusion of F species from Ni(OH)2 lattices can stabilize hierarchical structure and construct abundant heterostructure interfaces. Moreover, CeF3 can modulate electron distribution of Ni3N, thus simultaneously enhancing the surface adsorption kinetics and capability of methanol and OH‐, which is conducive to enhanced methanol oxidation reaction (MOR) activity and selectivity. Therefore, bifunctional CeF3@Ni3N/CC exhibits low potential of 1.43 V at 500 mA cm‐2, along with high stability over 72 h and high faradaic efficiency (FEs) in MOR, as well as an overpotential of 76 mV to achieve 50 mA cm‐2 for hydrogen evolution reaction (HER). Furthermore, membrane‐free CeF3@Ni3N/CC||CeF3@Ni3N/CC cell for MOR||HER delivers high electrocatalytic activity, long‐term stability and FEs at high current density of 300 mA cm‐2. This study highlights the importance of optimizing surface adsorption behavior of active species, as well as rational design of highly efficient heterostructure electrocatalysts for methanol upgrading coupled with hydrogen production.