Catalysts For Oxidation Research Articles

Modulating Surface Oxygen Valence States via Interfacial Potential in BiVO4/CoOx/Au Photoanode for Enhanced Selective Photoelectrochemical Oxidation of Glycerol to Dihydroxyacetone

AbstractThe concept of photoelectrochemical conversion of biomass into industrially valuable chemicals presents a compelling strategy to supplant the lower‐value oxygen evolution typically associated with photoanodes. Here, a surface potential manipulation method by regulating the surface oxygen valence states is put forward, which is demonstrated to be effective in enhancing the selective photoelectrochemical oxidation of glycerol to dihydroxyacetone (DHA). This involves the concurrent establishment of a BiVO4/CoOx heterojunction and a BiVO4/Au Schottky junction, aiming to fine‐tune the BiVO4 photoanode's surface potential and improve both its charge carrier separation and interfacial transfer kinetics. The BiVO4/CoOx/Au photoanode exhibits a photocurrent density of 6.15 mA cm−2 at 1.23 V versus reversible hydrogen electrode (RHE). Meanwhile, selective glycerol oxidation efficiency achieves a DHA evolution rate of 339.74 mmol m−2 h−1 and a selectivity exceeding 60%. Experiments and theoretical analysis underscore the pivotal role played by the surface potential in mediating glycerol and DHA adsorption and desorption processes. Additionally, the diminished surface potential attributed to the CoOx and Au amendments is responsible for the decreased Gibbs free energy of the dehydrogenation's rate‐limiting step involving the intermediate carbon species. This work demonstrates a method to design glycerol oxidation catalysts by modulating the interfacial molecular adsorption/desorption by surface potential regulation.

Challenging design of highly active Pt/CeO2–TiO2/ZSM-5 catalysts for VOCs low-temperature removal

Four Pt/CeO2–TiO2/ZSM-5 catalysts with different Pt species dispersion states and acidic properties were designed, and key factors affecting the oxidation activity of various VOCs (benzene, DCE, ethyl acetate and acetonitrile as typical organic compounds of aromatic hydrocarbon and halogen/oxygen/nitrogen-containing VOCs, respectively) were identified in the present work. The strength of the acid and oxidation sites on the surface of catalysts and their synergistic interaction play a crucial role. Highly dispersed Pt species and its strong redox ability promote low-temperature oxidation of benzene. A synergistic interaction between the acid and oxidation sites is required to achieve high DCE oxidation activity. An abundance of surface acid sites (particularly strong acid sites) favors the adsorption and dechlorination to form vinyl chloride of DCE, and the strong redox ability of oxidation sites would accelerate the deep oxidation of intermediates (such as vinyl chloride and acetic acid, etc.). For ethyl acetate or acetonitrile oxidation, the strong acidic property of the catalyst plays a prior role for their catalytic oxidation, which facilitates the low-temperature hydrolysis of ethyl acetate or acetonitrile. This work provides a significant thought to design and synthesize high activity catalysts for low-temperature oxidation of various VOCs pollutants.

The impact of surface-impregnated versus support-dispersed Fe in Fe–Ni/γ-Al2O3 catalysts for partial oxidation of methane: Insights into the effect of Fe incorporation method on coking and on the reaction mechanism

Two sets of Fe-modified Ni/γ-Al2O3 catalysts were prepared and tested in partial oxidation of methane. In one set, Fe was co-impregnated on the surface (NiFe) and in the other set Fe was incorporated in the support bulk (Ni/Fe). The two types showed significantly different coking resistance and performance. While Fe well dispersed in the support bulk significantly enhanced coking resistance, Fe co-impregnated with Ni on the surface enhanced the rate of coke deposition on the catalysts’ surfaces. The impact of Fe in the Ni/Fe catalysts is referred to its partially reduced ions (Fe2+) in redox reactions, and to the Ni-support strong interaction retarding the coke formation pathways. On the contrary, carbon formation on the NiFe catalysts is referred to the formation of Ni–Fe alloy particles which may block Ni active sites and can promote cracking of methane as well as CO molecules resulting in higher rates of coking.

Study on partial oxidation phenomena of post-injection fuel in diesel engines

In diesel engines, post fuel is injected in the expansion stroke, oxidized by the diesel oxidation catalysts and the high temperature gas re-generates the diesel particulate filters. However, it is empirically known that the post fuel at advanced injection timing is partially oxidized in the cylinder due to the high temperature-pressure conditions and it is a cause of the reduction of fuel consumption. The purpose of this research is to analyze post-injection fuel behaviors in cylinder and investigate the optimum fuel injections that maximize the unburnt hydrocarbons to the diesel oxidation catalysts. The engine employed in this research is a turbo charged 2.0 L four-cylinder DI diesel engine with two fuel injection systems to change the heterogeneity of air-fuel mixture and temperature distributions in cylinder; n-hexane is injected in the intake manifold to produce the homogeneous air-fuel mixture and diesel fuel is directly injected into the cylinder. The partial oxidation ratio of post fuel and the fuel loss mainly by fuel adhesion was calculated by injected fuel quantity, air quantity, and emission data. The 3D-CFD software was introduced to analyze the partial oxidation of post fuel and flow in the cylinder. The heterogeneity of burned gas mixture of post injection atmosphere and the post-injection timings were the parameters of engine tests and 3D-CFD simulations. The results suggest that the heterogeneity of equivalence ratio and the non-uniformity of gas temperature inside the cylinder at the start of post injection affect the partial oxidation of post-injection fuel. The more homogeneous these conditions are, the better the suppression of partial oxidation of post-injection fuel and the avoidance of fuel adhesion to the cylinder wall can be achieved.

Engine-out hydrocarbon speciation and DOC reaction modeling for dual-fuel combustion concept

The concerns for global warming have pushed very harsh regulations on conventional propulsion systems based on the use of fossil fuels. New technologies are being promoted, but their current technological status needs further research and development to become a competitive substitute for the ever-present internal combustion engine. Transition technologies like hybrid-electric platforms are the preferred solution, but their dependence on the internal combustion engine demands continued developing and improving this technology. Advanced combustion modes like dual-mode dual-fuel combustion are attractive solutions with room for improvement. This work evaluates the specifics of the hydrocarbon composition emitted during the operation of a medium-duty dual-mode dual-fuel engine, analyzing the specific requirements of a diesel oxidation catalyst for this application. Also, the modeling approach of this after-treatment component is revised for this type of application, proposing a new approach and evaluating numerically the performance of a conventional diesel oxidation catalyst. The results show that the new modeling approach brings better accuracy when modeling the transient operation of the engine.

Promotion of Different Active Phases in MnOX-CeO2 Catalysts for Simultaneous NO Reduction and o-DCB Oxidation

AbstractMnOX-CeO2 catalysts with different Mn and Ce content were prepared to evaluate the effect of metal content on catalytic properties and activity in the simultaneous NO reduction and o-DCB oxidation, in order to elucidate the most active species for the process. Catalytic properties were evaluated by ICP-AES, XRD, skeletal FTIR, STEM-HAADF, XPS, N2-physisorption, H2-TPR, NH3-TPD and pyridine-FTIR. Catalysts with 85%Mn and 15%Ce molar content have been found to be the most active. Their excellent catalytic performance is related to the coexistence of Mn in different phases, i.e., Mn species strongly interacting with Ce and segregated Mn species. The effect of the preparation methods has also been deeply investigated: Co-precipitation method (CP) leads to Mn segregation as Mn2O3, whereas sol-gel preparation method (SG) promotes the formation of an amorphous powder. The synergy between segregated Mn2O3 species and Mn species in high interaction with Ce (resulting in a mixed oxide phase) leads to the presence of Mn with different oxidation states. This effect, together with the high oxygen mobility caused by structural defects, enhances redox, acidic and oxidative properties. The improvement of catalytic properties with Mn content also favors NO reduction side-reactions, with N2O and NO2 being the most important by-products, whereas it limits the production of chlorinated organic by-products in o-DCB oxidation.

Nature of CuxCe1-xO2 solid solution catalysts

Identifying the local environments of active sites of CuxCe1-xO2 solid solution for low-temperature CO oxidation remains significant challenges. In this study, we coupled density functional theory and microkinetic modeling to thoroughly investigate local structures of CuxCe1-xO2 solid solution catalysts, as well as its catalytic performance for low-temperature CO oxidation. Combined with the infrared spectra simulations, we propose that the substitution of Cu3 or Cu4 clusters for one Ce atom accounts for the experimentally observed vibrational peaks of the adsorbed CO, rather than the Cu single atom or dimer. Cu single-atom and Cun clusters (n = 2–4) doped into CeO2 all exhibit an excellent stability against ripening and a promising catalytic activity for low-temperature CO oxidation. This research for the first time elucidates the nature of CuxCe1-xO2 solid solution catalysts and paves the way for the rational design of Cu/CeO2 catalysts for CO oxidation.

Facile one-step solvothermal synthesis of Co3O4/CuO nanoflowers as an excellent catalyst for CO oxidation in coal mines

In the present study, Cobalt oxide (Co3O4)/Copper oxide (CuO) nanoflower catalysts were synthesized through a one-step solvothermal method, and the impact of various factors, including reaction time, on the catalytic activity of the catalysts towards carbon monoxide (CO) was investigated. The results showed that the catalysts synthesized at 140 °C and a reaction time of 4 h provided the best catalytic performance for carbon monoxide, and the regular nanoflower-like morphology provided a larger specific surface area as well as a greater number of active sites, allowing the instantaneous 100 % elimination of CO at 200 °C. Additionally, a plausible reaction mechanism was elucidated, wherein CO initially adsorbed onto the sample's surface, subsequently reacting with lattice oxygen to form intermediate carbonate species. This process ultimately led to the production of carbon dioxide (CO2), followed by the desorption of CO2 molecules from the sample's surface. The results demonstrate that these composite catalysts effectively mitigate CO levels during CO over limit in coal mines, thereby enhancing the safety of production personnel.

A Cu doped RuO2 catalyst for efficient and durable acidic water oxidation

AbstractProducing hydrogen by water electrolysis in acidic system is essential for advancing the proton‐exchange membrane water electrolyzer (PEMWE) and maintaining the global sustainability. However, excavating highly active and durable catalysts for anodic oxygen evolution reaction (OER) in acid medium remains a great challenge due to the sluggish kinetics of OER and the severe catalyst dissolution. In this work, we developed a Cu doped RuO2 catalyst (Cu‐RuO2@CP) through simple drop casting and low temperature pyrolysis procedures. The incorporation of Cu into RuO2 executes complicated responsibilities: improving OER activity by raising more oxygen vacancies and accelerating the charge transfer between solid‐liquid interface; strengthening the long‐term durability via suppressing the over‐oxidation of RuO2 into soluble RuO4; lowering the catalyst cost by replacing with less expensive Cu. Hence, the Cu‐RuO2@CP exhibits excellent activity and stability in 0.5 M H2SO4 electrolyte, requiring a low overpotential of 200 mV to achieve 10 mA cm−2 and preserving stability for almost 500 h. Moreover, the overpotential is as low as 397 mV even when operating under an industrial‐level current density of 1000 mA cm−2, paving a new way to develop high performance OER electrocatalyst in acidic environment to promote the large‐scale utilization of PEMWE.

Design of Knölker‐Type Catalysts for the Anomeric Oxidation of Unprotected Mono‐ and Disaccharides

AbstractKnölker complexes have been recently used to perform the catalytic C1‐oxidation of unprotected sugars into sugar lactones. This oxidation method remained limited by the stability of the catalyst with the polyhydroxylated substrates. Our objective is now to overcome these limitations and extend this method to more challenging substrates such as disaccharides. We proposed in this paper two original designs of Knölker‐type complexes conceived to promote secondary H‐bond interactions with the OH groups of the substrates to stabilise the system and favour the transformation. In total, 8 novel pre‐catalysts were synthesised, fully characterised and applied in the anomeric oxidation of several sugar derivatives. Two of these new complexes proved to be more efficient than the Knölker complex for the oxidation of disaccharides. Moreover, a preliminary DFT study revealed the presence of H‐bonds interactions between the substrate and the oxygen atom on the ligand arm of the best complexes suggesting a beneficial role of this heteroatom on the catalytic efficiency.

Inside Back Cover: Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO2 Nano‐Islands

Inside Back Cover: Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO₂ Nano‐Islands

Oxidation of benzene with N2O on ZSM-5 zeolite: A comparison of gas-phase and supercritical conditions

The catalytic oxidation of benzene with nitrous oxide (N2O) over ZSM-5 zeolite has been carried out in a continuous-flow reactor under supercritical conditions and compared with the results of the gas-phase reaction. Aromatic substrates and nitrous oxide under the conditions of supercritical experiments (300–435 °C, 6.0–18.0 MPa) are both reagents and the supercritical medium. It has been established that the productivity of the supercritical oxidation of benzene into phenol significantly exceeds the productivity of the gas-phase process owing to the limited reversible deactivation of the catalyst under supercritical conditions and the in situ removal of the coke precursors by the dense reaction medium. In addition, it has been demonstrated that a successful in situ regeneration of the deactivated oxidation catalyst can be carried out during the transition from gas-phase reaction conditions to supercritical conditions in one experiment.

Inside Back Cover: Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO2 Nano‐Islands

Inside Back Cover: Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO₂ Nano‐Islands

S-scheme TiO2/Bi2WO6 heterojunction for enhanced photocatalytic selective oxidation of toluene

Selective activation of saturated C–H bonds in hydrocarbons, such as the activation of the C–H bond in toluene, is an effective method for the production of high value-added chemicals. However, improving the C–H bond activation of toluene remains a challenge. In this study, S-scheme TiO2/Bi2WO6 composites were synthesized by loading TiO2 nanoparticles on Bi2WO6 flakes using a simple hydrothermal method. The physical and chemical properties of the prepared materials were characterized using X-Ray Diffraction (XRD), Fourier Transform Infrared Spectoscopy (FT-IR), Scanning Electronic Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS) and other characterization methods. Selective oxidation of toluene to benzaldehyde under visible light irradiation using air as an oxidizing agent. When the molar ratio of TiO2 and Bi2WO6 was 0.20, the composites exhibited excellent photocatalytic performance with a benzaldehyde production rate of 1725.41 μmol g−1 h−1, which was 2.31 and 1.91 times higher than that of TiO2 and Bi2WO6, respectively. This excellent performance is attributed to the formation of heterojunction structure by the loaded TiO2 nanoparticles, which improves the separation efficiency of photogenerated carriers and thus enhances its photocatalytic performance. In addition, the active substances involved in the photocatalytic reaction were identified by free radical trapping experiments as ·O2− and h+. Finally, the photocatalytic mechanism of S-scheme TiO2/Bi2WO6 composites was proposed by energy band structure analysis and radical trapping experiments. This study provides a simple design pathway for the construction of visible-light responsive bismuth tungstate-based heterojunction photocatalysts and some ideas for the development of new and efficient photocatalytic toluene selective oxidation catalysts.

Synergistic catalytic effect of titanium and iron incorporated to spherical MCM-41 in selective catalytic oxidation of diphenyl sulphide with H2O2

Spherical mesoporous silicas of MCM-41 type modified with titanium, iron or both these metals were prepared by co-condensation method and tested in the role of catalysts for selective oxidation of diphenyl sulphide with H2O2 to diphenyl sulphoxide and diphenyl sulphone. The monometallic catalysts containing titanium or iron were found to be active catalysts of diphenyl sulphide mainly to diphenyl sulphoxide. A very significant increase in catalytic activity was observed for the bimetallic samples, containing both titanium and iron. Moreover, in the case of bimetallic catalysts with higher titanium loading, diphenyl sulphone is a dominating reaction product. The increased activity of the bimetallic catalysts has been related to the synergistic operation of titanium and iron in conversion of hydrogen peroxide into reactive species, which in the next step oxidise diphenyl sulphoxide.

The promotion of rare earth on Pt-SiO2-Al2O3 catalyst for NO oxidation in diesel exhaust

The effective oxidation of NO is the key to the catalytic treatment of diesel vehicle exhaust. Improving the NO oxidation ability is mainly to optimize the chemical state of the active site (Pt), followed by increasing the number of active centers. Considering that the atoms with electronegativity weaker than Pt can provide electrons to change the chemical state of Pt, rare earth elements with weak electronegativity are selected as additives to obtain Pt/M-SiO2-Al2O3 (M = Sc, Y, La, Ce, Pr, Nd, Sm, Eu) catalysts by co-impregnation method. Among them, the Pt/La-SiO2-Al2O3 catalyst has the best NO oxidation performance, compared with the Pt-SiO2-Al2O3, the NO conversion rate increased by 28 %. Due to the special outer electron arrangement of La, its electronegativity is the smallest in rare earth, which makes its outer electrons easy to transfer to Pt atoms, and has the strongest electron interaction. Thus, the highest content of Pt0 was detected in CO diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS) and X-ray photoelectron spectroscopy (XPS). In addition, CO chemisorption and transmission electron microscopy (TEM) confirmed that the introduction of La in the catalyst can significantly improve the dispersion of precious metals. Notably, this simple approach of affecting electron interaction by introducing weakly electronegative elements provides a reference for the design of noble metal catalysts with different valence states to solve complex problems.

Sulfonate Group Improves the Solubility and Electrocatalytic Performance of Ru‐Based bda‐ and pda‐Type Water Oxidation Catalysts under Neutral Conditions

AbstractFour ruthenium water oxidation catalysts that bear carboxylate and sulfonate groups in the active site have been synthesized and analyzed for their catalytic activity. The sulfonate‐containing catalysts show higher electrochemical activity in pH 7 phosphate buffer with 4 times larger catalytic current, improved durability with sacrificial oxidant, and increased solubility compared to similar species containing two carboxylate groups. Density functional theory calculations suggest that the sulfonate group provides a more favorable geometry for water nucleophilic attack, which is both the energetically most favorable mechanism calculated and the experimentally predicted mechanism under electrochemical conditions. Further experimental studies have been performed to show that under certain conditions catalysts can perform well electrochemically under pH conditions as low as 1.6 and that various structural components can greatly change solubility and catalytic operation.

Unveiling the Promoting Mechanism of H2 Activation on CuFeOx Catalyst for Low-Temperature CO Oxidation.

The effect of H2 activation on the performance of CuFeOx catalyst for low-temperature CO oxidation was investigated. The characterizations of XRD, XPS, H2-TPR, O2-TPD, and in situ DRIFTS were employed to establish the relationship between physicochemical property and catalytic activity. The results showed that the CuFeOx catalyst activated with H2 at 100 °C displayed higher performance, which achieved 99.6% CO conversion at 175 °C. In addition, the H2 activation promoted the generation of Fe2+ species, and more oxygen vacancy could be formation with higher concentration of Oα species, which improved the migration rate of oxygen species in the reaction process. Furthermore, the reducibility of the catalyst was enhanced significantly, which increased the low-temperature activity. Moreover, the in situ DRIFTS experiments revealed that the reaction pathway of CO oxidation followed MvK mechanism at low temperature (<175 °C), and both MvK and L-H mechanism was involved at high temperature. The Cu+-CO and carbonate species were the main reactive intermediates, and the H2 activation increased the concentration of Cu+ species and accelerated the decomposition carbonate species, thus improving the catalytic performance effectively.

A Recyclable Inorganic Lanthanide Cluster Catalyst for Chemoselective Aerobic Oxidation of Thiols.

Optimizing lanthanide catalyst performance with organic ligands often encounters significant challenges, including susceptibility to water or oxygen and complex synthesis pathways. To address these issues, our research focuses on developing inorganic lanthanide clusters with enhanced stability and functionality. In this study, we introduce the [Sm6O(OH)8(H2O)24]I8(H2O)8 cluster (Sm-OC) as a sustainable and efficient catalyst for the aerobic oxidation of thiols under heating conditions. The Sm-OC catalyst demonstrated remarkable stability, outstanding recyclability, and excellent chemoselectivity across a diverse range of functional groups in 38 different tests. Notably, it enables efficient unsymmetrical disulfide synthesis and prevents the formation of over-oxidized by-products, highlighting its superior performance. This Sm-OC catalyst provides a practical and robust tool for the precise construction of versatile disulfides, thus establishing a template for the broader use of lanthanide clusters in organic synthesis.

A broad-spectrum oxidation capability Ru-CeO2 catalyst for efficient synergistic selective oxidation of benzyl alcohol

Selective oxidation of alcohols to aldehydes by molecular oxygen is one of the most important transformations in multiphase catalysis. In this paper, a catalyst with selective oxidation ability was designed and synthesized for the selective catalytic oxidation of benzyl alcohol. N-doped carbon materials were prepared by high-temperature calcination using hydrothermal reaction products of citric acid and melamine as a carbon source, and a bimetallic catalyst supported by Ru-CeO2 was constructed using the mixture as the carrier for the selective oxidation of benzyl alcohol to benzaldehyde. The results showed that the introduction of CeO2 could effectively improve the oxidizing ability and catalytic activity of the catalyst. The Ru-Ce0.05/NC170–600 catalyst was able to convert 85.5 % benzyl alcohol into benzaldehyde at 140 °C, 6 h, and 2 MPa, and the selectivity for benzaldehyde was 100 %. It was demonstrated by DFT that it was theoretically feasible to generate benzaldehyde by extracting hydrogen atoms from benzyl alcohol molecules. Further, the selective oxidation experiments on other alcohols showed that the catalyst has high activity for the oxidation of various alcohols to generate the corresponding carbonyl products, and it is a catalyst with broad-spectrum selective oxidation ability. In this study, a green synthesis route of benzaldehyde was proposed to solve the problems in the traditional process. Meanwhile, it provides a new idea for the synthesis of carbonyl products by selective oxidation of alcohols.