Catalysts For Oxidation Research Articles

Ruthenium Nanoclusters and Single Atoms on α-MoC/N-Doped Carbon Achieves Low-Input/Input-Free Hydrogen Evolution via Decoupled/Coupled Hydrazine Oxidation.

The hydrazine oxidation-assisted H2 evolution method promises low-input and input-free hydrogen production. However, developing high-performance catalysts for hydrazine oxidation (HzOR) and hydrogen evolution (HER) is challenging. Here, we introduce a bifunctional electrocatalyst α-MoC/N-C/RuNSA, merging ruthenium (Ru) nanoclusters (NCs) and single atoms (SA) into cubic α-MoC nanoparticles-decorated N-doped carbon (α-MoC/N-C) nanowires, through electrodeposition. The composite showcases exceptional activity for both HzOR and HER, requiring -80 mV and -9 mV respectively to reach 10 mA cm-2. Theoretical and experimental insights confirm the importance of two Ru species for bifunctionality: NCs enhance the conductivity, and its coexistence with SA balances the H ad/desorption for HER and facilitates the initial dehydrogenation during the HzOR. In the overall hydrazine splitting (OHzS) system, α-MoC/N-C/RuNSA excels as both anode and cathode materials, achieving 10 mA cm-2 at just 64 mV. The zinc hydrazine (Zn-Hz) battery assembled with α-MoC/N-C/RuNSA cathode and Zn foil anode can exhibit 97.3 % energy efficiency, as well as temporary separation of hydrogen gas during the discharge process. Therefore, integrating Zn-Hz with OHzS system enables self-powered H2 evolution, even in hydrazine sewage. Overall, the amalgamation of NCs with SA achieves diverse catalytic activities for yielding multifold hydrogen gas through advanced cell-integrated-electrolyzer system.

Ruthenium Nanoclusters and Single Atoms on α‐MoC/N‐Doped Carbon Achieves Low‐Input/Input‐Free Hydrogen Evolution via Decoupled/Coupled Hydrazine Oxidation

AbstractThe hydrazine oxidation‐assisted H2 evolution method promises low‐input and input‐free hydrogen production. However, developing high‐performance catalysts for hydrazine oxidation (HzOR) and hydrogen evolution (HER) is challenging. Here, we introduce a bifunctional electrocatalyst α‐MoC/N−C/RuNSA, merging ruthenium (Ru) nanoclusters (NCs) and single atoms (SA) into cubic α‐MoC nanoparticles‐decorated N‐doped carbon (α‐MoC/N−C) nanowires, through electrodeposition. The composite showcases exceptional activity for both HzOR and HER, requiring −80 mV and −9 mV respectively to reach 10 mA cm−2. Theoretical and experimental insights confirm the importance of two Ru species for bifunctionality: NCs enhance the conductivity, and its coexistence with SA balances the H ad/desorption for HER and facilitates the initial dehydrogenation during the HzOR. In the overall hydrazine splitting (OHzS) system, α‐MoC/N−C/RuNSA excels as both anode and cathode materials, achieving 10 mA cm−2 at just 64 mV. The zinc hydrazine (Zn−Hz) battery assembled with α‐MoC/N−C/RuNSA cathode and Zn foil anode can exhibit 97.3 % energy efficiency, as well as temporary separation of hydrogen gas during the discharge process. Therefore, integrating Zn−Hz with OHzS system enables self‐powered H2 evolution, even in hydrazine sewage. Overall, the amalgamation of NCs with SA achieves diverse catalytic activities for yielding multifold hydrogen gas through advanced cell‐integrated‐electrolyzer system.

Supported nano-sized precious metal catalysts for oxidation of catalytic volatile organic compounds.

Volatile organic compounds (VOCs) are common contaminants found as indoor as well as outdoor pollutants, which can induce acute or chronic health hazards to the human physiological system. The catalytic oxidation method is widely considered as one of the effective methods for removing VOCs, and the development of highly effective catalysts is highly urgent for booming this interesting field. This review focuses on the recent progress of VOC oxidation catalyzed by supported nano-sized precious metal catalysts, and discusses the effects of metal composition, supports, size, and morphology on the catalytic activity. In addition, the roles played by both nano-sized precious metals and supports in enhancing the performance of catalytic VOCs are also systematically discussed, which will guide the further development of more advanced VOC catalysts.

Tailoring the textural and component properties of Mo-Bi based catalysts for the selective oxidation of tert-butanol to methacrolein by the assistance of polymethymethacrylate

Tailoring the textural and component properties of Mo-Bi based catalysts for the selective oxidation of tert-butanol to methacrolein by the assistance of polymethymethacrylate

High-Throughput Screening Strategy for Electrocatalysts for Selective Catalytic Oxidation of Formaldehyde to Formic Acid.

Electrocatalytic oxidation of formaldehyde (FOR) is an effective way to prevent the damage caused by formaldehyde and produce high-value products. A screening strategy of a single-layer MnO2-supported transition metal catalyst for the selective oxidation of formaldehyde to formic acid was designed by high-throughput density functional calculation. N-MnO2@Cu and MnO2@Cu are predicted to be potential FOR electrocatalysts with potential-limiting steps (PDS) of 0.008 and -0.009 eV, respectively. Electronic structure analysis of single-atom catalysts (SACs) shows that single-layer MnO2 can regulate the spin density of loaded transition metal and thus regulate the adsorption of HCHO (Ead), and Ead is volcanically distributed with the magnetic moment descriptor -|mM - mH|. In addition, the formula quantifies Ead and |mM - mH| to construct a volcano-type descriptor α describing the PDS [ΔG(*CHO)]. Other electronic and structural properties of SACs and α are used as input features for the GBR method to construct machine learning models predicting the PDS (R2 = 0.97). This study hopes to provide some insights into FOR electrocatalysts.

Theoretical study of adsorption properties and CO oxidation reaction on surfaces of higher tungsten boride

Most modern catalysts are based on precious metals and rear-earth elements, making some of organic synthesis reactions economically insolvent. Density functional theory calculations are used here to describe several differently oriented surfaces of the higher tungsten boride WB5-x, together with their catalytic activity for the CO oxidation reaction. Based on our findings, WB5-x appears to be an efficient alternative catalyst for CO oxidation. Calculated surface energies allow the use of the Wulff construction to determine the equilibrium shape of WB5-x particles. It is found that the (010) and (101) facets terminated by boron and tungsten, respectively, are the most exposed surfaces for which the adsorption of different gaseous agents (CO, CO2, H2, N2, O2, NO, NO2, H2O, NH3, SO2) is evaluated to reveal promising prospects for applications. CO oxidation on B-rich (010) and W-rich (101) surfaces is further investigated by analyzing the charge redistribution during the adsorption of CO and O2 molecules. It is found that CO oxidation has relatively low energy barriers. The implications of the present results, the effects of WB5-x on CO oxidation and potential application in the automotive, chemical, and mining industries are discussed.

Insight into the performance-boosting mechanism of Ag/MgAlOx for NH3 selective catalytic oxidation: Perspective from the support crystalline phase structures

Arranging an ammonia oxidation process after the selective catalytic reduction of NOx by NH3 (NH3-SCR) system is an effective way for ensuring the DeNOx efficiency and controlling the slip ammonia. To improve operability and reduce operating costs in ammonia selective catalytic oxidation (NH3-SCO), developing feasible and efficient catalysts becomes meaningful. Herein, focusing on the dilemma of Ag/Al2O3 catalysts in NH3-SCO applications, Ag/MgAlOx catalysts with different support different crystalline phase structures (5 %Ag/MgAl-LDO and 5 %Ag/MgAl2O4) were innovatively synthesized and systematically evaluated application potential in NH3-SCO. Results indicated that the introduction of Mg apparently broadened reaction temperature window and catalytic performance of 5 %Ag/MgAl2O4 was higher than 5 %Ag/MgAl-LDO, while the N2 selectivity was completely opposite. The combination of series characterization and density functional theory (DFT) calculations revealed that 5 %Ag/MgAl2O4 surface has more Ag0 species with small particle size, which is favorable for ammonia adsorption and activated dehydrogenation to further promote reaction of NOx species, resulting in a higher NH3-SCO activity. In contrast, 5 %Ag/MgAl-LDO readily induces oxidized Ag species and Ag0 is more inclined to be present in large particle sizes, which is more conducive to dissociation of O2 to produce reactive O species (O*) leading to the peroxidation of ammonia to nitrate and thus, positively affects the improvement of N2 selectivity. Model catalyst 5 %Ag/MgAl-650 (mixed-phase) was prepared by controlling the roasting conditions and exhibited excellent catalytic performance in NH3-SCO with almost 93 % of NH3 oxidized at 250 °C (N2 selectivity up to 71 %). This work could afford theoretical support for the optimization and application of catalysts with high performance at low temperatures in selective catalytic oxidation of slip ammonia.

A Cu doped RuO 2 catalyst for efficient and durable acidic water oxidation

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Design of Knölker‐type catalysts for the anomeric oxidation of unprotected mono‐ and disaccharides

Knölker 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.

Sulfonate Group Improves the Solubility and Electrocatalytic Performance of Ru‐based bda‐ and pda‐type Water Oxidation Catalysts Under Neutral Conditions

Four 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 3‐5 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 more a 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.

Opportunities of MXenes in Heterogeneous Catalysis: V2C as Aerobic Oxidation Catalyst

Opportunities of MXenes in Heterogeneous Catalysis: V₂C as Aerobic Oxidation Catalyst

Thermocatalytic oxidation potential of cobalt(II,III) oxide against gaseous formaldehyde in relation to hydrothermal synthesis temperature

The catalytic activity of various transition metal oxides has been reported to be tuned by controlling their synthesis conditions. In this perspective, the thermocatalytic oxidation performance of cobalt(II,III) oxides (Co3O4) against formaldehyde (FA) is studied in relation to the temperature selected for their hydrothermal synthesis (e.g., 30 (as room temperature (RT)), 60, 120, and 250℃) with the corresponding sample codes as Co3O4-RT, Co3O4-60, Co3O4-120, and Co3O4-250, respectively. The best performing Co3O4-RT records the lowest T90 (temperature required to obtain 90 % conversion) for 50 ppm FA at 72 °C when operated at 0 % relative humidity (RH), 30 mg (catalyst mass: mcat), and 100,000 mL g-1h−1 (weight hourly space velocity). The performance of Co3O4-RT, if assessed in terms of reaction kinetic rate (r) at XFA = 10 %, is 2.02E-02 mmol g-1h−1. According to X-ray photoelectron spectroscopy and temperature programmed characterization analysis, the catalytic activities of Co3O4-RT improve greatly through the synergistic combination of diverse factors (e.g., high Co3+ content, abundant oxygen vacancies (OVs) and surface adsorbed oxygen (Oβ) species, and good surface lattice oxygen (Oα) mobility). The analysis of in-situ diffuse reflectance infrared Fourier transform spectroscopy indicates that the FA should be oxidized into water (H2O) and carbon dioxide (CO2) via dioxymethylene (DOM) and formate (HCOO–) as reaction intermediates. The density functional theory simulations suggest the (111) surface of Co3O4 to be catalytically active against FA. The output of this research is expected to help establish effective strategies for designing high-performance transition metal oxide catalysts for the catalytic oxidation of FA.

Efficient catalytic oxidation of formaldehyde by defective g–C3N4–anchored single-atom Pt: A DFT study

Indoor volatile formaldehyde is a serious health hazard. The development of low-temperature and efficient nonhomogeneous oxidation catalysts is crucial for protecting human health and the environment but is also quite challenging. Single-atom catalysts (SACs) with active centers and coordination environments that are precisely tunable at the atomic level exhibit excellent catalytic activity in many catalytic fields. Among two-dimensional materials, the nonmagnetic monolayer material g-C3N4 may be a good platform for loading single atoms. In this study, the effect of nitrogen defect formation on the charge distribution of g-C3N4 is discussed in detail using density functional theory (DFT) calculations. The effect of nitrogen defects on the activated molecular oxygen of Pt/C3N4 was systematically revealed by DFT calculations in combination with molecular orbital theory. Two typical reaction mechanisms for the catalytic oxidation of formaldehyde were proposed based on the Eley-Rideal (E-R) mechanism. Pt/C3N4–V3N was more advantageous for path 1, as determined by the activation energy barrier of the rate-determining step and product desorption. Finally, the active centers and chemical structures of Pt/C3N4 and Pt/C3N4–V3N were verified to have good stability at 375 K by determination of the migration energy barriers and ab initio molecular dynamics simulations. Therefore, the formation of N defects can effectively anchor single-atom Pt and provide additional active sites, which in turn activate molecular oxygen to efficiently catalyze the oxidation of formaldehyde. This study provides a better understanding of the mechanism of formaldehyde oxidation by single-atom Pt catalysts and a new idea for the development of Pt as well as other metal-based single-atom oxidation catalysts.

Construction of spinel/biochar film/honeycomb monolithic catalyst for photothermal catalytic oxidation of VOCs

Construction of spinel/biochar film/honeycomb monolithic catalyst for photothermal catalytic oxidation of VOCs

High-index facets Pt concave nanocubes with small interface angles induced by N-defective sites in the integrated electrode for methanol oxidation

The construction of an integrated electrode with self-organized growth is of great significance in reducing the Pt loading and improving the performance of the membrane electrode assembly (MEA) in proton exchange membrane fuel cells (PEMFCs). Herein, the square-wave pulse electrodeposition method is used to grow Pt{510}CNC and Pt{720}CNC nanocrystals on carbon fiber paper (CFP)-based reduced graphene oxide (rGO/CFP) and nitrogen-doped reduced graphene oxide (N-rGO/CFP) supports, respectively. Experimental and density functional theory (DFT) calculations show that the introduction of N makes it easier for hydrogen to adsorb on Pt, and the arrangement order of more Pt atoms is disrupted by hydrogen, resulting in the formation of Pt concave nanocubes (Pt CNCs) with small interface angles (α), consisting of {720} facets with more atomic steps. Moreover, the catalytic activities of the prepared two catalysts for methanol oxidation are 3.17 and 2.35 times higher than that of commercial Pt/C, and the maximum power densities of direct methanol fuel cell (DMFC) are also better than that of commercial Pt/C. This work can provide important guidance for the future research of high-index facets noble metal nanocrystals for growth on the surface of defective carbon carriers as integrated electrodes in MEA.

Atomically dispersed MoNi alloy catalyst for partial oxidation of methane

The catalytic partial oxidation of methane (POM) presents a promising technology for synthesizing syngas. However, it faces severe over-oxidation over catalyst surface. Attempts to modify metal surfaces by incorporating a secondary metal towards C–H bond activation of CH4 with moderate O* adsorption have remained the subject of intense research yet challenging. Herein, we report that high catalytic performance for POM can be achieved by the regulation of O* occupation in the atomically dispersed (AD) MoNi alloy, with over 95% CH4 conversion and 97% syngas selectivity at 800 °C. The combination of ex-situ/in-situ characterizations, kinetic analysis and DFT (density functional theory) calculations reveal that Mo-Ni dual sites in AD MoNi alloy afford the declined O2 poisoning on Ni sites with rarely weaken CH4 activation for partial oxidation pathway following the combustion reforming reaction (CRR) mechanism. These results underscore the effectiveness of CH4 turnovers by the design of atomically dispersed alloys with tunable O* adsorption.

Analysis of Altitude and Ambient Temperature Effects on the Reactivity of Oxidation Catalysts in the Presence of H2

Worldwide emission standards are now required to cover engine operation under extreme ambient conditions, which affect the raw emissions and the efficiency of the exhaust aftertreatment systems. These regulations also target new combustion technologies for decarbonization, such as neat hydrogen (H2) combustion or dual-fuel strategies, which involve a challenge to the analysis of exhaust aftertreatment system requirements and performance. This work addresses the impact of high altitude and low ambient temperature conditions on the reactivity of an oxidation catalyst in the presence of H2. A reaction mechanism is proposed to cover the main conversion paths of CO, HC, and H2, including the formation and consumption of high-energy surface reaction intermediates. The mechanism has been implemented into a faster-than-real-time reduced-order model for multi-layer washcoat honeycomb catalytic converters. The model was utilized to investigate the effect of H2 concentration on the reactivity of CO and HC within the catalyst under various operating and ambient conditions. By applying the model and examining the selectivity towards different reaction pathways in the presence of H2, insights into surface intermediates and reactivity across different cross-sections of the monolith were obtained. This analysis discusses the underlying causes of reactivity changes promoted by H2 and its relative importance as a function of driving boundary conditions.

Construction of rose-type Co/Mo bimetal MOF and MOF-derived W embedded composites: Structure, reactivity, and dynamic simulation

Transition metal organic framework-derived materials are potential catalysts for cycloolefins oxidation, and it is essential to develop them with sufficient intrinsic activity and more efficient structure. Herein, we designed Co/Mo bimetallic MOF with rose-type structure as a support for synthesizing CoMo-ZIF@IL/W catalyst with lamelliform structure and abundant Co, Mo, and W active sites for cyclopentene tandem oxidation to glutaraldehyde. Characterization results reveal that: 1) Mo implantation dramatically increases pore size (2.15 → 28.91 nm) of monometallic MOF Co-ZIF; 2) IL introduction significantly improves active (Co2+ + Co3+) / satellite content ratio from 1.85 to 2.5; 3) MOF morphology can be completely changed through post-synthetic modification via IL, rather than just during the synthesis process. Meanwhile, CoMo-ZIF@IL/W exhibits high activity and excellent reuse properties in cyclopentene oxidation. Remarkably, dynamic simulation supported via detailed kinetic parameters (pre-exponential factors A1–3 = 1.17 × 1012, 1.45 × 108, 9.58 × 106 L mol−1 s−1, activation energies E1–3 = 89.4, 57.82, 86.01 kJ mol−1) and possible synergistic catalysis mechanism of Co/Mo/W active species were first explored.

A single Mn atom supported by a boron-vacancy in a BN monolayer: An encouraging catalyst for CO oxidation

Single-atom catalysts (SACs) are known for their exceptional activity, primarily attributed to the abundance of low-coordinated metal atoms, which enable efficient activation of robust chemical bonds, including CO bonds. In this work, we explore the prospective utilization of a specific SAC, isolated Mn atoms supported on Boron nitrogen (Mn/BN), for CO oxidation. By analyzing the adsorption/co-adsorption energies of CO, O2, O2+CO, and 2CO, we create a set of screening criteria and conduct a comparative analysis of the chemical processes involved in CO oxidation. The Langmuir-Hinshelwood (LH), Eley-Rideal (ER), termolecular Langmuir-Hinshelwood (TLH) and termolecular Eley-Rideal (TER) mechanisms are investigated. Results indicate the ER and LH mechanisms feature pronouncedly lower barrier of 0.33 and 0.41 eV, respectively, for the rate-limiting step, than those of the TLH (0.72 eV) and TER (3.00 eV) mechanisms, suggesting that the ER and LH mechanisms are favorable at normal temperature. This study offers valuable insights that can inform future developments in the design of low-temperature CO oxidation processes utilizing SACs.

Study on the active regeneration characteristics of DPF in diesel-methanol dual-fuel engine under different exhaust oxygen concentrations

This study proposes a method to control exhaust oxygen (O2) concentration by adjusting the intake throttle valve, achieving intake throttling, and reducing intake airflow. The impact of exhaust O2 concentration at the inlet of the diesel oxidation catalyst (DOC) the diesel particulate filter (DPF) performance during active regeneration in diesel engines is investigated. Experiments are conducted under methanol substitution rates (MSR) of 0% and 20% to investigate how different exhaust O2 concentrations affect the performance of the DOC and DPF during active regeneration. A comparative analysis of fuel consumption and cumulative CO2 emissions during DPF active regeneration under different exhaust O2 concentrations is performed. Research results indicate that decreasing exhaust O2 concentration reduces exhaust flow, raising DOC inlet temperature. This enhancement improves catalytic conversion efficiency, accelerating the rise in DPF inlet temperature. The average conversion efficiency of DOC to unburned methanol exceeds 98.07%. After initiating DPF active regeneration, O2 concentration sharply drops, leading to elevated CO2 emissions. As soot combustion advances, the required O2 diminishes, resulting in a gradual rise and eventual stabilization of O2 emissions. Economically and environmentally, irrespective of MSR (20% or 0%), there exists an optimal exhaust O2 concentration that minimizes effective regeneration time during DPF active regeneration, achieving minimal fuel consumption and the lowest CO2 mass emissions. This study offers theoretical support for optimizing energy-saving and emission-reduction processes during DPF active regeneration.