Efficient Oxidation Catalysts Research Articles

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.

Kinetic Study and Catalytic Activity of Cr3+ Catalyst Supported on Calcium Silicate Hydrates for VOC Oxidation

Volatile organic compounds (VOCs) are pollutants that pose significant health and environmental risks, necessitating effective mitigation strategies. Catalytic oxidation emerges as a viable method for converting VOCs into non-toxic end products. This study focuses on synthesizing a catalyst based on calcium silicate hydrates with chromium ions in the CaO-SiO2-Cr(NO3)3-H2O system under hydrothermal conditions and evaluating its thermal stability and catalytic performance. A catalyst with varying concentrations of chromium ions (10, 25, 50, 100 mg/g Cr3+) was synthesized in unstirred suspensions under saturated steam pressure at a temperature of 220 °C. Isothermal curing durations were 8 h, 16 h, and 48 h. Results of X-ray diffraction and atomic absorption spectroscopy showed that hydrothermal synthesis is effective for incorporating up to 100 mg/g Cr3+ into calcium silicate hydrates. The catalyst with Cr3+ ions (50 mg/g) remained stable up to 550 °C, beyond which chromatite was formed. Catalytic oxidation experiments with propanol and propyl acetate revealed that the Cr3+ catalyst supported on calcium silicate hydrates enhances oxygen exchange during the heterogeneous oxidation process. Kinetic calculations indicated that the synthesized catalyst is active, with an activation energy lower than 65 kJ/mol. This study highlights the potential of Cr3+-intercalated calcium silicate hydrates as efficient catalysts for VOC oxidation.

Fe-doped BN monolayer: A single-atom catalyst for efficient formaldehyde oxidation

Formaldehyde (HCHO) is a ubiquitous air pollutant, and the prolonged inhalation poses a serious threat to human health, thus it is imperative to develop HCHO oxidation catalysts with high activity. FeNx-based catalysts have shown brilliant catalytic performance due to their unique electronic structures. In this work, the active FeN3 site is designed by doping Fe atom at the B-vacancy in BN monolayer without introducing additional N atoms. Our first principles calculation results show that the Fe atom has good dispersibility, dynamical stability and thermal stability on the BN monolayer. Two oxidation mechanisms (Langmuir-Hinshelwood and Eley-Rideal) of HCHO on Fe-doped BN monolayer are investigated to explore the possible reaction pathways. The dissociation of O2 molecule is identified as the rate-limiting step, and the lowest energy barrier is 0.99 eV. Moreover, the excellent desorption behaviors of the produced CO2 and H2O molecules on substrate (small desorption energy of 0.20 and 0.75 eV, and short desorption time of 2.39 × 10−9 and 4.64 s) enable this catalyst to maintain high activity during the reaction cycle. Our results suggest the feasibility of Fe-doped BN monolayer for the catalytic oxidation of HCHO and broaden the application of BN-based single-atom catalysts.

A heterogeneous catalyst for oxidation of sulfides using a Mn(II) unsymmetrical Schiff base complex immobilized on MCM-41

An unsymmetrical Mn(II) Schiff base complex was attached to MCM-41. The synthesized catalyst was characterized by powder X-ray diffraction (XRD), nitrogen adsorption/desorption isotherms, inductivity coupled plasma (ICP), Fourier Transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The immobilized Schiff base complex was an efficient catalyst for oxidation of sulfides with hydrogen peroxide. In addition, this green oxidation system was used to oxidize various sulfides and the results showed that sulfoxides were the major products. Finally, the reuse of the catalyst was also investigated

Elucidation of synergism in Ce-Zr/SBA-15 mesoporous catalysts and the effects on the activity in selective glycerol to lactic acid reaction

The continued conversion of glycerol to value-added chemicals is essential in ensuring the sustainable development of the biodiesel industry. Selective catalytic oxidation of glycerol to lactic acid provides an alternative approach to valorizing glycerol. A mesoporous SBA-15 supported mixed-metallic oxide catalyst is deemed essential to selectively produce lactic acid in this mixed parallel and multi-step reaction. SBA-15-supported bimetallic Ce and Zr oxides were proved to be highly efficient catalysts for the selective glycerol oxidation into lactic acid in base-free media. The synergism between Ce and Zr in the bimetallic oxide compounds could enhance the creation of oxygen vacancies in the catalyst via the reduction of Ce4+ to Ce3+. The 2:1CeZr/SBA-15 catalyst exhibited prominent catalytic activity in selectively oxidizing glycerol to lactic acid, with a glycerol conversion of 91.8% and a lactic acid yield of 35.1%. This work achieved superior catalytic performance compared to previously conducted studies, primarily due to the significantly higher initial glycerol concentration employed in this study. To ascertain the intrinsic active sites of the catalyst, the physicochemical properties of the catalyst were thoroughly examined using BET, FTIR, XRD, FESEM, TEM, CO2-TPD, O2-TPD, and H2-TPR analysis. This work concluded that the synergistic interaction of the active sites, which led to the formation of active oxygen species, facilitated primary dehydrogenation of the terminal -OH bond in glycerol. Hence, in this work, a plausible glycerol conversion mechanism over the 2:1CeZr/SBA-15 catalyst was also proposed.

Iron-Based Catalysts Derived from Iron-Containing Sludge for Enhanced Catalytic Performance of H2S Selective Catalytic Oxidation.

In this work, iron-containing sludge is used to prepare iron-based catalysts for efficient H2S selective catalytic oxidation. First, the effect of calcination temperatures on the catalytic activities of H2S selective oxidation is carried out and it can be found that S-500 calcined at 500 °C performs excellent catalytic activity. Then, the catalytic performance of the S-500 catalyst is further optimized using alkaline treatment with different concentrations of NaOH solution. The results indicate that S-500(2.0) treated with 2 M NaOH solution has the highest catalytic activity of H2S selective oxidation. Next, various characterization methods are used to analyze the structure and physical-chemical of the sludge-based catalysts. N2-Brunauer-Emmett-Teller (N2-BET) and X-ray photoelectron spectroscopy analyses show that the S-500(2.0) catalyst has the smallest average particle (11.17 nm), the biggest ratio of S ext/S micro(17.98) with bigger external specific surface area (49.09 m2·g-1), a higher proportion of Fe3+ species (50.88%), and surface adsorbed oxygen species (48.07%). Meanwhile, O2-TPD and CO2-TPD analysis indicates that the S-500(2.0) catalyst has a bigger value of the Oads/OTotal ratio (50.56%) and (CO2)(weak+moderate) /(CO2)Total ratio of (31.41%), indicating that there are much more oxygen vacancies and weak alkaline sites. As a result, the excellent catalytic performance of H2S selective oxidation can be attributed to its outstanding physical-chemical properties.

Constructing Pd@Layered-CoOx/MFI Bifunctional Catalyst for Efficient Ethyl Acetate Oxidation: Boosted C═O Activation and *O Species Transformation.

Oxygenated volatile organic compounds (OVOCs), emitted in large quantities by the chemical industry, are a major contributor to the formation of ozone and subsequent particulate matter. For the efficient catalytic oxidation of OVOCs, the challenges of molecular activation and intermediate inhibition remain. The construction of bifunctional active sites with specific structures offers a promising way to overcome these problems. Here, the Pd@Layered-CoOx/MFI bifunctional catalyst with core-shell active sites was rationally fabricated though a two-step ligand pyrolysis method, which exhibits a superb oxidation efficiency toward ethyl acetate (EA). Over this, 13.4% of EA (1000 ppm) can be oxidized at just 140 °C with a reaction rate of 13.85 mmol·gPd-1·s-1, around 176.7 times higher than that of the conventional Pd-CoOx/MFI catalyst. The electronic coupling of the Pd-Co pair promotes the electron back-donation from Pd nanoparticles to the layered CoOx shell and facilitates the formation of Pd2+ species, which greatly enhances the adsorption and activation of the electron-rich C═O bond of the EA molecules. In addition, the synergy of these core-shell Pd@Layered-CoOx sites accelerates the activation and transformation of *O species, which inhibit the formation of acetaldehyde and ethanol byproducts, ensuring the rapid total oxidation of EA molecules via the Mars-van Krevelen mechanism. This work established a solid foundation for exploring robust bifunctional catalysts for deep OVOC purification.

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.

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

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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.

Characterization of the Bottlenecks and Pathways for Inhibitor Dissociation from [NiFe] Hydrogenase.

[NiFe] hydrogenases can act as efficient catalysts for hydrogen oxidation and biofuel production. However, some [NiFe] hydrogenases are inhibited by gas molecules present in the environment, such as O2 and CO. One strategy to engineer [NiFe] hydrogenases and achieve O2- and CO-tolerant enzymes is by introducing point mutations to block the access of inhibitors to the catalytic site. In this work, we characterized the unbinding pathways of CO in the complex with the wild-type and 10 different mutants of [NiFe] hydrogenase from Desulfovibrio fructosovorans using τ-random accelerated molecular dynamics (τRAMD) to enhance the sampling of unbinding events. The ranking provided by the relative residence times computed with τRAMD is in agreement with experiments. Extensive data analysis of the simulations revealed that from the two bottlenecks proposed in previous studies for the transit of gas molecules (residues 74 and 122 and residues 74 and 476), only one of them (residues 74 and 122) effectively modulates diffusion and residence times for CO. We also computed pathway probabilities for the unbinding of CO, O2, and H2 from the wild-type [NiFe] hydrogenase, and we observed that while the most probable pathways are the same, the secondary pathways are different. We propose that introducing mutations to block the most probable paths, in combination with mutations to open the main secondary path used by H2, can be a feasible strategy to achieve CO and O2 resistance in the [NiFe] hydrogenase from Desulfovibrio fructosovorans.

3D-interconnected N-doped porous carbon with hierarchical pore structure as a high-efficiency catalyst for H2S oxidation at room temperature

Nitrogen-doped porous carbons (NPCs) have been regarded as an efficient metal-free catalyst for H2S oxidation. However, critical factors affecting their desulfurization ability are still unclear, making it difficult to accurately adjust their desulfurization performance to meet industrial requirements. Herein, a novel 3D-interconnected NPC with hierarchical pore structure was synthesized by one-step “leavening” strategy using rice husk and (NH4)2C2O4 as a carbon source and foaming agent, respectively, for H2S oxidation at room temperature. Pyrolysis temperature is the major factor for physicochemical properties of NPCs, and breakthrough sulfur capacity of the optimal NPC reaches up to 1036.68 mg/g, which can remain stable during three desulfurization-regeneration cycles. Comparative experiment shows that H2S capacity of NPC is 1.8 and 4.0 times those of PC and NC, respectively, revealing the excellent desulfurization performance of NPC. The structure-effect relationships between H2S and NPC reveal that both textural and chemical properties of NPC, especially specific surface area, structural defect, and pyrrolic N, play dominant roles in H2S removal. It is very necessary to balance the relationship between textural performances and pyrrolic N to synthesize optimal NPC catalyst. This work provides a valuable reference for rational design of high-efficiency carbon-based catalysts for persistent desulfurization at room temperature.

Hierarchical Porous N-Doped Carbon Particles Derived from ZIF-8 as Highly Efficient H2S Selective Oxidation Catalysts.

In the selective oxidation of H2S, the catalytic activity over N-doped carbon-based catalysts is significantly influenced by the accessibility of active sites and the mass transfer rates of reactant molecules (e.g., H2S and O2) as well as generated sulfur monomers. Therefore, it is crucial for enhancing the initial performance via the controlled synthesis of carbon-based catalysts with highly exposed active sites and unique porous structures. Herein, we reported on an efficient strategy to synthesize nanosized N-doped carbon particles with hierarchical porous structures by directly pyrolyzing an oversaturated NaCl-encapsulated ZIF-8 precursor mixture. The introduction of NaCl not only serves as a pollution-free template to promote the formation of graphitic carbon layers but also acts as an intercalating agent to guide the derivation of hierarchical porous structures, as well as enhances the amount of active nitrogen species in the catalysts. As a result, the as-prepared H-NC800 catalyst shows excellent H2S selective oxidation performance (sulfur formation rate is 794 gsulfur·kgcat-1·h-1), good stability (>80 h), and antiwater vapor properties. The characterization results and DFT calculations indicate the crucial role of pyridinic N in the adsorbing and activating reactant molecules (H2S, O2). Furthermore, nanoscale N-doped carbon particles accelerated the rapid transport of generated sulfur monomers under a hierarchical porous structure. This investigation introduces a distinctive strategy for synthesizing ZIF-8-derived N-doped carbon nanosized with a hierarchical porous structure, while its efficient and stable H2S selective oxidation performance highlights significant potential for practical implementation in the industrial desulfurization process.

Catecholase activity assessment of In-Situ copper complexes derived from a novel Schiff base ligand

This study focuses on the synthesis, characterization, and evaluation of catecholase activity in a series of in-situ copper complexes derived from a novel Schiff base ligand, 2,2′{(methylimino)bis[propanediylnitrilo(Z)methylylidene]}bis(5-methoxyphenol) (MBPM). The ligand MBPM and its complex [Cu(MBPM)] were successfully synthesized and characterized using various analytical techniques, including X-ray crystallography, IR spectroscopy, and 1H NMR spectroscopy. Subsequently, we investigated the catalytic activity of these complexes in the oxidation of catechol to o-quinone. The results revealed a remarkable difference in catecholase activity between the Schiff base ligand-derived complex, [Cu(MBPM)], and in-situ copper complexes. The [Cu(MBPM)] complex exhibited significantly higher catalytic activity, underscoring its potential as an efficient catalyst for catechol oxidation. This enhanced activity can be attributed to structural differences and the presence of multiple active sites within the [Cu(MBPM)] complex.

Constructing Efficient CuAg Nanoalloys on Ce0.90In0.10Oδ for Methanol Deep Oxidation Catalysis at Low Temperature.

So far, it is still extremely challenging to develop an efficient catalyst for deep oxidation of methanol at low temperature. Herein, we report the construction of the highly dispersed CuAg alloy on the surface of Ce0.90In0.10Oδ nanorods support for catalyzing methanol deep oxidation. The composition, structure and properties of catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) spectroscopy and X-ray photoelectron spectroscopy (XPS). The results show that the CuxAg100-x/Ce0.90In0.10Oδ alloy catalysts exhibit superior catalytic activity and stability compared to pure Ag/Ce0.90In0.10Oδ, with the highest activity observed for Cu40Ag60/Ce0.90In0.10Oδ, accompanied by the light-off temperature (T50) and full conversion temperature (T90) of 115 and 145 °C, respectively. This is attributed to the synergistic effect of CuAg alloy, which results in electron transfer, generating more Ag0, and enhanced interaction between CuAg alloy and the support, leading to increased Ce3+ content and higher oxygen vacancy concentration. This work successfully applies CuAg alloy catalysts in thermo-catalytic reaction, offering promising prospects for CuAg alloy catalysts in the methanol deep oxidation.

Light-induced phase transformation to two-dimensional amorphous spinel CoAlOx nanosheets as a tandem photothermal catalyst for efficient and durable toluene oxidation

Low temperature fabrication of spinel oxides and development of efficient and durable toluene photothermal catalysts remain challenging. Herein, two-dimensional amorphous spinel CoAlOx nanosheets (CoAl-LDH-L2) have been fabricated via a light-induced phase transformation strategy using intense photooxidation. Light-induced decomposition and phase transformation process have been used to elucidate the growth mechanism. The CoAl-LDH-L2 exhibits improved toluene adsorption and photothermal conversion, with the highest photothermal catalytic toluene conversion (∼100 % at 500 ppm) at 90 °C, outperforming most previously reported catalysts. Irradiation with mild external heating significantly increases the mineralization rate (∼90 %) and improves the long-term and cycling stability (∼5% losses within 39 h) relative to that under single-light-driven conditions. In-situ DRIFT spectroscopy was also performed for revealing the “tandem photothermal catalysis” mechanism for toluene conversion. This work offers a novel strategy for developing spinel oxides as low-temperature photothermal catalyst in a green and sustainable way.

Correction to “Thermoresponsive Polymeric Nanoparticles as Efficient Pickering Interfacial Catalysts for Selective Oxidation of Sulfides”

Correction to “Thermoresponsive Polymeric Nanoparticles as Efficient Pickering Interfacial Catalysts for Selective Oxidation of Sulfides”

Cellulose conversion to 5-hydroxymethylfurfural via a simple and efficient phosphate-doped hafnium oxide catalyst

The efficient catalytic conversion of cellulose to 5-hydroxymethylfurfural (HMF) can provide a valuable reference for the high-value utilization of biomass. In this work, a series of simple phosphate-doped hafnium oxide catalysts (x-P-HfO2) were prepared, and their physicochemical properties were analyzed by ICP-OES, XRD, XPS, FTIR, SEM-EDX, N2 adsorption-desorption isotherms, NH3-TPD and Py-FTIR characterizes. Detailed evaluation of the reaction conditions demonstrated the ideal catalytic performance of the x-P-HfO2 catalysts, and the HMF yield from cellulose reached a satisfactory 61% in the water(NaCl)/tetrahydrofuran biphasic reaction system. Based on the captured intermediates and detected by-products, possible catalytic pathways are summarized. Meanwhile, the hydrothermal stability of the catalyst was also investigated, and the reason for its performance degradation after five cycles was determined to be the loss of useful Brønsted active sites. In addition, the effects of the phosphating and sulfating modification approaches on the catalyst activity were also compared, verifying that the introduction of phosphate is more conducive to the catalyst expressing high activity for the formation of HMF from cellulose.

Construction of Co3S4/MoS2 p-p heterojunction as an efficient catalyst for water splitting and electrochemical oxidation of organic molecules

Electrolysis of wastewater containing urea or small organic molecules while obtaining hydrogen energy is a promising strategy for realizing energy acquisition and environmental protection. Construction of semiconductor heterojunctions to regulate the transfer of interfacial electrons has been regarded as an efficient approach to improve the electrocatalytic performance of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) for the materials, and obtain the bifunctional electrocatalysts aiming to construct a water splitting cell using one non-precious metal material. Herein, a bifunctional Co3S4/MoS2 electrocatalyst with a p-p heterojunction and hollow structure has been successfully prepared through the precipitation-hydrothermal method, which presents the high bifunctional electrocatalytic performance due to the formed path of electron transfer in the heterojunction interface being favorable for OH- adsorption. The accelerated electron transfer in heterojunction interfaces endows Co3S4/MoS2 presenting the superior electrocatalytic performance including OER, urea oxidation reaction (UOR) and oxygen evolution reaction in lactic acid solution (OER-LA). At 50 mA cm−2, the voltages of HER, OER, UOR and OER-LA are −0.123, 1.511, 1.400, 1.440 V vs. RHE, respectively. In a two-electrode electrolytic cell using Co3S4/MoS2 as anode and cathode displays the outstanding electrocatalytic performance in 1 M KOH, 1 M KOH containing 0.5 M urea, and 1 M KOH containing 0.5 M lactic acid electrolytes, superior to the most reported materials. This research provides a strategy for the construction of advanced bifunctional electrocatalysts using metal sulfides to form heterojunction for realizing the high bifunctional catalytic activities in hydrogen production and organic molecule decontamination.

Interface Engineering of Electrocatalysts for Efficient and Selective Oxygen Evolution in Alkaline/Seawater

Electrochemical water splitting is regarded as an effective technology for producing green hydrogen, which is crucial for addressing energy and environmental challenges. In particular, direct seawater splitting offers significant economic and environmental advantages. However, its efficiency is hindered by the high overpotential required for the oxygen evolution reaction (OER) and the competition from chloride oxidation. This review highlights the potential of interface engineering to overcome these limitations and develop efficient OER electrocatalysts. We comprehensively explore recent advancements in interface engineering for OER in both alkaline and seawater environments. We begin by introducing the mechanisms of freshwater and seawater electrolysis, emphasizing key considerations for OER catalyst design. Subsequently, we review the recent progress made in various interface engineering strategies, analyzing their impact on OER performance in both electrolytes. Finally, we outline promising future directions for developing efficient seawater oxidation catalysts through interface engineering.