Efficient Oxidation Research Articles

Balancing the Binding of Intermediates Enhances Alkaline Hydrogen Oxidation on D-Band Center Modulated Pd Sites.

Exploring efficient alkaline hydrogen oxidation reaction (HOR) electrocatalysts is of great concern for constructing anion exchange membrane fuel cells (AEMFCs). Herein, d-band center modulated PdCo alloys with ultralow Pd content anchored onto the defective carbon support (abbreviated as PdCo/NC hereafter) are proposed as highly efficient HOR catalyst. The as-prepared catalyst exhibits exceptional HOR performance compared to the Pt/C catalyst, achieving thermodynamically spontaneous and kinetically preferential reactions. Specifically, the resultant PdCo/NC demonstrates a marked enhancement in alkaline HOR performance, with the highest mass and specific activities of 1919.6 mA mgPd-1 and 1.9 mA cm-2, 51.1 and 4.2 times higher than those of benchmark of Pt/C, along with an excellent stability in a chronoamperometry test. In the analysis of in situ Raman spectra, it was discovered that tetrahedrally coordinated H-bonded water molecules were formed during the HOR process. This indicates that the promotion of interfacial water molecule formation and enhancement of HOR activities in PdCo/NC are facilitated by defect engineering and the turning of d-band center in PdCo alloy. The essential knowledge obtained in this study could open up a new direction for modifying the electronic structure of cost-effective HOR catalysts through electronic structure engineering.

Efficient electrochemical oxidation of the biomass platform compound furfural on a Ni0.48Co0.36O0.16 electrode

Efficient electrochemical oxidation of the biomass platform compound furfural on a Ni0.48Co0.36O0.16 electrode

Convenient construction of electrocatalysts via combustion-assisted corrosion engineering for efficient water oxidation

Developing an efficient strategy for the universal synthesis of electrocatalysts is crucial for advancing the industrialization of water splitting, yet it remains a significant challenge. In this study, we propose combustion-assisted corrosion engineering as a rapid method to fabricate electrocatalysts for the oxygen evolution reaction (OER) within seconds. By utilizing a three-dimensional framework composed of nickel foam and the unique structure of the active species, we enable swift electrolyte diffusion and gas release. Consequently, the optimized S–NiO/NF exhibits remarkable OER catalytic activity, requiring a low overpotential of 236 mV to achieve a current density of 50 mA cm−2 in 1.0 M KOH solution. Notably, the reconfiguration during the OER process leads to the formation of actual catalytic active species, enhancing the number of active centers and thereby improving the catalyst's performance. This research presents a versatile method for industrially fabricating non-noble metal self-supporting electrodes with high efficiency, offering a practical solution for energy conversion and storage.

A Novel Approach for Efficient Water Oxidation and Supercapacitor Applications Based on Morphologically Transformed, Surface Rich Oxygen Vacancies of Co3o4 Nanostructures Co-Synthesized with Potato Starch Peel Extract

A Novel Approach for Efficient Water Oxidation and Supercapacitor Applications Based on Morphologically Transformed, Surface Rich Oxygen Vacancies of Co3o4 Nanostructures Co-Synthesized with Potato Starch Peel Extract

Unraveling Stoichiometry Effect in Nickel‐Tungsten Alloys for Efficient Hydrogen Oxidation Catalysis in Alkaline Electrolytes

Anion‐exchange membrane fuel cells provide the possibility to use platinum group metal‐free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel‐tungsten (Ni‐W) alloy catalysts, we show that the Ni:W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen‐bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state‐of‐the‐art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next‐generation catalysts for fuel cells.

Unraveling Stoichiometry Effect in Nickel-Tungsten Alloys for Efficient Hydrogen Oxidation Catalysis in Alkaline Electrolytes.

Anion-exchange membrane fuel cells provide the possibility to use platinum group metal-free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel-tungsten (Ni-W) alloy catalysts, we show that the Ni:W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen-bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state-of-the-art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next-generation catalysts for fuel cells.

A Low-Noble-Metal Ru@CoMn2O4 Spinel Catalyst for the Efficient Oxidation of Propane

Noble metals have become a research hotspot for the oxidation of light alkanes due to their low ignition temperature and easy activation of C-H; however, sintering and a high price limit their industrial applications. The preparation of effective and low-noble-metal catalysts still presents profound challenges. Herein, we describe how a Ru@CoMn2O4 spinel catalyst was synthesized via Ru in situ doping to promote the activity of propane oxidation. Ru@CoMn2O4 exhibited much higher catalytic activity than CoMn2O4, achieving 90% propane conversion at 217 °C. H2-TPR, O2-TPD, and XPS were used to evaluate the catalyst adsorption/lattice oxygen activity and the adsorption and catalytic oxidation capacity of propane. It could be concluded that Ru promoted synergistic interactions between cobalt and manganese, leading to electron transfer from the highly electronegative Ru to Co2+ and Mn3+. Compared with CoMn2O4, 0.1% Ru@CoMn2O4, with a higher quantity of lattice oxygen and oxygen mobility, possessed a stronger capability of reducibility, which was the main reason for the significant increase in the activity of Ru@CoMn2O4. In addition, intermediates of the reaction between adsorbed propane and lattice oxygen on the catalyst were monitored by in situ DRIFTS. This work highlights a new strategy for the design of a low-noble-metal catalyst for the efficient oxidation of propane.

Dually functional NiSi intermetallic compounds for the efficient hydrogenation and oxidation of cinnamaldehyde

Intermetallic compounds (IMCs) are promising catalysts for upgrading biomass-derived platform chemicals. Herein, bifunctional NiSi IMCs catalysts were developed for the hydrogenation and oxidation of cinnamaldehyde (CAL). A solvent-free arc-melting method was employed for the synthesis of NiSi IMCs within 5 min. The NiSi IMCs catalysts afforded 99 % conversion of CAL and presented ∼ 71 % yield of 2-phenyl propanol and ∼ 34 % yield of benzaldehyde for the hydrogenation and base-free oxidation of CAL, respectively. Moreover, NiSi IMCs could be used for five runs without deactivation. Characterizations and theoretical calculation results indicated the formation of intermetallic structure and the existence of Si vacancy sites, which could not only facilitate the efficient hydrogenation of CAL but also expose NiOx species as catalytic centers for the oxidation of CAL, leading to the high performance and stability in both hydrogenation and oxidation process.

Homogenous Oxidizing Oligomerization Coupled with Coagulation for Water Purification

Natural manganese oxides could induce the intermolecular coupling reactions among small-molecule organics in aqueous environments, which is one of the fundamental processes contributing to natural humification. These processes could be simulated to design novel advanced oxidation technology for water purification. In this study, periodate (PI) was selected as the supplementary electron-acceptor for colloidal manganese oxides (Mn(IV)aq) to remove phenolic contaminants from water. By introducing polyferric sulfate (PFS) into the Mn(IV)aq/PI system and exploiting the flocculation potential of Mn(IV)aq, a post-coagulation process was triggered to eliminate soluble manganese after oxidation. Under acidic conditions, periodate exists in the H4IO6− form as an octahedral oxyacid capable of coordinating with Mn(IV)aq to form bidentate complexes or oligomers (Mn(IV)-PI*) as reactive oxidants. The Mn(IV)-PI* complex could induce cross-coupling process between phenolic contaminants, resulting in the formation of oligomerized products ranging from dimers to hexamers. These oligomerized products participate in the coagulation process and become stored within the nascent floc due to their catenulate nature and strong hydrophobicity. Through coordination between Mn(IV)aq and H4IO6−, residual periodate is firmly connected with manganese oxides in the floc after coagulation and could be simultaneously separated from the aqueous phase. This study achieves oxidizing oligomerization through a homogeneous process under mild conditions without additional energy input or heterogeneous catalyst preparation. Compared to traditional mineralization-driven oxidation techniques, the proposed novel cascade processes realize transformation, convergence, and separation of phenolic contaminants with high oxidant utilization efficiency for low-carbon purification.

Spatial isolation effect improves the acidity and redox capacity of ZSM-5 encapsulating Pt catalyst to achieve efficient toluene oxidation

This paper introduces a novel approach of encapsulating Pt nanoparticles within the pores of a molecular sieve. By comparing the dispersion, reducibility and surface acid sites, the effect of the combination of molecular sieves and Pt particles on the catalytic performance of toluene was studied. The findings demonstrate that Pt nanoparticles were encapsulated within the molecular sieve framework of ZSM-5 molecular sieves using an in-situ synthesis method, exhibiting remarkable catalytic activity towards toluene oxidation (T90=172 ℃). Mainly due to the spatial confinement of the ZSM-5 molecular sieve framework reduces the size of Pt nanoparticles, enhances their dispersion of the Pt@ZSM-5 catalysts. In addition, the space separation effect of ZSM-5 on Pt metal enhances their interaction and promotes the valence state conversion of Pt species. It leads to a large number of acid sites and oxygen vacancies in the catalyst, which improves the adsorption and migration of toluene, thereby improving the catalytic activity. This study will provide valuable insights into the preparation of new nanocatalysts and the catalytic treatment of toluene.

A colorimetric sensor for rapid discrimination of tea polyphenols and tea authentication based on Rh-decorated Pd nanocubes with high peroxidase-like activity

The rapid development of nanozymes has offered substantial opportunities for the fields of biomedicine, chemical sensing, and food safety. Among these applications, multichannel sensors, with the capability of simultaneously detecting multiple target analytes, hold promise for the practical application of nanozymes in chemical sensing with high detection efficiency. In this study, Rh-decorated Pd nanocubes (Pd–Rh nanocubes) with significantly enhanced peroxidase-like activity are synthesized through the mediation of underpotential deposition (UPD) and subsequently employed to develop a multichannel colorimetric sensor for discriminating tea polyphenols (TPs) and tea authentication. Based on a single reactive unit of efficient catalytic oxidation of 3,3′,5,5′-tetramethylbenzidine dihydrochloride (TMB), the nanozyme-based multichannel colorimetric sensor responds to each analyte in as short as 1 min. With the aid of principal component analysis (PCA) and hierarchical cluster analysis (HCA), various TPs and types of tea can be accurately identified. This work not only provides a new type of simply structured and highly active nanozymes but also develops a concise and rapid multichannel sensor for practical application in tea authentication and quality inspection.

O‐2p Hybridization Enhanced Transformation of Active γ‐NiOOH by Chromium Doping for Efficient Urea Oxidation Reaction

O‐2p Hybridization Enhanced Transformation of Active γ‐NiOOH by Chromium Doping for Efficient Urea Oxidation Reaction

Grain boundary defect engineering in rutile iridium oxide boosts efficient and stable acidic water oxidation.

PEMWEis considered a promising technology for coupling with renewable energy sources to achieve clean hydrogen production. However, constrained by the sluggish kinetics of the anodic OERand the acidic abominable environment render the grand challenges in developing the active and stable OER electrocatalyst, leading to low efficiency of PEMWE. Herein, we develop the rutile-type IrO2 nanoparticles with abundant grain boundaries and the continuous nanostructure through the joule heating and sacrificial template method. DFT calculations verified that grain boundaries can modulate the electronic structure of Ir sites and optimize the adsorption of oxygen intermediates, resulting in the accelerated kinetics. The 350-IrO2affords a rapid OER process with 20 times higher mass activity (0.61 A mgIr-1) than the commercial IrO2 at 1.50 V vs. RHE. Benefiting from the reduced overpotential and the preservation of the stable rutile structure, 350-IrO2 exhibits the stability of 200 h test at 10 mA cm-2 with only trace decay of 11.8 mV. Moreover, the assembled PEMWE with anode 350-IrO2 catalyst outputs the current density up to 2 A cm-2 with only 1.84 V applied voltage, long-term operation for 100 h without obvious performance degradation at 1 A cm-2.

Novel strategy to regulate the geometric and electronic structure of Pt catalyst for efficient propane combustion

The geometric and electronic structure of Pt active sites plays a crucial role in determining the catalysts performance, but precise regulation remains challenging. Herein, we propose a novel approach to modulate the nature of Pt active sites by combining photo-deposition of Pt nanoparticles with ultra-low Mo loading (0.1 wt%) modification on Pt/SiO2 catalysts. The addition of ultra-low loading Mo promoter not only effectively reduces the size of Pt particles but also donates electrons to the Pt particles. Furthermore, the photo-deposited Pt particles exhibit a higher proportion of metallic Pt species, which is more stable than that metallic Pt species obtained by H2 reduction, compared to those prepared using traditional wetness impregnation methods. Propane oxidation activity evaluations confirm that the photo-deposited and Mo-modified Pt/0.1Mo/SiO2-P catalyst exhibits the highest activity among all the prepared catalysts. Combined with experiments of C3H8-TPSR and in-situ DRIFT spectra of propane oxidation, it is found that the Pt/0.1Mo/SiO2-P catalyst remarkably promotes propane activation and C-H bond cleavage due to the nature change of Pt active sites, and the presence of gaseous oxygen benefits propane cleavage on active sites. Our primary results provide a promising strategy for designing superior platinum catalysts by regulating Pt active sites nature for efficient propane complete oxidation.

Silica-supported ionic liquid for efficient gaseous arsenic oxide removal through hydrogen bonding

The emission of highly-toxic gaseous As2O3 (As2O3 (g)) from nonferrous metal smelting poses environmental concerns. In this study, we prepared an adsorbent (SMIL-X) by loading an ionic liquid (IL) ([HOEtMI]NTf2) into MCM-41 through an impregnation–evaporation process and then applied it to adsorb As2O3 (g). SMIL-20% exhibited an As2O3 (g) adsorption capacity of 35.48 mg/g at 400 °C, which was 490% times higher than that of neat MCM-41. Characterization of SMIL-X indicated that the IL was mainly supported on MCM-41 through O–H…O bonds formed between the hydroxyl groups (–OH) and the silanol groups (Si–OH) and the O–H…F bonds formed between the C–F groups and the Si–OH groups. The hydrogen bonds significantly contributed to the adsorption of As2O3 (g), with –NH and –OH groups forming hydrogen bonds with As–O species (i.e., N–H…O and O–H…O). This showed superior performance to traditional adsorbents that rely on van der Waals forces and chemisorption. Moreover, after exposure to high concentrations of SO2, the adsorption capacities remained at 76% of their initial values, demonstrating some sulfur resistance. This study presents an excellent adsorbent for the purification of As2O3 (g) and shows promising application potential for treating flue gas emitted by nonferrous metal smelting processes.

Investigation of nanoparticle (Fe3O4) addition to 3rd generation biodiesel (spirulina microalgae)/diesel mixture as an innovative fuel according to different engine variables: An RSM optimization

In order to reduce dangerous air pollution and lessen the hazards associated with climate change, biofuels made from vegetable biomass can be utilized as fuel in diesel engines. However, feedstocks and the crop space needed for their cultivation are unavoidable barriers that hinder its adoption and result in a shortage of farmland for increasing food profits. Nevertheless, microalgae are the most reliable and competent biodiesel supply because they are not edible and do not require cropland. Additionally, the addition of nanoparticles has become popular to improve the negative aspects of biodiesel. Based on these, in this study, multi-purpose optimization research was conducted on the addition of iron oxide (Fe3O4) nanoparticles in three different amounts (25, 50, and 75 ppm) to 20 % synthesized spirulina microalgae biodiesel (SSMB)/80 % diesel mixtures. Tests were conducted at three different compression ratios (14.5:1, 15.5:1, and 16.5:1) (CoR) and four different engine loads (25 %, 50 %, 75 %, and 100 %). The response surface methodology (RSM) optimization process was performed with the test results. According to RSM, a desirability coefficient of 0.8299, 15.80:1 CoR, 68 ppm AoN, and 45 % LoE were the ideal conditions. The optimum responses under these circumstances were 421.9653 g/kWh, 19.4014 %, 0.0939 %, 4.0785 %, 73.1716 ppm and 253.0620 ppm for brake-specific fuel consumption (BSFC), brake-thermal efficiency (BTHE), carbon monoxide (CO), carbon dioxide (CO2), hydrocarbon (HC), and nitrogen oxide (NOx), respectively. RSM could be used successfully because the error rates (maximum 6.5 %) when comparing the test results with the RSM optimization outcomes were within reasonable bounds.

Simultaneous catalytic oxidation of Hg0 and NO over CoxCuy metal oxides catalyst

In this work, Co3O4, CoxCuy and CuO metal oxides catalysts were synthesized by coprecipitation method and tested in catalytic oxidation of Hg0 and NO. The Co3Cu1 catalyst exhibited nearly 100% Hg0 oxidation efficiency at 100-400 ℃ and 84% NO oxidation efficiency at 250 ℃. Respectively, 1155.2μgg-1 Hg0 adsorption capacity and 92.9 μmol g-1 NOx adsorption capacity over Co3Cu1 catalyst were measured by Hg0-TPD and NOx-TPD. The largest BET specific surface area of Co3Cu1 catalyst was obtained, reaching 26.2 m2 g-1. And H2-TPR demonstrated that the first reduction peak temperature (192 ℃) of Co3Cu1 catalyst was much lower than that of other catalysts. O2-TPD illustrated that the oxygen storage capacity and oxygen mobility ability of Co3Cu1 catalyst were higher than that of other catalysts. These results were consistent with the results of Hg0 and NO oxidation activity tests. In addition, in-situ DRIFTS spectra of NO adsorption indicated that the band at 1390cm-1 over Co3Cu1 catalyst disappeared after the pretreatment of Hg0. And the transient experiments of Hg0 adsorption suggested that Hg0 could also be extruded from the surface of Co3Cu1 catalyst after the introduction of NO. It was speculated that there might be competitive adsorption between Hg0 and NO over Co3Cu1 catalyst. Finally, the XPS characterization demonstrated that the Oα and the redox cycle of Co3+ + Cu+ ↔ Co2+ + Cu2+ were involved in Hg0-NO simultaneous oxidation. The Co3Cu1 catalyst was an excellent candidate for Hg0-NO oxidation reaction.

Comprehensive first principles to investigate optoelectronic and transport phenomenon of lead-free double perovskites Ba2AsBO6 (B[bond, double bond]Nb, Ta) compounds.

In the current work we studied the structural, elastics, electrical, optical, thermoelectric, as well as spectroscopic limited maximum efficiency (SLME) of oxide based Ba2AsBO6 (B[bond, double bond]Nb, Ta) materials. All the calculations were performed using first-principles calculation by employing the WIEN2k code. We checked the stability in diverse forms such as optimization, phonon dispersion, mechanical, formation energy, cohesive energy, and thermal stability is computed. The semiconducting nature of these Ba2AsBO6 (B[bond, double bond]Nb, Ta) systems is revealed by calculating the direct band gap values are 1.97eV and 1.49eV respectively. Additionally, we determined the optical properties which analyze the utmost absorption and transition of carriers versus photon energy (eV). Moreover, Ba2AsNbO6 has an estimated SLME of 32%, making it an encouraging alternative for single-junction solar cells. Lastly, we studied the transport properties against temperature, the chemical potential for p-type and n-type charge carriers at various temperatures. At 300K, the zT values are found to be 0.757 and 0.751 for Ba2AsBO6 (B[bond, double bond]Nb, Ta) compounds respectively. Both materials were examined as having strong absorption patterns and an excellent figure of merit (ZT), indicating that materials are appropriate for daily life applications.

Engineering crystal plane of NiCo2O4 to regulate oxygen vacancies and acid sites for alkali-free oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

The catalytic oxidation of HMF involves a cascading reaction with multiple intermediate products, making it crucial to enhance the oriented adsorption capacity of specific functional groups for accelerating the entire process. To achieve the efficient selective oxidation of HMF to FDCA, a series of NiCo2O4 catalysts with different morphologies, such as flaky, echinoids, pompon and corolla, were prepared and characterized by XRD, SEM, TEM, BET, XPS, and FTIR. Among the four catalysts, flaky NiCo2O4 exhibited the most excellent catalytic activity and stability, with a FDCA yield of 60.1% within 12 h at 80 °C without alkali participation. The excellent performance of flaky NiCo2O4 catalyst is attributed to the oxygen vacancies and acid sites generated by the exposed (400) facets. The oxygen vacancies and acid sites on the catalyst surface can precisely adsorb -CHO and -CH2-OH of HMF, respectively, and this synergistic effect promotes the efficient production of FDCA. This work is of great significance for fundamentally study the effect of micro-topography or crystal-plane reaction properties on surfaces.

Electron transfer-mediated peroxymonosulfate activation through monoatomic Fe–pyridinic N4 moiety in biochar-based catalyst for electron-rich pollutants degradation in groundwater

Pollution of groundwater by electron-rich refractory organic pollutants (e-ROPs) is detrimental to ecological integrity and human health. Biochar (BC)-based single-atom Fe catalysts (Fe–SACs) triggering nonradical peroxymonosulfate (PMS) process has shown great potential in addressing this problem. Nevertheless, the successful formation and precise regulation of active sites on BC remain formidable challenges. Herein, co-pyrolysis of BC derived from shrimp shells and N-containing supramolecular organic frameworks with a hexagonal cavity structure of Fe3+–N3 (Fe–SOFs) was, for the first time, used to prepare an efficient and inexpensive BC-based Fe–SAC (Fe–MCA@SS). The Fe–N bond was successfully grafted from Fe–SOFs onto BC and subsequently transformed into monoatomic Fe–pyridinic N4. Moreover, Fe–MCA@SS successfully triggered an efficient nonradical PMS process, degrading 94.5 % of aniline (AN) within 5 min. Mediated electron transfer (MET) mechanism was primarily responsible for AN removal. MET was attributed to the following factors: the synergistic effect of the stronger chemical adsorption of PMS with an Fe atom in Fe–pyridinic N4 active sites, the higher redox potential of [Fe–MCA@SS/PMS]*, and the value of the lowest unoccupied molecular orbital of AN being larger than the value of highest occupied molecular orbital of [Fe–MCA@SS/PMS]*. This study sheds new light on the preparation of BC-based SACs catalyst with efficient nonradical oxidation ability and an excellent feasibility to remove electron-rich organic pollutants in groundwater.