Enhancement Of Catalytic Performance Research Articles

Advancements in cobalt‐based oxide catalysts for soot oxidation: Enhancing catalytic performance through modification and morphology control

AbstractThe widespread use of diesel engines results in significant environmental contamination due to emitted pollutants, particularly soot particles. These pollutants are detrimental to public health. At present, one of the most effective ways to remove soot particles is the catalytic diesel particulate filter after‐treatment technology, which requires the catalyst to have superior low temperature activity. Compared with cerium oxide which is widely used, cobalt oxide in transition metal oxides has been widely studied in recent years because of its high redox ability and easy to control morphology. This paper elaborates on the influence of modification techniques such as doping, loading, and solid solution on the catalytic performance of cobalt‐based catalysts in soot oxidation. Along the same lines, it further reviews the research progress on cobalt‐based oxide catalysts with specific dimensional structures and morphologies in soot oxidation. Finally, it provides an outlook on the challenges faced by the theoretical basis and applied research of cobalt‐based catalysts in soot oxidation.

Strengthening the activity and CO tolerance with bi-component PtNi/NbN-C catalyst for methanol alkaline electrooxidation

It is critical to create the anodic catalysts with high efficiency and economy for direct methanol fuel cells (DMFCs). Here, a series of PtNi/NbN-C catalysts (M=Co, Sn, Ni) are developed using the glycol solvothermal process, to investigate the catalytic effficiency for alkaline methanol oxidation reaction (MOR). Catalytic performance evaluation experiments show that the doped Ni species bring the enhancement effect on Pt/NbN-C for the alkaline MOR. The mass activities of PtxNiy/NbN-C show a volcanic trend with the increased Ni contents. PtNi/NbN-C has the highest mass activity (6025.5 mA·mg-1Pt) for alkaline MOR, 18.3 times greater than that of the Pt/C commercial catalyst. The LSV, EIS, Tafel, CA and CO stripping results imply PtNi/NbN-C also exhibits the lowest onset potential, charge transfer resistance, fastest kinetics, highest CO tolerance and stability. When the XRD, HRTEM, and XPS analysis are combined, it is discovered that the electronic effect between the Pt, Ni, and NbN species is mostly responsible for the catalytic performance enhancement is mainly depend on the electronic effect among the Pt, Ni and NbN species. The presence of Pt in an electron-deficient state can enhance the conversion of adsorbed methanol and intermediates, evidenced by a direct relationship between the d-band centers and the mass activities for MOR of different catalysts. This study may provide guidance for the development of anodic materials for DMFCs.

Effect of A-site cation doping on the catalytic oxidation of toluene over mullite catalyst GdMn2O5

Manganese-based mullite (AMn2O5) catalysts are promising for the catalytic oxidation of VOCs, with their oxidation reaction performance being tunable by modifying the composition of the A-site elements. In this work, various manganese-based mullite catalysts (Gd0.9X0.1Mn2O5, X =Sr, Ce, or Ca) with different A-site elements doping were prepared by the citric acid sol–gel method and applied to the catalytic oxidation of toluene. The activity tests indicated that the enhancement of catalytic performance by doping elements was in the order of Sr > Ce > Ca. Notably, the T90 of the Gd0.9Sr0.1Mn2O5 catalyst was 235.6 °C, a lower 37.8 °C than that of the GdMn2O5. Comprehensive characterization and density functional theory (DFT) simulations revealed that Sr doping facilitates the reduction of Mn4+ to Mn3+, increases the electron occupancy of the eg orbitals in octahedral Mn sites, and elevates the Mn-d band center, thus facilitating the adsorption and activation of O2. Additionally, the raised O-p band center caused by Sr doping enhances lattice oxygen mobility. In situ DRIFTS analysis indicated that the introduction of Sr at the A-site optimizes the toluene reaction pathway and accelerates the reaction rate. This work reveals that a simple A-site cation doping strategy can effectively regulate manganese-based mullite catalysts’ electronic structure and surface reaction activity, providing a feasible method for the large-scale preparation of manganese-based mullite catalysts with excellent catalytic performance.

Neural network potential calculations for melamine adsorption onto Pt (111) compared with density functional theory

Abstract The investigation of Pt-adsorbed melamine is important in elucidating the effect of molecular decoration on the enhancement of catalytic performance for fuel cells, and is an interesting system in which covalent stabilization between the surface and the molecule competes with resonance destabilization by the coordination. The present work discusses whether graph neural network potentials can predict the adsorption structure with the competition. The most stable structure predicted by preferred potential was consistent with that by density functional theory but underestimated resonance destabilization.

In-situ Fe–O co-doped carbon nitride heterogenous catalyst for enhanced photo-Fenton oxidation performance towards recalcitrant organic pollutants

One-step and in-situ FeCl3-participated molten urea thermal polymerization strategy is designed to prepare Fe–O co-doped carbon nitride photo-Fenton catalyst (Fe/OCN). Fe/OCN exhibits remarkable photo-Fenton catalytic oxidation capacity towards recalcitrant organic pollutants, in which 0.31 wt% Fe/OCN with optimal Fe-doping level exhibits significantly 60 and 6.3 times higher pseudo-first-order kinetic constant than single photocatalysis and Fenton system in the degradation of methyl orange. The enhancement of photo-Fenton catalytic performance is mainly ascribed to the realization of ideal Fe–O and Fe–N coordination structure in the framework of polymeric carbon nitride, which can not only serve as prime sites for the adsorption of target pollutants molecules and transfer channels for directed migration of photogenerated charges, but also well-modulate electronic structure and band structure of Fe/OCN. Accordingly, the resulting boosted charge carriers separation and transfer dynamics and increased electron density around Fe active centers facilitate ≡Fe(II) regeneration and H2O2 activation, leading to the significant production of plentiful reactive species responsible for degradation and mineralization of organic pollutants. The present work provides new insight into the optimized design and precise regulation of carbon nitride-based photo-Fenton system for advanced wastewater treatment.

Substrate access tunnel engineering of a Fe-type nitrile hydratase from Pseudomonas fluorescens ZJUT001 for substrate preference adjustment and catalytic performance enhancement

Substrate access tunnel engineering is a useful strategy for enzyme modification. In this study, we improved the catalytic performance of Fe-type Nitrile hydratase (Fe-type NHase) from Pseudomonas fluorescens ZJUT001 (PfNHase) by mutating residue Q86 at the entrance of the substrate access tunnel. The catalytic activity of the mutant PfNHase-αQ86W towards benzonitrile, 2-cyanopyridine, 3-cyanopyridine, and 4-hydroxybenzonitrile was enhanced by 9.35-, 3.30-, 6.55-, and 2.71-fold, respectively, compared to that of the wild-type PfNHase (PfNHase-WT). In addition, the mutant PfNHase-αQ86W showed a catalytic efficiency (kcat/Km) towards benzonitrile 17.32-fold higher than the PfNHase-WT. Interestingly, the substrate preference of PfNHase-αQ86W shifted from aliphatic nitriles to aromatic nitrile substrates. Our analysis delved into the structural changes that led to this altered substrate preference, highlighting an expanded entrance tunnel region, theenlarged substrate-binding pocket, and the increased hydrophobic interactions between the substrate and enzyme. Molecular dynamic simulations and dynamic cross-correlation Matrix (DCCM) further supported these findings, providing a comprehensive explanation for the enhanced catalytic activity towards aromatic nitrile substrates.

Enhancing low-temperature CO2 methanation performance by selectively covering Ni with CeO2 to form Ni-O-Ce interface active sites

The methanation of CO2 is crucial for resource utilization, however, achieving excellent CO2 methanation performance with Ni-based catalysts at low temperatures remains highly challenging. In this study, a high-performance 10Ni-0.1Ce/Al catalyst was synthesized using a simple and efficient one-pot combustion method. Unlike other catalysts with the same components, this catalyst exhibits a unique feature where a small amount of the CeO2 promoter is dispersed on the support, while the majority selectively binds to and coats the Ni nanoparticles. This distinctive structure allows it to achieve approximately 80 % CO2 conversion and 99.9 % CH4 selectivity under conditions of 260 °C, 0.1 MPa, and a GHSV of 48,000 mL·g−1·h−1. The high catalytic performance is attributed to the unique structure of Ni nanoparticles and CeO2, which promotes the formation of numerous Ni-O-Ce interface active sites. These Ni-O-Ce interfaces enhance the reducibility and increase the content of weak basic sites in the catalyst. The combination of in-situ DRIFTS and TPSR reveals that the decomposition of bridged HCOO– to *CO is the rate-determining step. The presence of Ni-O-Ce interface active sites in the 10Ni-0.1Ce/Al catalyst facilitates the generation of abundant bridged HCOO– intermediates with higher activity than the 10Ni/Al catalyst, leading to a substantial enhancement in catalytic performance.

Pt/facet-Engineered Hydroxyapatite Co-Catalyst for Highly Efficient Hydrolysis of Ammonia Borane

Ammonia borane (AB, NH3BH3) is a promising candidate for a hydrogen-storage material because of its high stability as a solid state at room temperature under atmospheric pressure. This study demonstrated a novel catalyst design for highly efficient hydrolysis of AB by hybridizing Pt catalyst with hydroxyapatite (HAp, Ca10(PO4)6(OH)2) as an “active support”, possessing Lewis-acidic Ca2+ sites in the a-plane and Lewis-basic PO43- sites in the c-plane. Facet-engineered HAp particles were synthesized via the microwave-assisted hydrothermal reaction using Ca-EDTA chelates. Varying the Ca/P ratio of HAp precursor (from 1.5 to 1.8) affected the particle morphology, exposed facet ratio of {300} to {002}, and the percentage of phosphate anion species (PO43- and HPO42-). The rod-like HAp sole catalysts performed approximately 2-fold higher activity for the hydrolysis of AB, compared with spherical HAp with low crystallinity. Moreover, the Pt/rod-like HAp co-catalyst demonstrated superior catalytic performance with a turnover frequency (TOF) of 623 molH2 molPt-1 min-1 than the Pt/spherical HAp (<232 molH2 molPt-1 min-1). We proposed a possible mechanism of a synergistic effect in the significant enhancement of the hydrogen release rate from AB. Lewis basic PO43- and Lewis acidic Ca2+ sites on HAp would affect preferential adsorption of electron-deficient BH3 and electron-rich NH3 groups in AB, catalyzing cleavage of B-N bonds. Besides, PO43- sites play a critical role in anchoring Pt particles towards electron transfer from Pt to PO43-, resulting in considerable enhancement of catalytic performance in dissociative adsorption of water molecules, which is a rate-determining step in the hydrolysis.Graphical

Microwave-assisted PMS activation Ti3C2/LaFe0.5Cu0.5O3-P catalysts for efficient degradation of CIP: Enhancement of catalytic performance by phosphoric acid etching

The LaFe0.5Cu0.5O3 perovskite synthesised by MOFs template method was compounded with Mxene Ti3C2, and the novel catalyst M-Ti3C2/LFCO-P was subsequently prepared by phosphoric acid etching. This catalyst effectively induced microwave activation of peroxymonosulfate (PMS), and ciprofloxacin (CIP) was efficiently degraded with a degradation rate reaching 95.48 % within 14 min. Characterization results revealed that the MOFs template method and phosphoric acid etching increased specific surface area (from 25.91 m2/g to 142.41 m2/g) of catalyst and improved its pore size distribution. Phosphoric acid etching successfully introduced phosphorus functional groups and promoted the formation of more oxygen vacancies, thereby significantly enhancing the catalytic activity of the catalyst. The conversion of free radicals and the transformation of free radicals to non-free radicals were demonstrated. Additionally, the catalyst exhibited higher electron transfer efficiency. The catalytic reaction was primarily driven by O2– and 1O2, with OH, SO4−, and e- playing auxiliary roles. Furthermore, the degradation pathway and toxicity of CIP were also evaluated. This work provides a new perspective for improving the catalytic degradation activity of antibiotics by perovskite catalysts.

Nanozyme Catalytic Performance Enhancement through Defect and Electronic Structure Regulation of Metal-Doped NiCo2O4@Pd.

Spinel oxides have emerged as a promising candidate in the realm of nanozymes with variable oxidation states, while their limited active sites and low conductivity hinder further application. In this work, we synthesize a series of metal-doped NiCo2O4 nanospheres decorated with Pd, which are deployed as highly efficient nanozymes for the detection of cancer biomarkers. Through meticulous modulation of the molar ratio between NiCo2O4 and Pd, we orchestrated precise control over the oxygen vacancies and electronic structure within the nanozymes, a key factor in amplifying the catalytic prowess. Leveraging the superior H2O2 reduction catalytic properties of Fe-NiCo2O4@Pd, we have successfully implemented its application in the electrochemical detection of biomarkers, achieving unparalleled analytical performance, much higher than that of Pd/C and other reported nanozymes. This research paves the way for innovative electron modification strategies in the design of high-performance nanozymes, presenting a formidable tool for clinical diagnostic analyses.

Unlocking Quantum Catalysis in Topological Trivial Materials: A Case Study of Janus Monolayer MoSMg

The emerging field of topological catalysis has received significant attention due to its potential for high‐performance catalytic activity in the hydrogen‐evolution reaction (HER). While topological materials often possess fragile surface states, trivial topological materials not only offer a larger pool of candidates but also demonstrate robust surface states. As a result, the search for topological catalysts has expanded to include trivial schemes. In this study, a novel 2D Janus monolayer, MoSMg, which demonstrates exceptional obstructed atomic insulating behavior, is presented. Crucially, this trivial metallic topological state exhibits clean obstructed surface states, leading to a significant enhancement in catalytic performance for the HER in electrochemical processes, particularly under high hydrogen coverage. Moreover, the edge sites of this MoSMg monolayer exhibit even more superior catalytic activity, characterized by near‐zero Gibbs free energies. In these findings, the way is paved for exploring new avenues in the design of quantum electrocatalysts, especially within the realm of trivial topological materials.

Preparation of defect-enriched Cu-doped FeOCl/g-C3N4Z-scheme composites for efficient photo-Fenton-like performance

In this study, a Z-scheme heterojunction with abundant oxygen vacancies (OVs) formed by Cu-doped FeOCl (Cu-FeOCl) and graphitic carbon nitride nanosheets (CNNS) was successfully synthesized for the removal of tetracycline hydrochloride (TC). The prepared Cu-FeOCl/CNNS had excellent catalytic properties under hydrogen peroxide and light illumination, and the maximum reaction rate was nearly 156 and 48 times higher than that of FeOCl and CNNS, respectively. The enhancement of catalytic performance was due to the synergistic effect of Cu species, Fe species and Ovs, which effectively promoted the adsorption and activation of H2O2, and inhibited the recombination of photogenerated carriers. We further studied the effects of different reaction conditions (catalyst dosage, H2O2 dosage, initial pH, TC concentration, and coexisting substances) on the degradation reaction. 1O2, h+, •O2−, and •OH were active species participating in the reaction, and a possible TC degradation mechanism was studied. This work provided insights into the synergetic action of interface engineering, ion doping, and oxygen defects in the photo-Fenton-like system.

Boosting photo-thermal co-catalysis CO2 methanation by tuning interface electron transfer via Mott-Schottky heterojunction effect

Photo-thermal co-catalytic reduction of CO2 to synthesize value-added chemicals presents a promising approach to addressing environmental issues. Nevertheless, traditional catalysts exhibit low light utilization efficiency, leading to the generation of a reduced number of electron-hole pairs and rapid recombination, thereby limiting catalytic performance enhancement. Herein, a Mott-Schottky heterojunction catalyst was developed by incorporating nitrogen-doped carbon coated TiO2 supported nickel (Ni) nanometallic particles (Ni/x-TiO2@NC). The optimal Ni/0.5-TiO2@NC sample displayed a conversion rate of 71.6 % and a methane (CH4) production rate of 65.3 mmol/(gcat·h) during photo-thermal co-catalytic CO2 methanation under full-spectrum illumination, with a CH4 selectivity exceeding 99.6 %. The catalyst demonstrates good stability as it shows no decay after two reaction cycles. The Mott-Schottky heterojunction catalysts display excellent efficiency in separating photo-generated electron-hole pairs and elevate the catalysts’ temperature, thus accelerating the reaction rate. The in-situ experiments revealed that light-induced electron transfer effectively facilitates H2 dissociation and enhances surface defects, thereby promoting CO2 adsorption. This study introduces a novel approach for developing photo-thermal catalysts for CO2 reduction, aiming to enhance solar energy utilization and facilitate interface electron transfer.

Fabrication of robust layered double-hydroxide nanoparticles for α-Amylase immobilization: Enhancing catalytic performance, stability, and prospective sustainable biocatalysis applications

Fabrication of robust layered double-hydroxide nanoparticles for α-Amylase immobilization: Enhancing catalytic performance, stability, and prospective sustainable biocatalysis applications

Theoretical Insights into Enhancing Catalytic Performance of Al-Cu Alloy for CO2 Electroreduction toward Ethene Production.

The understanding of the reaction mechanism of CO2 electroreduction (CO2RR) is essential for the precise design of catalysts for specific products with high selectivity. In this work, combined with the computational hydrogen electrode model and kinetic energy barrier calculations, CO2RR pathways on Cu(100) and Al1Cu3(100) are intensively investigated. The free energy barrier of the rate-determining step of ethylene formation is reduced from 1.08 eV for *CCOH formation on Cu(100) to 0.51 eV for *CH2OCHOH formation on Al1Cu3(100) and enhances the catalytic activity. The reaction free energy of *CO-*CO coupling is remarkably reduced from 0.86 eV on Cu(100) to -0.43 eV on Al1Cu3(100) and the coupling barrier is reduced from 0.97 to 0.37 eV, suppressing the production of gas phase CO and enhancing the production of C2 products. Furthermore, the selectivity toward C-O breaking of *CH2CHOH on Cu(100) and *CH2CH2OH on Al1Cu3(100) ensures high selectivity toward ethene rather than ethanol.

Axially coordinated dual-atomic-site catalysts for nearly 100% peroxymonosulfate conversion to 1O2 in membrane filtration

Reactive membrane filtration, integrating membrane technology with catalytic processes, offers a promising avenue for efficiently generating and utilizing active species in environmental remediation. Herein, a dual-atom Co-Mn site achieved through axial coordination on N-doped graphene catalyst (sp-CoMn@NG) has been developed and applied in membrane filtration for the targeted removal of specific pollutants. Experimental investigations, alongside density functional theory (DFT) calculations, have substantiated that axial coordination can effectively reduce the adsorption energy and activation barrier of PMS, thereby facilitating nearly 100% conversion of PMS to 1O2 and enhancing catalytic performance. Mechanistic studies further elucidate the 1O2 production mechanism through a superoxide-mediated chain reaction at the axially coordinated Co-Mn center, as well as the inactivation mechanism of catalytic membranes via the addition reaction of 1O2 and phenolic-hydroxyl compounds. This research underscores the intelligent prefabrication of axial coordination in dual-atomic-site catalysts, offering an efficient approach for scalable 1O2 production in reactive membrane filtration.

Study on the specific photodegradation performance of Fe3O4@SiO2@TiO2@MIPs for berberine hydrochloride

Abstract Adsorption is crucial for the performance of photocatalysts in degrading new pollutants. Here, we report a magnetic molecularly imprinted material Fe3O4@SiO2@TiO2@MIPs with a semiconductor/insulator/semiconductor structure, which achieved up to 81% preferential degradation of berberine hydrochloride (BH). The significant enhancement of catalytic performance can be attributed to the interaction between BH and the imprinted cavity, as well as size matching, which proposes new solutions to address the current problem of difficult degradation of new pollutants.

Oxygen vacancy engineering and rare earth ion modification in Er-doped Bi0.5Na0.5TiO3–BaTiO3 for piezo-photocatalysis

The pursuit of high-performance piezo-photocatalysts through structural modifications has been a focal point of investigation within the realm of related scientific disciplines. In this study, we successfully designed Er-doped Bi0.5Na0.5TiO3–BaTiO3 combined with rare earth ion doping and solid solution modification, and the prepared particles exhibited homogeneous grain sizes and optimized concentrations of oxygen vacancies (OV). The synergistic incorporation of OV (accelerator for catalytic reaction) and Er3+ results in an impressive 12-fold enhancement of the piezo-photocatalytic rate when degrading the Rhodamine B dye. The optimal composition 0.96BNT-0.04BT-Er demonstrates outstanding electrochemical properties, including a superior photocurrent response and minimal impedance, highlighting its exceptional performance in piezo-photocatalysis. The fundamental enhancement in catalytic performance can be attributed to the reconfiguration of the band structure of 0.96BNT-0.04BT-Er, which has been meticulously calculated utilizing DRS and VB-XPS and the internal mechanism was explained in detail. This research serves as a source of inspiration for the investigation of solid solutions among piezo-photocatalysts and sheds light on the vital role of band structure in governing catalytic performance.

High-entropy oxide based biomimetic catalysis system enables robust oxidative desulfurization with an excellent regeneration ability

Sulfur-containing compounds from the usage of fossil fuel have severe impacts on the ecological environment and human health. To eliminate sulfur species in fuels, oxidative desulfurization is served as an effective technology, whose core lies in constructing an efficient catalytic system under mild conditions. High-entropy oxides (HEOs) with maximized conformational entropy normally generates abundant catalytically active sites, which are beneficial for the enhancement in catalytic performance. On this basis, a biomimetic catalytic system coupling HEO with deep eutectic solvent (DES) was designed for oxidative desulfurization with molecular O2 oxidant by following the electron transfer mechanism. This catalytic system not only exhibited excellent sulfide removal with O2 oxidant under the ambient pressure, but also can resist the adverse effects of naphthalene and indole in an appropriate concentration range. Uniquely, this HEO was capable to be recovered from the DES phase, ensuring a good recycling and regeneration ability. During the whole catalytic process, the electron was transferred in the sequence of sulfide → DES → HEO → O2. These extraordinary features make it to be an alternative candidate for industrial applications under mild conditions.

A Bioinspired Copper-Pair Catalyst in Metal-Organic Frameworks for Molecular Dioxygen Activation and Aerobic Oxidative C-N Coupling.

Open Cu sites were loaded to the UiO-67 metal-organic framework (MOF) skeleton by introduction of flexible Cu-binding pyridylmethylamine (pyma) side chains to the biphenyldicarboxylate linkers. Distance between Cu centers in the MOF pores was tuned by controlling the density of metal-binding side chains. "Interacted" Cu-pair or "isolated" monomeric Cu sites were achieved with high and low (pyma)Cu side chain loading, respectively. Spectroscopic and theoretical studies indicate that "interacted" Cu pairs can effectively bind and activate molecular dioxygen to form Cu2O2 clusters, which showed high catalytic activity for aerobic oxidative C-N coupling. On the contrary, MOF catalyst bearing isolated monomeric Cu sites only showed modest catalytic activity. Enhancement in catalytic performance for the Cu-pair catalyst is attributed to the remote synergistic effect of the paired Cu site, which binds molecular dioxygen and cleaves the O═O bond in a collaborative manner. This work demonstrates that noncovalently interacted metal-pair sites can effectively activate inert small molecules and promote heterogeneous catalytic processes.