Catalytic Performance Research Articles

Construction of Cs2AgBiCl6/COF Heterojunction for Boosted Photocatalytic Thioester Oxidation.

Lead-free halide perovskites as a new kind of potential candidate for photocatalytic organic synthesis have attracted much attention recently. The rational heterojunction construction is regarded as an efficient strategy to delicately regulate their catalytic performances. Herein, a semi-conductive covalent organic framework (COF) nanosheet, C4N, is employed as the functional component to construct Cs2AgBiCl6/C4N (CABC/C4N) heterojunction. It is found that the C4N nanosheets with rich surface functional groups can serve as heterogeneous nucleation sites to manipulate the growth of CABC nanocrystals and afford close contact between each other, therefore facilitate the transfer and spatial separation of photogenerated charge carriers, as verified by in situ X-ray photoelectronic spectroscopy and Kelvin probe force microscopy. Moreover, the oxygen affinity of C4N endows the heterojunctions with outstanding aerobic reactivity, thus improving the photocatalytic performance largely. The optimal CABC/C4N heterojunction delivers a thioanisole conversion efficiency of 100% after 6h, which is 2.2 and 7.7-fold of that of CABC and C4N. This work provides a new ideal for the design and application of lead-free perovskite heterojunction photocatalysts for organic reactions.

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.

Changeable Active Sites by Pr Doping CuSA-TiO2 Photocatalyst for Excellent Hydrogen Production.

Photocatalytic water splitting for clean hydrogen production has been a very attractive research field for decades. However, the insightful understanding of the actual active sites and their impact on catalytic performance is still ambiguous. Herein, a Pr-doped TiO2-supported Cu single atom (SA) photocatalyst is successfully synthesized (noted as Cu/Pr-TiO2). It is found that Pr dopants passivate the formation of oxygen vacancies, promoting the density of photogenerated electrons on the CuSAs, and optimizing the electronic structure and H* adsorption behavior on the CuSA active sites. The photocatalytic hydrogen evolution rate of the obtained Cu/Pr-TiO2 catalyst reaches 32.88mmolg-1h-1, 2.3 times higher than the Cu/TiO2. Innovatively, the excellent catalytic activity and performance is attributed to the active sites change from O atoms to CuSAs after Pr doping is found. This work provides new insight for understanding the accurate roles of single atoms in photocatalytic water splitting.

Constructing Ionic Interfaces for Stable Electrochemical CO2 Reduction.

The electrochemical CO2 reduction reaction (CO2RR) has emerged as a promising approach for sustainable carbon cycling and valuable chemical production. Various methods and strategies have been explored to boost CO2RR performance. One of the most promising strategies includes the construction of stable ionic interfaces on metallic or molecular catalysts using organic or inorganic cations, which has demonstrated a significant improvement in catalytic performance. The stable ionic interface is instrumental in adjusting adsorption behavior, influencing reactive intermediates, facilitating mass transportation, and suppressing the hydrogen evolution reaction, particularly under acidic conditions. In this Perspective, we provide an overview of the recent advancements in building ionic interfaces in the electrocatalytic process and discuss the application of this strategy to improve the CO2RR performance of metallic and molecular catalysts. We aim to convey the future trends and opportunities in creating ionic interfaces to further enhance carbon utilization efficiency and the productivity of CO2RR products. The emphasis of this Perspective lies in the pivotal role of ionic interfaces in catalysis, providing a valuable reference for future research in this critical field.

Thermal Shock Synthesis for Loading Sub-2nm Ru nanoclusters on Titanium Nitride as a Remarkable Electrocatalyst towards Hydrogen Evolution Reaction.

Heterogeneous catalysts embracing metal entities on suitable supports are profound in catalyzing various chemical reactions, and substantial synthetic endeavors in metal-support interaction modulation have been made to enhance catalytic performance. Here, it is reported the loading of sub-2nm Ru nanocrystals (NCs) on titanium nitride support (HTS-Ru-NCs/TiN) via a special Ru-Ti interaction using high temperature shock (HTS) method. Direct dechlorination of the adsorbed RuCl3, ultrafast nucleation process and short coalescence duration at ultrahigh temperatures contribute to the immobilization of Ru NCs on TiN support via producing the Ru-Ti interfacial perimeter. HTS-Ru-NCs/TiN shows remarkable activity towards hydrogen evolution reaction (HER) in alkaline solution, yielding ultralow overpotentials of 16.3 and 86.6mV to achieve 10 and 100mAcm-2, respectively. The alkaline and anion exchange membrane water electrolyzers assembled using HTS-Ru-NCs/TiN yield 1.0Acm-2 at 1.65 and 1.67V, respectively, which validate its applicability in hydrogen production industry. Theoretical simulations reveal the favorable formation of Ru-O and Ti-H bond at the interfacial perimeters between Ru NCs and TiN, which accelerates the prerequisite water dissociation kinetics for the enhanced HER activity. This exemplified work motivates the design of specific interfacial perimeters via the HTS strategy to improve the performance of diverse catalysis. This article is protected by copyright. All rights reserved.

Ultrasound-Triggered Piezoelectric Catalysis of Zinc Oxide@Glucose Derived Carbon Spheres for the Treatment of MRSA Infected Osteomyelitis.

Currently, methicillin-resistant Staphylococcus aureus (MRSA)-induced osteomyelitis is a clinically life-threatening disease, however, long-term antibiotic treatment can lead to bacterial resistance, posing a huge challenge to treatment and public health. In this study, glucose-derived carbon spheres loaded with zinc oxide (ZnO@HTCS) are successfully constructed. This composite demonstrates the robust ability to generate reactive oxygen species (ROS) under ultrasound (US) irradiation, eradicating 99.788% ± 0.087% of MRSA within 15min and effectively treating MRSA-induced osteomyelitis infection. Piezoelectric force microscopy tests and finite element method simulations reveal that the ZnO@HTCS composite exhibits superior piezoelectric catalytic performance compared to pure ZnO, making it a unique piezoelectric sonosensitizer. Density functional theory calculations reveal that the formation of a Mott-Schottky heterojunction and an internal piezoelectric field within the interface accelerates the electron transfer and the separation of electron-hole pairs. Concurrently, surface vacancies of the composite enable the adsorption of a greater amount of oxygen, enhancing the piezoelectric catalytic effect and generating a substantial quantity of ROS. This work not only presents a promising approach for augmenting piezoelectric catalysis through construction of a Schottky heterojunction interface but also provides a novel, efficient therapeutic strategy for treating osteomyelitis.

Weakening Mn-O Bond Strength in Mn-Based Perovskite Catalysts to Enhance Propane Catalytic Combustion.

Exploring highly efficient and robust non-noble metal catalysts for VOC abatement is crucial but challenging. Mn-based perovskites are a class of redox catalysts with good thermal stability, but their activity in the catalytic combustion of light alkanes is insufficient. In this work, we modulated the Mn-O bond strength in a Mn-based perovskite via defect engineering, over which the catalytic activity of propane combustion was significantly enhanced. It demonstrates that the oxygen vacancy concentration and the Mn-O bond strength can be efficiently modulated by finely tuning the Ni content in SmNixMn1-xO3 perovskite catalysts (SNxM1-x), which in turn can enhance the redox ability and generate more active oxygen species. The SN0.10M0.90 catalyst with the lowest Mn-O bond strength exhibits the lowest apparent activation energy, over which the propane conversion rate increases by 3.6 times compared to that on the SmMnO3 perovskite catalyst (SM). In addition, a SN0.10M0.90/cordierite monolithic catalyst can also exhibit a remarkable catalytic performance and deliver excellent long-term durability (1000 h), indicating broad prospects in industrial applications. Moreover, the promotional effect of Ni substitution was further unveiled by density functional theory (DFT) calculations. This work brings a favorable guidance for the exploration of highly efficient perovskite catalysts for light alkane elimination.

Nanocavity in hollow sandwiched catalysts as substrate regulator for boosting hydrodeoxygenation of biomass-derived carbonyl compounds.

Hydrodeoxygenation of oxygen-rich molecules toward hydrocarbons is attractive yet challenging in the sustainable biomass upgrading. The typical supported metal catalysts often display unstable catalytic performances owing to the migration and aggregation of metal nanoparticles (NPs) into large sizes under harsh conditions. Here, we develop a crystal growth and post-synthetic etching method to construct hollow chromium terephthalate MIL-101 (named as HoMIL-101) with one layer of sandwiched Ru NPs as robust catalysts. Impressively, HoMIL-101@Ru@MIL-101 exhibits the excellent activity and stability for hydrodeoxygenation of biomass-derived levulinic acid to gamma-valerolactone under 50°C and 1-megapascal H2, and its activity is about six times of solid sandwich counterparts, outperforming the state-of-the-art heterogeneous catalysts. Control experiments and theoretical simulation clearly indicate that the enrichment of levulinic acid and H2 by nanocavity as substrate regulator enables self-regulating the backwash of both substrates toward Ru NPs sandwiched in MIL-101 shells for promoting reaction with respect to solid counterparts, thus leading to the substantially enhanced performance.

Peroxymonosulfate activation by superparamagnetic mixed-valent Cu/N-(L-cysteine)-O-(carboxymethyl)chitosan/cobalt ferrate-rice hull hybrid nanocomposite for efficient degradation of naproxen: Synergetic adsorption-catalysis, kinetics, pathway, and relevant mechanism.

Naproxen (NPX) as an emerging anthropogenic contaminant was detected in many water sources, which can pose a serious threat to the environment and human health. Peroxymonosulfate (PMS) decomposed by Cu(I) has been considered an effective activation method to produce reactive species. However, this decontamination process is restricted by the slow transformation of Cu(II)/Cu(I) by PMS. Herein, new N-(L-cysteine/triazine)-O-(carboxymethyl)-chitosan/cobalt ferrate-rice hull hybrid biocomposite was constructed to anchor the mixed-valent Cu(I)-Cu (II) (CuI, II-CCCF) for removing pharmaceutical pollutants (i.e., naproxen, ciprofloxacin, tetracycline, levofloxacin, and paracetamol). The structural, morphological, and catalytic properties of the CuI,II-CCCF have been fully identified by a series of physicochemical characterizations. Results demonstrated that the multifunctional, hydrophilic character, and negative ζ-potential of the activator, accelerating the redox cycle of Cu(II)/Cu(I) with hydroxyl amine (HA). The negligible metal leaching, well-balanced thermodynamic-kinetic properties, and efficient adsorption-catalysis synergy are the main reasons for the significantly enhanced catalytic performance of CuI,II-CCCF in the removal of NPX (98.6 % at 7.0 min). The main active species in the catalytic degradation of NPX were identified (●OH > SO4●- > 1O2 > > O2●-) and consequently suggested a degradation path. It can be noted that these types of carbohydrate-based nanocomposite offer numerous advantages, encompassing simple preparation, excellent decontamination capabilities, and long-term stability.

Engineering the Activity and Stability of the Zn-MOF Catalyst via the Interaction of Doped Zr with Zn.

Metallic atoms within metal-organic framework (MOF) materials exhibit a distinctive and adaptable coordination structure. The three-dimensional (3D) pore configuration of MOFs enables the complete exposure of metal active sites, rendering them prevalent in various catalytic reactions. In this study, zinc (Zn) atoms within Zn-based MOF materials, characterized by an abundance of valence electrons, are utilized for the transesterification of dimethyl carbonate (DMC). Additionally, the introduction of zirconium (Zr) effectively addresses the susceptibility of the MOFs' crystal structure to dissolution in organic solvents. The formulated catalyst, Zn-10%Zr-MOF(300), demonstrates remarkable catalytic performance with 91.5% DMC selectivity, 61.9% propylene carbonate (PC) conversion, and 56.6% DMC yield. Impressively, the catalyst maintains its high performance over five cycles. Results indicate that Zr interacts with Zn, forming new coordination bonds and enhancing the catalyst crystal structure stability. Moreover, electron transfer intensifies the alkalinity of the active Zn atoms, enhancing the overall catalyst performance. This research informs the development of transesterification heterogeneous catalysts and broadens the application scope of MOF catalysts.

METHANOL STEAM REFORMING FOR HYDROGEN PRODUCTION OVER Ni-BASED CATALYSTS: STATE-OF-THE-ART REVIEW AND FUTURE PROSPECTS.

With increasing global emphasis on environmental sustainability, the reliance on traditional energy sources such as coal, natural gas, and oil is encountering significant challenges. H2, known for its high energy content and pollution-free usage, emerges as a promising alternative. However, despite the great potential of H2, approximately 95% of hydrogen production still depends on non-renewable resources. Hence, the shift towards producing H2 from renewable sources, particularly through methods like steam reforming of methanol - a renewable resource - represents a beacon of hope for advancing sustainable energy practices. This review comprehensively examines recent advancements in efficient H2 production using Ni-based catalysts in methanol steam reforming (MSR) and proposes the future prospects. Firstly, the fundamental principles of MSR technology and the significance in clean energy generation are elucidated. Subsequently, the design, synthesis techniques, and optimization strategies for enhancing the catalytic performance of Ni-based catalysts are discussed. Through the analysis of various catalyst compositions, structural adjustments, surface active sites, and modification methods, the review uncovers effective approaches for boosting the activity and durability of MSR reactions.By offering a comprehensive critical analysis, this review serves as a valuable reference to enhance MSR hydrogen production efficiency and catalyst performance.

High-Entropy La(FeCuMnMgTi)O3 Nanoparticles as Heterogeneous Catalyst for CO2 Electroreduction Reaction.

In this work, La(FeCuMnMgTi)O3 HEO nanoparticles with a perovskite-type structure are synthesized and used in the electrocatalytic CO2 reduction reaction (CO2RR). The catalyst demonstrates high performance as an electrocatalyst for the CO2RR, with a Faradaic efficiency (FE) of 92.5% at a current density of 21.9 mA cm-2 under -0.75 V vs a saturated calomel electrode (SCE). Particularly, an FE above 54% is obtained for methyl isopropyl ketone (C5H10O, MIPK) at a partial current density of 16 mA cm-2, overcoming all previous works. Besides, the as-prepared HEO catalyst displays robust stability in the CO2RR. The excellent catalytic performance of La(FeCuMnMgTi)O3 is ascribed to the synergistic effect between the electronic effects associated with five cations occupying the high-entropy sublattice sites and the oxygen vacancies within the perovskite structure of the HEO. Finally, DFT calculations indicate that Cu plays a vital role in the catalytic activity of the La(FeCuMnMgTi)O3 HEO nanoparticles toward C2+ products.

In situ N-doping engineered biochar catalysts for oxidation degradation of sulfadiazine via nonradical pathways: Singlet oxygen and electron transfer.

Understanding the structure of non-metallic heteroatom-doped carbon catalysts and the subsequent degradation of new pollutants is crucial for designing more efficient carbon catalysts. Environmentally friendly in situ N-doped biochar catalysts were prepared for peroxymonosulfate (PMS) activation and sulfadiazine (SDZ) degradation. The acid washing process and calcination temperature of catalyst increased π-π* shake up, graphitic N percentage, specific surface area and defects, promoting the transformation of pollutant degradation mechanism from radical pathway to non-radical pathway. 100 % of the SDZ with the initial concentration of 10 mg/L was quickly degraded within 60 min using 0.2 g/L catalysts and 0.5 mM PMS. Excellent catalytic performance was attributed to singlet oxygen and electron transfer-dominated non-radical pathways. The four potential degradation pathways of SDZ were proposed, and toxicity predication indicated that overall biotoxicity of the intermediates during SDZ degradation was decreased. This research deepens our understanding of the mechanisms of non-radical pathways and guides the synthesis of carbon-based catalysts.

Ni-based catalysts supported on Hbeta zeolite for the hydrocracking of waste polyolefins.

Polyolefin plastics are the most popular polymer materials worldwide, and the catalytic degradation of post-consumer polyolefins has attracted increased attention as a viable process. In this study, two types of Ni-based catalysts supported on Hbeta zeolite, Ni-Hbeta and NiS2-Hbeta, have been successfully synthesized for the hydrocracking of waste polyolefin. The experimental results indicated that the synergistic effect between Ni or NiS2 and the acidic sites of Hbeta zeolites can significantly enhance the tandem cracking and hydrogenation of polyolefin plastics, which suppresses the formation of gas products and coke. Ni-Hbeta employed as a catalyst can effectively degrade HDPE into high value liquid and gas products with high yield of 94% under 523 K and 3 MPa H2, while also exhibiting excellent cycle stability. In particular, Ni-Hbeta shows better catalytic performance than NiS2-Hbeta during the hydrocracking of HDPE at a relatively low temperature of 523 K. Furthermore, Ni-Hbeta catalyst also exhibits a remarkable capability for efficient depolymerization of unsorted post-consumer polyolefin plastics (HDPE, LDPE, PP) containing various additives and pollutants. These findings underscore the application potential of employing noble metal-free and recyclable catalysts for hydrocracking plastic waste, thereby facilitating the realization of a circular economy for plastics.

Propelling gold nanozymes: catalytic activity and biosensing applications.

Recently, gold nanomaterials have been rapidly developed owing to their high stability, good biocompatibility, and multifunctionality. The unique catalytic activity of gold nanomaterials has driven the emergence of the concept for a"gold nanozyme." Understanding the characteristics of gold nanozymes is crucial for improving their catalytic performance as well as expanding their applications. In this review, we provide an overview of the intrinsic enzyme-like activities of gold nanozymes, including peroxidase-, catalase-, superoxide dismutase-, and glucose oxidase-like activities, and the catalytic mechanisms involved. In addition, strategies for modulating the catalytic activity of gold nanozymesand theirapplications in biosensing were discussed in detail. Moreover, we highlight the current challenges of gold nanozymes and look forward to attracting more attention for propelling the developments in this field.

Material Engineering Strategies for Efficient Hydrogen Evolution Reaction Catalysts.

Water electrolysis, a key enabler of hydrogen energy production, presents significant potential as a strategy for achieving net-zero emissions. However, the widespread deployment of water electrolysis is currently limited by the high-cost and scarce noble metal electrocatalysts in hydrogen evolution reaction (HER). Given this challenge, design and synthesis of cost-effective and high-performance alternative catalysts have become a research focus, which necessitates insightful understandings of HER fundamentals and material engineering strategies. Distinct from typical reviews that concentrate only on the summary of recent catalyst materials, this review article shifts focus to material engineering strategies for developing efficient HER catalysts. In-depth analysis of key material design approaches for HER catalysts, such as doping, vacancy defect creation, phase engineering, and metal-support engineering, are illustrated along with typical research cases. A special emphasis is placed on designing noble metal-free catalysts with a brief discussion on recent advancements in electrocatalytic water-splitting technology. The article also delves into important descriptors, reliable evaluation parameters and characterization techniques, aiming to link the fundamental mechanisms of HER with its catalytic performance. In conclusion, it explores future trends in HER catalysts by integrating theoretical, experimental and industrial perspectives, while acknowledging the challenges that remain.

Insight of hydrogen evolution reaction in slab SnO2 loaded with transition metal atoms

The utilization of hydrogen energy has emerged as a promising solution for clean and sustainable energy sources. The development of cost-effective catalysts with high activity and stability is crucial for efficient hydrogen production. In this work, we investigated the hydrogen evolution reaction (HER) catalytic activity of single transition metal atom (TM = V, Cr, Mn, Fe, Co, Ni) on slab SnO2 by using density functional theory. Our results revealed that the catalytic activity of the slab SnO2 can be significantly enhanced by loading the transition atom. By calculating the Gibbs free energies and exchange current densities in different adsorption configurations of TM-SnO2, single-atom catalyst (SAC) of Mn-loaded SAC exhibits excellent catalytic performance, characterized by a low Gibbs free energy barrier (−0.05 eV). Introducing a TM on the SnO2 surface breaks its local symmetry, while the strong coupling between the metal and H atoms enhances catalytic performance. The synergetic effect of symmetry breaking and metal-H interaction boosts overall catalytic activity. This work not only proposes a novel non-platinum HER catalyst based on SnO2 but also lays a solid foundation for future applications of SnO2-based catalysts.

Impact of the Copper Second Coordination Sphere on Catalytic Performance and Substrate Specificity of a Bacterial Lytic Polysaccharide Monooxygenase

Impact of the Copper Second Coordination Sphere on Catalytic Performance and Substrate Specificity of a Bacterial Lytic Polysaccharide Monooxygenase

Protector-free, non-plasmonic silver quantum clusters by femtosecond pulse laser irradiation: in situ binding on nanocellulose filaments for improved catalytic activity and cycling performance.

This study introduces a new, facile method to synthesize silver clusters from aqueous silver ion solution by using high intensity femtosecond pulse laser irradiation. The particles obtained in the absence of reducing or capping agents are 1-17 nm in size and presented quantum properties, as characterized by fluorescence, but did not exhibit plasmon signals, which is not a common characteristic of conventional silver nanoparticles. In a further development, small silver quantum clusters (∼1 nm) were bound in situ to wet-spun filaments of cellulose nanofibrils by pulsed laser irradiation. The obtained hybrid filaments as well as free silver quantum clusters revealed a catalytic activity remarkably higher than that of free gold quantum clusters; moreover, the hybrid filaments were found to show improved stability and cycling performance for silver-based catalysis. The present results indicate the potential of femtosecond laser irradiation to generate clusters as well as hybrid systems with excellent performance and reactivity.

Preparation and Evaluation of FeMnTi Monolithic Catalysts for High‐Efficiency CO Oxidation

AbstractA comprehensive study was conducted on the synthesis of FeMnTi monolithic catalysts using plasma electrolytic oxidation (PEO) process combined with hydrothermal method followed by depositing active nanostructures. As synthesized catalysts were characterized using a series of techniques for morphology, structure and surface chemical state investigations. Meanwhile, the CO light‐off curves demonstrate that they possess excellent low‐temperature catalytic performance compared with TiO2 based single transition oxides. Specifically, FeMnTi(0.10, 4) can achieve 100 % conversion at 201 °C, which is due to the homogeneous elements distribution, large surface area and high surface activity. The supersaturation of the deposited solution and deposition time determine the growth of MnOx and the FeMnTi(0.10, 4) has the most suitable Fe/Mn atom ratio of 2.5. Furthermore, the electron transfer between Fe (Fe2+ and Fe3+) and Mn (Mn2+, Mn3+ and Mn4+) ensures the excellent redox properties. The synthetic strategy proposed in this work has general applicability for synthesizing multiple transition oxides monolithic catalysts not only for CO oxidation.