Catalytic Reaction Research Articles

Coupling of the catalytic reactions from formate dehydrogenase and hydrogenase in solution: Insights from computations and in situ IR spectroscopy

Coupling of the catalytic reactions from formate dehydrogenase and hydrogenase in solution: Insights from computations and in situ IR spectroscopy

Mechanical-vibration-driven piezocatalytic degradation of organic pollutants over microcrystalline SnSe with selenium vacancies

Two-dimensional piezoelectric materials are attractive candidates to trigger piezoelectric catalytic reactions for organics degradation. Microcrystalline structures can endow them with enhanced piezocatalytic activity due totheir large surface area and abundant defect structures. In this work, microcrystalline SnSe with selenium vacancies (mc-SeVs SnSe) was synthesized and employed for piezocatalytic degradation of aqueous organics for the first time. Various instrumental testing results demonstrated that this unique microcrystalline SnSe has strong piezoelectric responses, abundant selenium vacancy defects and large active edges. Compared with crystalline SnSe, mc-SeVs SnSe showed superior piezocatalytic activity for the degradation of various organics in water. More importantly, mc-SeVs SnSe could induce the piezoelectric effect through mild mechanical energy to facilitate the efficient degradation of organic pollutants. The degradation efficiency of Crystal violet, p-nitrophenol, Malachite green, Congo red and Rhodamine B approached 100 % within 60 min reaction time. Superoxide and hydroxyl radicals were detected as the main reactive oxygen species generated in the piezocatalytic process. The degradation pathways of Rhodamine B were proposed based on high performance liquid chromatography-quadrupole-time of flight mass spectrum. The impact of strain on the alterations of dipole moment and electronic structure was investigated using density functional theory. The change in electron band structure induced by the polarized electric field was the underlying reason for the generation of hydroxyl radicals. This work will enrich the piezoelectric materials for organics degradation and provide fresh light on the mechanism of mechanically driven piezoelectric catalytic reactions.

Unraveling the Interplay between Stability and Flexibility in the Design of Polyethylene Terephthalate (PET) Hydrolases.

The accumulation of polyethylene terephthalate (PET), a widely used polyester plastic in packaging and textiles, has led to a global environmental crisis. Biodegradation presents a promising strategy for PET recycling, with PET hydrolases (PETase) undertaking the task at the molecular level. Unfortunately, PETase operates only at ambient temperatures with low efficiency, limiting its industrial application. Current engineering efforts focus on enhancing the thermostability of PETase, but increased stability can reduce the structural dynamics needed for substrate binding, potentially slowing enzymatic activity. To elucidate the balance between stability and flexibility in optimizing PETase catalytic activity, we performed theoretical investigations on both wild-type PETase (WT-PETase) and a thermophilic variant (Thermo-PETase) using molecular dynamics simulations and frustration analysis. Despite being initially designed to stabilize the native structure of the enzyme, our findings reveal that Thermo-PETase exhibits an unprecedented increase in structural flexibility at the PET-binding and catalytic sites, beneficial for substrate recruitment and product release, compared to WT-PETase. Upon PET binding, we observed that the structural dynamics of Thermo-PETase is largely quenched, favoring the proximity between the catalytic residues and the carbonyl of the PET substrate. This may potentially contribute to a higher probability of a catalytic reaction occurring in Thermo-PETase compared to WT-PETase. We suggest that Thermo-PETase can exhibit higher PET-degradation performance than WT-PETase across a broad temperature range by leveraging stability and flexibility at high and low temperatures, respectively. Our findings provide valuable insights into how PETase optimizes its enzymatic performance by balancing stability and flexibility, which may contribute to future PETase design strategies.

NiFe2O4 in MoSe2 Exhibits Bifunctional Water Oxidation and Oxygen Reduction (OER and ORR) Catalytic Reactions for Energy Applications

NiFe₂O₄ in MoSe₂ Exhibits Bifunctional Water Oxidation and Oxygen Reduction (OER and ORR) Catalytic Reactions for Energy Applications

Enhancement of oxygen flux through Nb-doped La0.4Sr0.6FeO3-δ ceramic hollow fiber membranes by Fe exsolution

In recent years, numerous studies have focused on the use of mixed ionic-electronic conducting oxides for coupled oxygen separation and catalytic reactions in membrane reactors. A promising strategy for the efficient fabrication of oxygen separation membranes involves modification of the membrane surface via exsolved metal nanoparticles decoration. Here, we present a detailed characterization of the structural and transport properties of a novel membrane material La0.4Sr0.6Fe0.95Nb0.05O3−δ (LSFNb5). The exsolution of Fe nanoparticles was observed after heating of LSFNb5 in a reducing atmosphere (5 % Н2/Ar) and was confirmed by X-ray diffraction analysis, Mössbauer spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. The formation of Fe nanoparticles on the surface of LSFNb5 hollow fiber membrane in the reduction process leads to the enhancement of oxygen fluxes and reduces the apparent activation energy. Kinetic parameters for oxygen transport through LSFNb5 hollow fiber membrane estimated using two different models, are in good agreement with the experimental results. Furthermore, LSFNb5 hollow fiber membrane demonstrates stable performance both before and after surface treatment.

Efficient Encapsulation of β-Lapachone into Self-Immolative Polymer Nanoparticles for Cyclic Amplification of Intracellular Reactive Oxygen Species Stress.

The selective upregulation of intracellular oxidative stress in cancer cells presents a promising approach for effective cancer treatment. In this study, we report the integration of enzyme catalytic amplification and chemical amplification reactions in β-lapachone (Lap)-loaded micellar nanoparticles (NPs), which are self-assembled from reactive oxygen species (ROS)-responsive self-immolative polymers (SIPs). This integration enables cyclic amplification of intracellular oxidative stress in cancer cells. Specifically, we have developed ROS-responsive SIPs with phenylboronic ester triggering motifs and hexafluoroisopropanol moieties in the side chains, significantly enhancing Lap loading efficiency (98%) and loading capacity (33%) through multiple noncovalent interactions. Upon ROS activation in tumor cells, the Lap-loaded micellar NPs disassemble, releasing Lap and generating additional ROS via enzyme catalytic amplification. This process elevates intracellular oxidative stress and triggers polymer depolymerization in a positive feedback loop. Furthermore, the degradation of SIPs via chemical amplification produces azaquinone methide intermediates, which consume intracellular thiol-related substrates, disrupt intracellular redox hemostasis, further intensify oxidative stress, and promote cancer cell apoptosis. This work introduces a strategy to enhance intracellular oxidative stress by combining enzymatic and chemical amplification reactions, providing a potential pathway for the development of highly efficient anticancer agents.

Exploring single-entity electrochemistry beyond conventional potential windows: mechanistic insights into hydrazine/hydrazinium ion oxidation.

Single-entity electrochemistry (SEE) enables research into the electrochemical properties of nanoparticles (NPs) at the individual NP level. Recent studies on active particle-active electrode systems have expanded the scope of SEE measurements, moving beyond the limitations of inert electrode-based methods that rely on distinct NP-electrode catalytic differences, thereby enhancing mechanistic understanding of catalytic reactions. In this study, we investigated SEE signals from Pt NPs colliding with Au ultramicroelectrodes (UME) at elevated potentials where both Pt and Au UME exhibit electrocatalytic activity. Under conditions where Au UME is activated for hydrazine oxidation, distinctive combined spike and staircase current responses were observed. SEE signals exhibited varied shapes depending on pH and hydrazine concentration. Analyzing these variations provided insights into changes in reaction mechanisms according to pH and hydrazine concentration.

Electrochemical detection of quercetin at a Pt nanoaggregate-decorated Ti3C2-modified electrode

The surface chemical state of the electrode modification material, particularly crystal defects, significantly affects electrochemical detection properties. In this study, Ti3C2 decorated by Pt nanoaggregates (Pt NAs-Ti3C2) with enhanced crystal defect was developed for quercetin detection, where Pt nanoaggregates on Ti3C2 exhibit improved dispersibility and smaller particle size, generating a more favorable environment for interfacial catalytic reactions. A large specific surface area, the Pt NAs-Ti3C2 composite is beneficial for the adsorption and transfer of quercetin on the electrode surface. In comparison to Pt nanoaggregates with complete crystals, the Pt NA-Ti3C2-modified glassy carbon electrode (Pt NA-Ti3C2/GCE) demonstrates superior quercetin detection capabilities, achieving a detection sensitivity of 72.3 μA μM−1 and an outstanding detection linear region of 0.1–1500 nM. Besides, the electrode showcases excellent reproducibility with RSD of 2.41 %, repeatability with RSD of 1.08 %, and long-term stability with 92.3 % of the original signal retained, and resistance to interference, achieving accurately and selectively quercetin detection even in the presence of other ions and compounds. In addition, the Pt NA-Ti3C2/GCE allows for precise quercetin detection in real-life samples. Our findings establish a theoretical guideline and furnish the material foundation for the development of high-performance electrochemical sensors.

Tantalum Catalyzed Hydroaminoalkylation Enables a Telescoping Catalytic Reaction Sequence for the Synthesis of Benzoannulated Indolizidines and Quinolizidines

Tantalum Catalyzed Hydroaminoalkylation Enables a Telescoping Catalytic Reaction Sequence for the Synthesis of Benzoannulated Indolizidines and Quinolizidines

Lactonization of Diols Over Highly Efficient Metal-Based Catalysts.

Lactones has gained increasing attention in recent years due to wide application in polymer and pharmaceutical industries. Traditional synthetic methods of lactones often involve harsh operating temperature, use of strong alkalis and toxic oxidants. Therefore, lactonization of diols under milder conditions have been viewed as the most promising route for future commercialization. A variety of metal catalysts (Ru, Pt, Ir, Au, Fe, Cu, Co, and Zn) have been developed for highly efficient oxidant-, acceptor-, base- and additive-free lactonization processes. However, only a few initial attempts have been reported with no further details on catalytic mechanism being disclosed in literature. There demands a systematic study of the mechanistic details and the structure-function relationship to guide the catalyst design. In this work, we critically reviewed and discussed the structure-function relationship, the catalytic reaction mechanism, the catalyst stability, as well as the effect of oxidant and solvent for lactonization of diols. This work may provide additional insights for the development of other oxygen-containing functional molecules for material science and technologies.

Preparation of iron selenide decorated 1T/2H molybdenum disulfide catalysts for peroxymonosulfate activation: Effect of phase transition

The sulfate radical-based advanced oxidation process is recognized as an effective approach for acetaminophen (ACT) degradation. Modification of MoS2 through phase engineering can contribute to enhancing peroxymonosulfate (PMS) activation performance. In this work, we decorated MoS2 with FeSe2, aiming to alter the 1T/2H phase ratio of MoS2. Experiments and calculations suggested that the incorporation of FeSe2 increases the activation pathway through the Fe(III)/Fe(II) cycle and prompts a phase transition from 2H to 1T, providing active sites and boosting charge transfer between FeSe2 and MoS2. The optimum catalyst (FeSe2@MoS2-10) showed high efficiency in PMS activation, achieving complete removal of ACT within 20 min. The pseudo-first-order rate constant (kapp) on this catalyst is 17.7 times higher than that of the MoS2/PMS system. This study provides a new direction for promoting phase transition and improving the catalytic reactivity of MoS2-based catalysts, expanding their potential applications in pharmaceutical wastewater treatment.

Remarkable Active Site Utilization in Edge-Hosted-N Doped Carbocatalysts for Fenton-Like Reaction.

Improving the utilization of active sites in carbon catalysts is significant for various catalytic reactions, but still challenging, mainly due to the lack of strategies for controllable introduction of active dopants. Herein, a novel "Ar plasma etching-NH3 annealing" strategy is developed to regulate the position of active N sites, while maintaining the same nitrogen species and contents. Theoretical and experimental results reveal that the edge-hosted-N doped carbon nanotubes (E-N-CNT), with only 0.29 at.% N content, show great affinity to peroxymonosulfate (PMS), and exhibit excellent Fenton-like activity by generating singlet oxygen (1O2), which can reach as high as 410 times higher than the pristine CNT. The remarkable utilization of edge-hosted nitrogen atom is further verified by the edge-hosted-N enriched carbocatalyst, which shows superior capability for 4-chlorophenol degradation with a turnover frequency (TOF) value as high as 3.82 min-1, and the impressive TOF value can even surpass those of single-atom catalysts. This work proposes a controllable position regulation of active sites to improve atom utilization, which provides a new insight into the design of excellent Fenton-like catalysts with remarkable atom utilization efficiency.

Visible-Light-Mediated, Organophotocatalytic C-H Thiocyanation of Pyrazolo[1,5-a]pyrimidines.

Herein, we report a metal-free, organophotoredox-catalyzed sustainable C-H thiocyanation of a biologically active class of N-heterocycles, pyrazolo[1,5-a]pyrimidines, with potassium thiocyanate (KSCN) using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst (PC) and molecular oxygen as the terminal oxidant under blue-light-emitting diode irradiation at room temperature. The developed catalytic protocol features mild reaction conditions, a broad substrate scope, a high yield of products, and a straightforward scalability. Mechanistic studies revealed a radical pathway involving reductive quenching of the PC by KSCN.

Enhancing Compatibility of Two-Step Tandem Catalytic Nitrate Reduction to Ammonia Over P-Cu/Co(OH)2.

Electrochemical nitrate reduction reaction (NO3RR) is a promising approach to realize ammonia generation and wastewater treatment. However, the transformation from NO3 - to NH3 involves multiple proton-coupled electron transfer processes and by-products (NO2 -, H2, etc.), making high ammonia selectivity a challenge. Herein, a two-phase nanoflower P-Cu/Co(OH)2 electrocatalyst consisting of P-Cu clusters and P-Co(OH)2 nanosheets is designed to match the two-step tandem process (NO3 - to NO2 - and NO2 - to NH3) more compatible, avoiding excessive NO2 - accumulation and optimizing the whole tandem reaction. Focusing on the initial 2e- process, the inhibited *NO2 desorption on Cu sites in P-Cu gives rise to the more appropriate NO2 - released in electrolyte. Subsequently, P-Co(OH)2 exhibits a superior capacity for trapping and transforming the desorbed NO2 - during the latter 6e- process due to the thermodynamic advantage and contributions of active hydrogen. In 1m KOH + 0.1m NO3 -, P-Cu/Co(OH)2 leads to superior NH3 yield rate of 42.63mgh- 1cm- 2 and NH3 Faradaic efficiency of 97.04% at -0.4V versus the reversible hydrogen electrode. Such a well-matched two-step process achieves remarkable NH3 synthesis performance from the perspective of optimizing the tandem catalytic reaction, offering a novel guideline for the design of NO3RR electrocatalysts.

Enhanced Fenton-like process on Co9S8 catalyst with Mixed-Valence Cobalt(0)/Cobalt(Ⅱ)

Peroxymonosulfate (PMS)-based Fenton-like reactions have great potential to revolutionize wastewater treatment, but achieving highly efficient decontamination at low chemical input remains extremely challenging. In this study, a carbon carrier-supported Co9S8 catalyst with Mixed-Valence Cobalt(0)/Cobalt(Ⅱ) was prepared, which enables 70.72 % PMS decomposition-rate and complete, highly efficient tetracycline (TC) removal. Through the cyclic conversion pathways of polyvalent cobalt and the auto-decomposition of PMS, which produced SO4•-, 1O2, •OH, and high-valence metals, the material’s efficiency in degrading TC through PMS activation was effectively enhanced (99.92 %). S2-, as one of the active sites, not only promotes the participation of Co3+/Co2+/Co0 in the generation of reactive oxygen species but also significantly facilitates electron transfer to further increase the catalytic reaction rate. Through metal-chelating agents, it is illustrated that Co2+ directly activates PMS to produce reactive oxygen species (ROS), while Co3+ promotes cycling. The normalized kinetic constant of Co9S8/Co-C (105.6 min−1M−1) was even four times larger than that of Co9S8 (26.4 min−1M−1). Co9S8/Co-C exhibited rapid degradation over a wide pH range and extensive cycling experiments, demonstrating its versatility and stability in various environments. Possible degradation pathways were speculated using liquid chromatography-mass spectrometry (LC-MS). Toxicological evaluations and mung bean germination toxicity tests indicated that the Co9S8/Co-C+PMS system effectively reduced toxicity. It enables the complete degradation of TC while remarkably reducing the toxic intermediates, ensuring that the catalyst is suitable for wastewater treatment applications.

A C-modified engineering strategy of porous In2O3 catalysts for point-concentrated solar-driven photothermal CO2 hydrogenation

The solar-driven photothermal CO2 conversion serves as an effective approach for addressing the substantial challenges of energy crises and global environmental issues. In this work, various forms of In2O3 catalysts, including In2O3-c, In2O3-r, In2O3-s, and porous spherical In2O3, along with a C-modified porous spherical In2O3 catalyst (C-In2O3), were successfully synthesized through a hydrothermal method. An in-depth analysis was conducted to evaluate the performance of these catalysts in the point-concentrated solar-driven photothermal CO2 hydrogenation. As a result, the porous C-In2O3 catalyst exhibited a superior CO2 conversion rate of approximately 13.2 % under simulated sunlight irradiation, with a light intensity of 44.6 mW/cm2. Notably, all catalysts demonstrated nearly 100 % selectivity towards CO (CO production rate of around 8.51 mmol gcat−1h−1) during the photothermal catalytic reaction, without any formation of CH4. The outstanding performance of the C-In2O3 catalyst was attributed to the modification of In2O3 band structure by the incorporation of C, which significantly enhanced the intensive solar light absorption of the catalyst. Furthermore, incorporating C into In2O3 substantially augments its basic strength and significantly elevates the quantity of basic sites, thereby endowing it with outstanding CO2 adsorption and conversion capabilities. This work provides a C-modified engineering strategy to design efficient photothermal catalysts for boosting point-concentrated photothermal CO2 hydrogenation.

Rigid Ligand Confined Synthesis of Carbon Supported Dimeric Fe Sites with High-performance Oxygen Reduction Reaction Activity for Quasi-solid-state Rechargeable Zn-air Batteries.

Dimeric metal sites (DiMSs) in carbon-based single atom catalysts (SACs) offer distinct advantages in optimizing the adsorption energies of the catalytic intermediates and reaction pathways over single atom sites, and thus inspires the investigations on the rational design of DiMSs-based SACs and the accurate discernment of catalytic mechanisms. Here, dimeric Fe sites on carbon blacks (DiFe-N/CBs) are prepared using the precursor of metal-organic complex with a controlled structure, and the rigid ligand confinement secures the preservation of dimeric Fe sites during the thermal treatment. DiFe-N/CBs shows excellent electrocatalytic performance for oxygen reduction reaction (ORR) with a positive half-wave potential of 0.917 V, and excellent durability with negligible activity decay. Theoretical studies reveal that the dimeric Fe sites have an optimal adsorption of OOH* with the Yeager-type binding, illustrating the advantages of DiMSs over SAs in catalyzing ORR. The rechargeable aqueous and quasi-solid-state Zn-air battery assembled using DiFe-N/CBs-based air cathodes achieve small voltage gaps after long term charge/discharge test, showing great promises for practical applications. This synthetic strategy serves a novel platform to produce a scope of catalysts incorporating multimeric metal sites, and studies on the catalytic mechanism lay the foundation for establishing cooperative effect for multidentate adsorption reactions.

Rigid Ligand Confined Synthesis of Carbon Supported Dimeric Fe Sites with High‐performance Oxygen Reduction Reaction Activity for Quasi‐solid‐state Rechargeable Zn‐air Batteries

Dimeric metal sites (DiMSs) in carbon‐based single atom catalysts (SACs) offer distinct advantages in optimizing the adsorption energies of the catalytic intermediates and reaction pathways over single atom sites, and thus inspires the investigations on the rational design of DiMSs‐based SACs and the accurate discernment of catalytic mechanisms. Here, dimeric Fe sites on carbon blacks (DiFe‐N/CBs) are prepared using the precursor of metal‐organic complex with a controlled structure, and the rigid ligand confinement secures the preservation of dimeric Fe sites during the thermal treatment. DiFe‐N/CBs shows excellent electrocatalytic performance for oxygen reduction reaction (ORR) with a positive half‐wave potential of 0.917 V, and excellent durability with negligible activity decay. Theoretical studies reveal that the dimeric Fe sites have an optimal adsorption of OOH* with the Yeager‐type binding, illustrating the advantages of DiMSs over SAs in catalyzing ORR. The rechargeable aqueous and quasi‐solid‐state Zn‐air battery assembled using DiFe‐N/CBs‐based air cathodes achieve small voltage gaps after long term charge/discharge test, showing great promises for practical applications. This synthetic strategy serves a novel platform to produce a scope of catalysts incorporating multimeric metal sites, and studies on the catalytic mechanism lay the foundation for establishing cooperative effect for multidentate adsorption reactions.

Hierarchical Bi2Fe4O9/BiOI S-scheme heterojunctions with exceptional hydraulic shear induced photo-piezoelectric catalytic activity

Hierarchical Bi2Fe4O9/BiOI S-scheme nanoflower heterostructures are prepared by hydrothermal method, which exhibit exceptional photo-piezoelectric catalytic performance. The tight binding between the sheets ensures the efficient electron transport, and provides a large interface area and adequate reaction sites for photo-piezoelectric catalytic reactions. At the same time, because the water flow in the water body produces hydraulic shear force on the material, the material produces piezoelectric effect. Bi2Fe4O9/BiOI exhibit a remarkable degradation efficiency of 99.4% for tetracycline and a hydrogen production rate of 4089.36 µmol h−1 g−1. The observed behavior can be explained by the combined influence of the formation of S-scheme structure and the process of photo-piezoelectric catalysis, confirmed by in-situ XPS, transient/steady-state fluorescence and piezoelectric response force test. The excellent stability of the material suggests its possible use in the sectors of energy and environment. This work introduces novel concepts for the future advancement of photo-piezoelectric synergistic catalysis.

Ir(III)-Catalyzed Tandem Annulation of Aromatic Amides with 1,6-Diynes via Dual C-H Bond Activation.

An Ir(III)-catalyzed annulation of aryl amides with 1,6-diynes via ortho- as well as meta-dual C-H bond activation reaction is reported. The scope of the annulation reaction was examined with various substituted aryl amides, as well as 1,6-diynes. In this protocol, 1,6-diynes exhibit diverse reactivity compared with internal alkynes. It is important to note that the three C-C bond formation takes place consecutively via ortho followed by meta-dual C-H bond annulation by using a weak chelating group in one pot. A possible catalytic reaction mechanism was proposed to account for the annulation reaction.