Advances In Catalysis Research Articles

Thermally Stable High-Entropy Layered Double Hydroxides for Advanced Catalysis.

Layered double hydroxides (LDHs), especially high-entropy LDHs (HE-LDHs), have gained increasing attention. However, HE-LDHs often possess poor thermal stability, restricting their applications in thermo-catalysis. Herein, a novel complexing nucleation method is proposed for engineering HE-LDHs with enhanced thermal stability. This approach precisely controls the nucleation of metal ions with different solubility products, achieving homogeneous nucleation and effectively mitigating phase segregation and transformation at elevated temperatures. The prepared HE-LDH sample demonstrated exceptional thermal stability at temperatures up to 300°C, outperforming all previously reported LDHs. Importantly, these HE-LDHs preserve both Lewis and Brønsted acidic sites, enabling the 100% removal of aromatic sulfides and alkaline nitrogen compounds from fuel oils in thermo-catalytic oxidation reactions. Experimental and characterization findings reveal that the metal-hydroxide bonds in the prepared HE-LDHs are strengthened by associated hydroxyl groups, inducing negative thermal expansion and augmenting the presence of acidic sites, thereby ensuring structural stability and enhancing catalytic activity. This study not only proposes a strategy for engineering HE-LDHs with remarkable thermal stability but also highlights potential applications of LDHs in thermo-catalysis.

Breaking the Conversion-Selectivity Trade-Off in Methanol Synthesis from CO2 Using Dual Intimate Oxide/Metal Interfaces.

The selective hydrogenation of carbon dioxide (CO2) to value-added chemicals, e.g., methanol, using green hydrogen retrieved from renewable resources is a promising approach for CO2 emission reduction and carbon resource utilization. However, this process suffers from the competing side reaction of reverse water-gas shift (RWGS) and methanol decomposition, which often leads to a strong conversion-selectivity trade-off and thus a poor methanol yield. Here, we report that InOx coating of PdCu bimetallic nanoparticles (NPs) to construct intimate InOx/Cu and InOx/PdIn dual interfaces enables the break of conversion-selectivity trade-off by achieving ∼80% methanol selectivity at ∼20% CO2 conversion close to the thermodynamic limit, far superior to that of conventional metal catalysts with a single active metal/oxide interface. Comprehensive microscopic and spectroscopic characterization revealed that the InOx/PdIn interface favors the activation of CO2 to formate, while the adjacent InOx/Cu interface readily converts formate intermediates to methoxy species in tandem, which thus cooperatively boosts methanol production. These findings of dual-interface synergies via oxide coating of bimetallic NPs open a new avenue to the design of active and selective catalysts for advanced catalysis.

Advanced Catalysis for Green Fuel Production from Biomass and Wastes

Advanced Catalysis for Green Fuel Production from Biomass and Wastes

Charge-Transfer Complexes: Fundamentals and Advances in Catalysis, Sensing, and Optoelectronic Applications.

Supramolecular assemblies, formed through electronic charge transfer between two or more entities, represent a rich class of compounds dubbed as charge-transfer complexes (CTCs). Their distinctive formation pathway, rooted in charge-transfer processes at the interface of CTC-forming components, results in the delocalization of electronic charge along molecular stacks, rendering CTCs intrinsic molecular conductors. Since the discovery of CTCs, intensive research has explored their unique properties including magnetism, conductivity, and superconductivity. Their more recently recognized semiconducting functionality has inspired recent developments in applications requiring organic semiconductors. In this context, CTCs offer a tuneable energy gap, unique charge-transport properties, tailorable physicochemical interactions, photoresponsiveness, and the potential for scalable manufacturing. Here, an updated viewpoint on CTCs is provided, presenting them as emerging organic semiconductors. To this end, their electronic and chemical properties alongside their synthesis methods are reviewed. The unique properties of CTCs that benefit various related applications in the realms of organic optoelectronics, catalysts, and gas sensors are discussed. Insights for future developments and existing limitations are described.

Pinning-effect single-atom NiCo alloy embedded graphene-aerogel in electro-fenton process for rapid degradation of emerging contaminants

Inspired by the growing development of dual single-atom catalysts (SACs), a bimetallic single-atom alloy (SAA) based macro-assembled graphene aerogel (MAGA) was synthesized in this study. The single-atom NiCo alloy-based graphene aerogel (i.e., NiCo/GO aerogel) with pinning effect was used as a sustainable cathode material in an in-situ H2O2 generation system (i.e., electro-Fenton (EF) process). The atomic structure of NiCo/GO aerogel was identified by the combined microscopic and spectroscopic techniques. The SAA cathode exhibited a remarkable catalytic activity towards the two-electron-dominated oxygen reduction reaction (ORR) with the EF process for wastewater treatment. The energy consumption was calculated to be around 0.660 kW·h/t for treatment of water containing 2 mg L−1 ibuprofen (IBU). Density functional theory (DFT) analysis revealed the specific roles of the dual-functional NiCo SAA in the GO aerogel cathode, i.e., the Co sites more preferentially adsorb O2 molecules for H2O2 generation while the Ni sites function as the active sites for H2O2 dissociation and activation. The research findings shed light on the controlled synthesis of SAAs for advanced catalysis and its potential application in the treatment of emerging organic contaminants for water safety and pollution control.

Value‐Added Cascade Synthesis Mediated by Paired‐Electrolysis Using an Ultrathin Microenvironment‐Inbuilt Metalized Covalent Organic Framework Heterojunction

AbstractEnergy‐saving and value‐added management in advanced catalysis is highly desirable but is challenged by the limitations of multifunctional catalysts and catalytic modules. Herein, an azo‐linked phthalocyanine‐porphyrin covalent organic framework (COF) with the ultrathin layered nanostructure grown on carbon nanotubes (NiPc‐azo‐H2Pp@CNTs) has been designed and synthesized, which can serve as a highly active and stable bifunctional heterojunction electrocatalyst for selective paired‐electrosynthesis through coupling anodic iodide oxidation reaction and cathodic CO2 conversion. Particularly, the inbuilt local microenvironment conferred by the dihydroporphyrin moieties in COF can act as a proton reservoir to promote the proton relay at the heterojunction interface during the electrocatalytic process. Moreover, through the cascade construction of dual electrocatalytic/organocatalytic modules, the cathode‐generated CO can be further converted to dimethyl carbonate with a yield of 6.21 mmol L−1 h−1, while the anode‐produced iodine can be derived into iodoform on the hundred‐milligram scale. It is worth noting that the value‐added cascade synthesis mediated by paired‐electrolysis using the distinctive and high‐powered electrocatalysts will help advance the sustainable development of industrial intelligent manufacturing.

Versatile Synthesis of Nanofoams through Femtosecond Pulsed Laser Deposition

Nanofoam materials are gaining increasing interest in the scientific community, thanks to their unique properties such as ultralow density, complex nano‐ and microstructure, and high surface area. Nanofoams are attractive for multiple applications, ranging from advanced catalysis and energy storage to nuclear fusion and particle acceleration. The main issues hindering the widespread use of nanofoams are related to the choice of synthesis technique, highly dependent on the desired elemental composition and leading to a limited control over the main material properties. Herein, femtosecond pulsed laser deposition is proposed as a universal tool for the synthesis of nanofoams with tailored characteristics. Nanofoams made by elements with significantly different properties—namely, boron, silicon, copper, tungsten, and gold—can be produced by suitably tuning the deposition parameters. The effect of the background pressure is studied in detail, in relation to the morphological features and density of the resulting nanofoams and nanostructured films. This, together with the analysis of the specific features shown by nanofoams made of different elements, offers fresh insights into the aggregation process and its relation to the corresponding nanofoam properties down to the nanoscale, opening new perspectives toward the application of nanofoam‐based materials.

Using the Photo-Piezoelectric Effect of AuPt@BaTiO3 Oxidase Mimetics for Colorimetric Detection of GSH in Serum.

Nanozymes possess major advantages in catalysis and biosensing compared with natural nanozymes. In this study, the AuPt@BaTiO3 bimetallic alloy Schottky junction is prepared to act as oxidase mimetics, and its photo-piezoelectric effect is investigated. The synergy between the photo-piezoelectric effect and the local surface plasmon resonance enhances the directional migration and separation of photogenerated electrons, as well as hot electrons induced by the AuPt bimetallic alloy. This synergy significantly improves the oxidase-like activity. A GSH colorimetric detection platform is developed based on this fading principle. Leveraging the photo-piezoelectric effect allows for highly sensitive detection with a low detection limit (0.225 μM) and reduces the detection time from 10 min to 3 min. The high recovery rate (ranging from 99.91% to 101.8%) in actual serum detection suggests promising potential for practical applications. The development of bimetallic alloy heterojunctions presents new opportunities for creating efficient nanozymes.

Promoted hydrogenation of CO2 to methanol over single-atom Cu sites with Na+-decorated microenvironment.

Although single-atom Cu sites exhibit high efficiency in CO2 hydrogenation to methanol, they are prone to forming Cu nanoparticles due to reduction and aggregation under reaction conditions, especially at high temperatures. Herein, single-atom Cu sites stabilized by adjacent Na+ ions have been successfully constructed within a metal-organic framework (MOF)-based catalyst, namely MOF-808-NaCu. It is found that the electrostatic interaction between the Na+ and Hδ- species plays a pivotal role in upholding the atomic dispersion of Cu in MOF-808-NaCu during CO2 hydrogenation, even at temperatures of up to 275°C. This exceptional stabilization effect endows the catalyst with excellent activity (306 g·kgcat-1·h-1), high selectivity to methanol (93%) and long-term stability at elevated reaction temperatures, far surpassing the counterpart in the absence of Na+ (denoted as MOF-808-Cu). This work develops an effective strategy for the fabrication of stable single-atom sites for advanced catalysis by creating an alkali-decorated microenvironment in close proximity.

Gold Nanoclusters Synthesized within Single-Chain Nanoparticles as Catalytic Nanoreactors in Water.

Metalloenzymes are able to catalyze complex biochemical reactions in cellular (aqueous) media with high efficiency. In recent years, a variety of metal-containing single-chain nanoparticles (SCNPs) have been synthesized as simplified metalloenzyme-mimetic nano-objects. However, most of the metal-containing SCNPs reported so far contained complexed metal ions but not metal nanoclusters (NCs) with diameter <5 nm, which could be used as powerful, emerging catalysts. Herein, we report the synthesis of gold nanoclusters (Au-NCs) within SCNPs and the further use of Au-NCs/SCNPs as catalytic nanoreactors in water. We demonstrate that a common motif contained in several drugs (i.e., the aminophenyl-oxazolidinone fragment present in Rivaroxaban, Sutezolid, and Linezolid) can be efficiently prepared in water from a hydrophobic precursor compound by using the Au-NCs/SCNPs as efficient catalytic nanoreactors. In summary, this work paves the way forthe synthesis of metal-NCs/SCNPs for advanced catalysis in aqueous media.

Tetrazine-Linked Covalent Organic Frameworks With Acid Sensing and Photocatalytic Activity.

The first synthesis and comprehensive characterization of two vinyl tetrazine-linked covalent organic frameworks (COF), TA-COF-1 and TA-COF-2, are reported. These materials exhibit high crystallinity and high specific surface areas of 1323 and 1114 m2 g-1. The COFs demonstrate favorable band positions and narrow band gaps suitable for light-driven applications. These advantages enable TA-COFs to act as reusable metal-free photocatalysts in the arylboronic acids oxidation and light-induced coupling of benzylamines. In addition, these TA-COFs show acid sensing capabilities, exhibiting visible and reversible color changes upon exposure to HClsolution, HCl vapor, and NH3 vapor. Further, the TA-COFs outperform a wide range of previously reported COF photocathodes. The tetrazine linker in the COF skeleton represents a significant advancement in the field of COF synthesis, enhancing the separation efficiency of charge carriers during the photoreaction and contributing to their photocathodic properties. TA-COFs can also degrade 5-nitro-1,2,4-triazol-3-one (NTO), an insensitive explosive present in industrial wastewater, in 20 min in a sunlight-driven photocatalytic process; thus, revealing dual functionality of the protonated TA-COFs as both photodegradation and Brønsted acid catalysts. This pioneering work opens new avenues for harnessing the potential of the tetrazine linker in COF-based materials, facilitating advances in catalysis, sensing, and other related fields.

Borocarbonitride materials as metal-free catalysts for advanced catalysis

Heterogeneous catalysis has been inseparable from the fields of energy-related conversion and organic synthesis, etc. By virtue of the merits of low cost, earth-abundance, and low toxicity, metal-free catalysts, as...

Synergistic dual sites of Zn-Mg on hierarchical porous carbon as an advanced oxygen reduction electrocatalyst for Zn-air batteries.

The development of cost-effective and high-performance non-noble metal catalysts for the oxygen reduction reaction (ORR) holds substantial promise for real-world applications. Introducing a secondary metal to design bimetallic sites enables effective modulation of a metal-nitrogen-carbon (M-N-C) catalyst's electronic structure, providing new opportunities for enhancing ORR activity and stability. Here, we successfully synthesized an innovative hierarchical porous carbon material with dual sites of Zn and Mg (Zn/Mg-N-C) using polymeric ionic liquids (PILs) as precursors and SBA-15 as a template through a bottom-up approach. The hierarchical porous structure and optimized Zn-Mg bimetallic catalytic centers enable Zn/Mg-N-C to exhibit a half-wave potential of 0.89 V, excellent stability, and good methanol tolerance in 0.1 M KOH solution. Theoretical calculations indicated that the Zn-Mg bimetallic sites in Zn/Mg-N-C effectively lowered the ORR energy barrier. Furthermore, the Zn-air batteries assembled based on Zn/Mg-N-C demonstrated an outstanding peak power density (298.7 mW cm-2) and superior cycling stability. This work provides a method for designing and synthesizing bimetallic site catalysts for advanced catalysis.

Synthesis of pyrano-pyrimidines: recent advances in catalysis by magnetically recoverable nanocatalysts

Synthesis of pyrano-pyrimidines: recent advances in catalysis by magnetically recoverable nanocatalysts

Defect-engineered Ni-Fe-LDH with porous flower-like architecture enables boosted advanced oxidation processes: Experimental and theoretical studies

In this paper, oxygen vacancies (VO) enriched flower-like Ni-Fe layered double hydroxide (VO-Ni-Fe-LDH) was prepared for activating peroxymonosulfate (PMS) to remove Tetracycline hydrochloride (TC). Sufficient experimental exploration and density functional theory (DFT) calculations clearly demonstrated the 3D morphology prevented the aggregation of VO-Ni-Fe-LDH and VO alter the electronic state of the surface. Thus, VO-Ni-Fe-LDH/PMS not only showed a 4 times enhancement in the reaction rate constant in comparison to Ni-Fe-LDH/PMS, but also exhibited a stable and efficient performance in continuous flow experiment up to 4.5 h. Quenching test and EPR experiments proved that degradation of TC was dominated by singlet oxygen (1O2), rather than sulfate radicals or hydroxyl radicals found by traditional LDH catalysts. The Chemical intermediates in TC oxidation process were identified through liquid chromatography-mass spectrophotometry, and degradation paths were provided for system optimization. In application, the VO-Ni-Fe-LDH/PMS system was able to withstand the effects of the water matrix, various pH values and remove the contaminants from real hospital wastewater with efficiency. This work emphasized the significance of rational architectural design combined with defect engineering in catalyst development, which holds the potential for advanced catalysis.

Covalent Triazine Framework Nanosheets: Synthesis and Energy Conversion and Storage†

Comprehensive SummaryCovalent triazine framework nanosheets (CTF NSs), an emerging class of two‐dimensional nanomaterials, have received great attention due to their abundant active sites, permanent porosity, molecular structural diversity, superior chemical/thermal stability, and short charge diffusion path, enabling technological breakthroughs in a myriad of applications. The forefront developments and applications of CTF NSs as photocatalysts and electrochemical electrodes have conferred superior performance and made great impact in the field of energy and advanced catalysis. This forward‐looking review aims to summarize the research trends, synthesis, properties of CTF NSs and their CTF counterpart, and highlight their progress in applications with respect to energy storage and conversion devices. Finally, the current challenges and future perspectives for CTF NSs are also presented.

The Identity of Nickel Peroxide as a Nickel Superoxyhydroxide for Enhanced Electrocatalysis.

Nickel peroxides are a class of stoichiometric oxidants that can selectively oxidize various organic compounds, but their molecular level structure remained elusive until now. Herein, we utilized structural prediction using the Stochastic Surface Walking method based on a neural network potential energy surface and advanced characterization using the as-synthesized nickel peroxide to unravel its chemical identity as the bridging superoxide containing nickel hydroxide, or nickel superoxyhydroxide. Superoxide incorporation tunes the local chemical environment of nickel and oxygen beyond the conventional Bode plot, offering a 6.4-fold increase in the electrocatalytic activity of urea oxidation. A volcanic dependence of the activity on the oxygen equivalents leads to the proposed active site of the Ni(OO)(OH)Ni five-membered ring. This work not only unveils the possible structures of nickel peroxides but also emphasizes the significance of tailoring the oxygen environment for advanced catalysis.

Dual-functional single-atomic Mo/Fe clusters–decorated C3N5 via three electron-pathway in oxygen reduction reaction for tandemly removing contaminants from water

Inspired by the development of single-atom catalysts (SACs), the fabrication of multimetallic SACs can be a promising technical approach for the in situ electro-Fenton (EF) process. Herein, dual-functional atomically dispersed Mo-Fe sites embedded in carbon nitride (C3N5) (i.e., MoFe/C3N5) were synthesized via a facile SiO2 template method. The atomically isolated bimetallic configuration in MoFe/C3N5 was identified by combining the microscopic and spectroscopic techniques. The MoFe/C3N5 catalyst on the cathode exhibited a remarkable catalytic activity toward the three electron-dominated oxygen reduction reaction in sodium sulfate, leading to a highly effective EF reaction with a low overpotential for the removal of organic contaminants from wastewater. The new catalyst showed a superior performance over its conventional counterparts, owing to the dual functions of the dual-metal active sites. Density functional theory (DFT) analysis revealed that the dual-functional 50-MoFe/C3N5 catalyst enabled a synergistic action of the Mo-Fe dual single atomic centers, which can alter the adsorption/dissociation behavior and decrease the overall reaction barriers for effective organic oxidation during the EF process. This study not only sheds light on the controlled synthesis of atomically isolated catalyst materials but also provides deeper understanding of the structure-performance relationship of the nanocatalysts with dual active sites for the catalytic EF process. Additionally, the findings will promote the advanced catalysis for the treatment of emerging organic contaminants in water and wastewater.

Hydrogen-bond-acceptor ligands enable distal C(sp3)-H arylation of free alcohols.

The functionalization of C-H bonds in organic molecules is one of the most direct approaches for chemical synthesis. Recent advances in catalysis have allowed native chemical groups such as carboxylic acids, ketones and amines to control and direct C(sp3)-H activation1-4. However, alcohols, among the most common functionalities in organic chemistry5, have remained intractable because of their low affinity for late transition-metal catalysts6,7. Here we describe ligands that enable alcohol-directed arylation of δ-C(sp3)-H bonds. We use charge balance and a secondary-coordination-sphere hydrogen-bonding interaction-evidenced by structure-activity relationship studies, computational modelling and crystallographic data-to stabilize L-type hydroxyl coordination to palladium, thereby facilitating the assembly of the key C-H cleavage transition state. In contrast to previous studies in C-H activation, in which secondary interactions were used to control selectivity in the context of established reactivity8-13, this report demonstrates the feasibility of using secondary interactions to enable challenging, previously unknown reactivity by enhancing substrate-catalyst affinity.

Recent Advances in Catalysis Using Organoborane-Mediated Hydride Abstraction

AbstractC–H functionalization is widely regarded as an important area in the development of synthetic methodology, enabling the design of more time- and atom-efficient syntheses. The ability of electron-deficient organoboranes to mediate hydride abstraction from α-amino C–H bonds is therefore of great interest, as the reactive iminium and hydridoborate moieties generated are able to participate in a range of synthetically useful transformations. In this review, we cover the recent advances made in organoborane-mediated hydride abstraction, and focus on the catalytic applications of electron-deficient boranes in α- or β-functionalization, α,β-difunctionalization, and the dehydrogenation of amines.1 Introduction2 α-Functionalization of Amines3 β-Functionalization of Amines4 α,β-Difunctionalization of Amines5 Dehydrogenation of Amines6 Summary and Future Prospects