Field Of Catalysis Research Articles

Structure and Dissociation of Water at the Electrode-Solution Interface Studied by In Situ Vibrational Spectroscopic Techniques.

In aqueous electrochemistry, water in contact with charged surfaces is ubiquitous and indispensable, dictating the binding of solutes to electrode surfaces as well as the transport process of protons and electrons in the interfacial region. A comprehensive understanding of the structure and dissociation of interfacial water at the molecular level is extremely important yet challenging, given its critical role in various physical, chemical, and biological processes. In situ vibrational spectroscopic techniques serve as a powerful tool for acquiring the molecular structure of electrode surfaces and probing interfacial reaction mechanisms in real time. In this review, we briefly summarize the latest advances in the electric double layer model and the experimental methods employed at the electrode-solution interface. Particular emphasis is placed on in situ vibrational spectroscopic techniques that have unveiled new insights into the molecular structure of interfacial water across diverse electrode surfaces under ambient conditions. And then, it also provides an overview of recent progress on the subtle relationship between the structure of interfacial water and its dissociation activity, aiming to provide novel insights into the fields of electrochemistry, energy and catalysis.

Chiral Spirobipyridine Synthesis by Cobalt‐Catalyzed Enantioselective Double [2 + 2 + 2] Cycloaddition

AbstractChiral spirobiindanes are recognized as the privileged structures in the field of asymmetric catalysis. However, the structurally similar chiral spirobipyridines have not yet been explored as chiral ligands or organocatalysts due to the absence of efficient synthetic methods. Herein, we report a cobalt‐catalyzed enantioselective synthesis of spirobipyridines via double [2 + 2 + 2] cycloaddition reaction. Spirobipyridines with ortho‐ or meta‐substituents could be obtained with exclusive regioselectivity and up to 99% ee in the presence of cobalt and bisoxazolinephosphine ligands. Spirobipyridines coordinate with transition metals as chiral ligands. Spirobipyridine dioxides can be applied as chiral organocatalysts in the asymmetric allylation of aldehydes.

Molecularly Imprinted Polymer-Supported Ceramic Catalysts for Environmental Applications: A Comprehensive Review

Molecularly imprinted polymers (MIPs) are synthetic polymers designed to exhibit selective recognition and binding capabilities toward target molecules and have been widely combined with advanced ceramic-based materials toward better performance in many catalytic applications of interest and beyond. What sets MIPs apart is their molecularly imprinted cavities, which are formed during polymerization in the presence of a template molecule. Upon template removal, these cavities retain the shape, size, and chemical functionality of the template molecule, allowing for highly specific recognition and binding of target molecules. In recent years, there has been a growing interest in leveraging these molecularly imprinted cavities not only for molecular recognition and sensing but also as catalytic sites and supports. Complementary to experimental studies, density functional theory (DFT) calculations are increasingly used to elucidate the molecular interactions, catalytic mechanisms, and optimize the design of MIP–ceramic catalysts. This review aims to provide a comprehensive overview of the current state of research on advanced ceramic-based catalysts supported by MIPs for environmental applications. Additionally, the review will discuss challenges and future directions in the field, focusing on enhancing the catalytic efficiency, stability, and scalability of MIP-based ceramic catalysts. By exploring these aspects, this review seeks to illustrate the promising role of MIP-modified ceramic materials in advancing the field of catalysis and catalytic supports.

Perovskite Materials for Efficient Utilization of Thermal Energy

ABSTRACTGlobal warming is the primary concern of the world because it results in environmental damage and eventually causes serious effects on human health. Thermal energy storage and conversion systems can be opted to reduce the temperature hike caused by global warming and make effective transformation of thermal waste into electricity. Thermochemical energy storage system (TCES) show high energy density, wide operating temperature, and long‐term durability whereas thermoelectric (TE) materials are capable of doing efficient conversion of thermal energy into electricity. TCES are prominent energy storage system that offers significant heat storage capacity with minimal thermal losses. Furthermore, it reduces the greenhouse effect to sustain environment‐friendly conditions. TE systems have fairly dominant over conventional electric generators in terms of light weight, low noise pollution, small volume, and easy maintenance that could be better for thermal energy application. Perovskite materials have shown potential to be used for both TCES and TE application owing to their chemical flexibility and structural and thermal stability. They also possess tunable redox properties, high oxidation resistance and low cost. Perovskite materials are unique because of their ability to accommodate large cations of rare‐earth elements among close packed oxides. The structure of perovskites indulges partial substitution of almost all the elements on both cationic sites. They exhibit unique characteristics features such as tilt of octahedral complexes, off‐centering of octahedrally coordinated cations, and distortion of octahedral cage. The available oxygen vacancies in pervoskite compounds commence ionic transport that provides fast redox kinetics and better rate of energy storage capability. Perovskites display multiple applications in the field of electronics, geophysics, nuclear, optics, optoelectronics, environment, solar cells, catalysis, and thermal energy. In this review, the recent developments and optimization of perovskite materials for TCES and TE application are presented. Many of perovskite oxides and halides exhibit excellent performance under practical operating conditions. Recent works on complex perovskite systems for thermoelectricity and their future perspectives are highlighted. The role of perovskite compounds for efficient utilization of thermal energy has been extended and discussed. Finally, strategic approaches to improve TCES and TE parameters are emphasized.

Ionic liquid-assisted stabilization of MXene in polysaccharide-chitosan hydrogels with mechanical enhancement for catalytic and sensor applications.

Ionic liquid-assisted stabilization of MXene in polysaccharide-chitosan hydrogels with mechanical enhancement for catalytic and sensor applications.

Polymer-induced self-assembly strategy toward 3D printable porous MoO3/Al2O3 catalyst for efficient oxidative desulfurization.

Polymer-induced self-assembly strategy toward 3D printable porous MoO3/Al2O3 catalyst for efficient oxidative desulfurization.

Mn-N5 structure between poly-porphyrin manganese and 3D N-doped graphene to enhance bifunctional oxygen catalytic performance.

Mn-N5 structure between poly-porphyrin manganese and 3D N-doped graphene to enhance bifunctional oxygen catalytic performance.

Chiral Spirobipyridine Synthesis by Cobalt-Catalyzed Enantioselective Double [2+2+2] Cycloaddition.

Chiral spirobiindanes are recognized as the privileged structures in the field of asymmetric catalysis. However, the structurally similar chiral spirobipyridines have not yet been explored as chiral ligands or organocatalysts due to the absence of efficient synthetic methods. Herein, we report a cobalt-catalyzed regiodivergent and enantioselective synthesis of spirobipyridines via double [2+2+2] cycloaddition reaction. Spirobipyridines with ortho- or meta-substituents could be obtained with exclusive regioselectivity and up to 99% ee in the presence of cobalt and bisoxazolinephosphine ligands. Spirobipyridines coordinate with transition metals as chiral ligands. Spirobipyridine dioxides can be applied as chiral organocatalysts in the asymmetric allylation of aldehydes.

A mini review on revolutionizing hydrogenation catalysis: unleashing transformative power of artificial intelligence.

The field of hydrogenation catalysis has undergone a revolution due to the application of artificial intelligence (AI) and machine learning (ML), which have opened up new avenues for improving catalyst design, reaction efficiency, and pathway optimization. Trial-and-error techniques are a major component of traditional catalyst discovery methods, and they can be resource and time-intensive when it comes to real-world applications. On the other hand, real-time reaction condition optimization, predictive modelling, and quicker catalyst screening are made possible by AI-based techniques. Using methods like neural networks, Bayesian optimization, and generative models, this paper emphasizes how artificial intelligence has been revolutionizing catalyst creation along with mechanistic knowledge and process intensification. AI has the ability to completely transform catalytic research, as demonstrated by a number of case studies that demonstrate its use in CO₂ hydrogenation, biomass upgrading, and metal catalyzed reactions. This review synthesizes recent developments in AI-enhanced catalytic modelling, kinetic parameter estimation, and multi-scale reaction simulations and explores machine learning models such as Random Forest, Gradient Boosting, Artificial Neural Networks, and Gaussian Processes to predict key catalytic performance indicators. Additionally, high-throughput simulated screening and computational methods such as Density Functional Theory simulations and molecular descriptor-based modelling have been used to improve catalyst design tactics. Summary of the ML models which were trained and validated using open source frameworks such as scikit-learn, TensorFlow, and PyTorch is also presented in this paper. Most of the research studies datasets were using the resource data from Catalysis Hub and the materials project. Techniques for data processing and pre-processing include methods for choosing the component features, such as d-band center analysis, adsorption energy calculations, and algorithm normalization. This review study consists of an in-depth analysis of how data-driven modelling improves catalyst performance, and its prediction and optimization in hydrogenation catalysis reactions by artificial intelligence and machine learning driven approaches.

Dynamic Kinetic Asymmetric Hydroacylation: Racemization by Soft Enolization.

We report a dynamic kinetic asymmetric transformation (DyKAT) of racemic aldehydes by Rh-catalyzed hydroacylation of acrylamides. This intermolecular hydroacylation generates 1,4-ketoamides with high enantio- and diastereoselectivity. DFT and experimental studies provide mechanistic insights and reveal an unexpected Rh-catalyzed pathway for aldehyde racemization. Our study represents a pioneering kinetic resolution by intermolecular hydroacylation and contributes to the growing field of stereoconvergent catalysis featuring C-C bond construction.

Recent Advances in Stereoselective Synthesis of Amino‐Phosphine Oxides

AbstractChiral amino‐phosphines and amino‐phosphine oxides have garnered significant attention due to their unique biological properties and widespread applications as chiral ligands and organocatalysts in asymmetric catalysis. The importance of these compounds is underscored by the growing interest in developing various stereoselective synthetic methods to access chiral α‐, β‐, and γ‐aminophosphine and phosphine oxides. This review provides a comprehensive overview of the advances in stereoselective synthesis of chiral α‐, β‐, and γ‐aminophosphine oxides from 1999 to 2025, highlighting key developments and their implications in the field of asymmetric catalysis.

Potential-Driven Dynamic Spring-Effect of Pd─Cu Dual-Atoms Empowered Stability and Activity for Electrocatalytic Reduction.

Atomic-level catalysts are extensively applied in heterogeneous catalysis fields. However, it is a general but ineluctable issue that active metal atoms may migrate, aggregate, deactivate, or leach during reaction processes, suppressing their catalytic performances. Designing superior intrinsic-structural stability of atomic-level catalysts with high activity and revealing their dynamic structure evolution is vital for their wide applications in complex reactions or harsh conditions. Herein, high-stable Pd─Cu dual-atom catalysts with PdN3─CuN3 coordination structure are engineered via strong chelation of Cu2+-ions with electron pairs from palladium-source, achieving the highest turnover frequency under the lowest overpotential for Cr(VI) electrocatalytic reduction detection in strong-acid electrolytes. In situ X-ray absorption fine structure spectra reveal dynamic "spring-effect" of Cu─Pd and Cu─N bonds that are reversibly stretched with potential changes and can be recovered at 0.6V for regeneration. The modulated electron-orbit coupling effect of Pd─Cu pairs prevents Cu-atoms from aggregating as metallic nanoparticles. Pd─Cu dual-atoms interact with two O atoms of H2CrO4, forming stable bridge configurations and transferring electrons to promote Cr─O bond dissociation, which prominently decreases reaction energy barriers. This work provides a feasible route to boost the stability and robustness of metal single-atoms that are easily affected by reaction conditions for sustainable catalytic applications.

Orientation of Nonspherical Nanoparticles in Ordered Block Copolymer for Functional Materials.

In the fields of controllable catalysis, electromagnetic field manipulation, and nanoscience, mediated self-assembly has become a key method for controlling the orientation of nonspherical nanoparticles. The ordered structures formed by block copolymer self-assembly can provide an orientation matrix for nonspherical nanoparticles. Based on self-consistent field theory, this study investigates the orientation effects of monaxially symmetric cylindrical nanoparticles in the lamellar phases formed by block copolymers. Using cylindrical and pore-containing ring nanoparticles as models for nonspherical particles, we successfully describe the particles' anisotropy and nonconvex surface properties. Numerical results show that the orientation effect of the lamellar ordered structure exhibits a nontrivial dependence on the geometric and topological properties of nonspherical particles. In addition to interfacial tension effects, the orientation mechanism of small-sized nanoparticles mainly arises from the stretching effect of the polymer, manifested in two main effects: (1) the particle deforms the polymer chain, reducing its conformational entropy, thus tending to align in a specific orientation; (2) the orientation field at the polymer chain ends is discontinuous, and the nanoparticles can embed and adopt a specific orientation. For nonconvex nanoparticles, the geometric size of the pore structure adjusts the polymer's free volume, influencing the orientation effect. This study not only deepens the understanding of the orientation mechanism in block copolymer-mediated nanoparticle self-assembly, but also provides potential theoretical insights for the design and application of energy catalysis, biomedical materials, and functional nanostructures.

A charge calibration strategy for describing the charge transfer during the electrochemical elementary step.

Constant potential modeling of electrocatalytic processes remains a significant challenge in the field of computational catalysis, primarily due to the difficulty in simultaneously considering the influence of constant potential conditions, explicit solvent environment, and the double-layer structure. In this work, we propose a charge calibration strategy for electrocatalytic processes. This strategy accounts for charge transfer in systems with explicit solvation and ions during constant-potential free energy modeling. In our strategy, interfacial counter-ions are employed to model the Helmholtz layer and determine the surface charge density, which defines the electrode potential. During the simulation of electrochemical reactions, extra charges are introduced/extracted to/from the system to compensate for electron transfer between the electrode and the reaction species and keep a constant surface charge density along the reaction profile. Our method showcases the impact of potential-dependent solvent reorganization on reaction kinetics and underscores the importance of constant potential kinetics. We anticipate that the strategy presented here will inspire further theoretical and experimental studies for electrochemistry interfaces.

Magnetically Induced Catalysis: Definition, Advances, and Potential.

The rapidly growing importance of electrification in the chemical industry opens room for disruptive innovations regarding energy input into catalytic processes. Energy efficiency and dynamics of renewable energy supplies represent important challenges, but the design of catalytic systems to cope with such new frameworks may also stimulate the discovery of new catalyst materials and reaction pathways. In this context, many opportunities arise when catalysts are activated in a rapid, localized, and energy-efficient manner. Among the various concepts to achieve adaptivity in catalysis, magnetic induction heating applied directly at the catalyst or in vicinity of the active site has gained increasing attention recently. In this Scientific Perspective, we provide a coherent framework to the emerging field of catalysis using magnetic fields-and in particular alternating current magnetic fields-to activate catalytic materials and define it as magnetically induced catalysis. Promising approaches and selected examples are described to illustrate the scientific concept and to highlight its broad potential for innovation in catalysis from laboratory to industrial scale.

Ten‐Electron Count Rule of MXene‐Supported Single‐Atom Catalysts for Sulfur Reduction in Lithium–Sulfur Batteries

ABSTRACTLithium–sulfur (Li–S) batteries are proposed as next‐generation energy storage devices due to their high theoretical capacity and specific energy. However, the actual capacity utilization is greatly limited by the poor reactivity of the sulfur reduction reaction (SRR), which motivates us to develop corresponding high‐efficient catalysts. Inspired by the application of MXene and single‐atom catalysts (SACs) in improving SRR, a virtual screening on the MXene‐supported SACs from the imp2d database is carried out. Finally, six kinds of top catalysts are identified for SRR, and most of them can be considered as variants of the previous representative SRR catalysts, which reflects the rationality of our screening. Meanwhile, the stability and reactivity metrics of the SACs are calculated by density functional theory (DFT) and show obvious trends depending on the type of adatom/MXene. For the critical intermediate binding that can tune SRR activity, further electronic structure analysis reveals the so‐called 10‐electron count rule, whose decisive role is also reflected by the Shapley value analysis from machine learning (ML). It is noteworthy that this count rule was used to analyze the SACs for hydrogen/carbon/nitrogen‐related reactions before, and our successful attempt to optimize SRR further indicates its universality in catalysis fields. Overall, the 10‐electron count rule not only rationalizes the nature of SAC–adsorbate interactions but also provides intuitive design guidance for novel SRR catalysts.

Controlled Synthesis of Dy/Cu Bimetallic Atoms for Efficient Artificial Photosynthesis.

The birth of metal atom catalysts marked a new historical stage in the field of catalysis, allowing scientists to better understand the science of catalysis at the atomic level. On the basis of anchoring independent metal atoms, bimetal dysprosium-copper atoms are successfully anchored on graphdiyne (DyCu/GDY). Dy and Cu metal atoms are selectively anchored in triangular holes of GDY and stabilized by non-integer charge transfer and the confined space effect between the metals and GDY. The dynamic charge-transfer equilibrium caused by the inherent non-integer charge transfer between GDY and metal atoms produces sustained high activity, inducing a redistribution of surface charge. This result shows that the non-integer charge transfer strongly promotes the adsorption activation of CO2 and the desorption of the reaction intermediates, realizing the unpredictable selectivity and activity of CO2 conversion in the process of artificial photosynthesis, where the selectivity and yield of CO are 98% and 279µmol gcat. -1h-1, respectively.

Enhanced methane generation using zeolitic imidazolate framework (ZIF-8) during biogas production

Metal–organic frameworks (MOFs) are increasingly being utilized in catalysis, fuel cells, and related fields due to their unique characteristics. This study explores the use of Zeolitic Imidazolate Framework-8 (ZIF-8) MOF during co-digestion of tuber and fruit waste to enhance biogas production and methane content. The ZIF-8 was synthesized and characterized using Fourier Transform Infra-Red spectroscopy, to confirm the presence of functional groups. The following properties of the feedstock and inoculum were evaluated: moisture content, volatile solids, total volatile solids, biodegradability index, total dissolved solids, pH, and electrical conductivity. The effect of solution pH and MOF mass was assessed. FTIR spectra were obtained with an FTIR spectrometer over a wavenumber range of 4500–500 cm⁻1. The pH values were near neutral, i.e., 6.9 (fruit waste), 6.7 (tuber waste), and 7.4 (inoculum). The biogas yield increased with ZIF-8 catalyst dosage, the highest biogas production of 1851 mL at ZIF-8 dosage of 0.5 g was attained which is twice as much as the control experiment (without ZIF-8) attained 914 mL. The use of ZIF-8 resulted in a 103% increase in biogas yield and showed that the application of ZIF-8 catalyzed the methanogenesis step resulting in increased yield and efficiency of the process.

Piezo‐Electro‐Catalytic Hydrogen Production via Piezoelectric Fluoropolymers

Producing future fuels, such as green hydrogen, using less external energy input is a key factor in making such fuels truly environmentally friendly. In addition, the requirement of reducing the amount of catalyst used per mass of fuel produced is key for resource stability, particularly for platinum group metals which dominate such catalysis fields. Herein, a proof‐of‐principle approach is demonstrated to achieve both targets through piezo‐electro‐catalysis from chemically stable, flexible, fluoropolymers. Highly polarized MXene‐poly(vinylidene‐difluoride)‐co‐(trifluoro‐ethylene) interfaces, with an embedded platinum mesh electrode, are shown to decrease the onset overpotential of the mesh by 200 mV, thus lowering the overall energy and Pt required to produce a given mass of hydrogen. The simple approach used herein can be applied to other, advanced catalysts, to boost performance and efficiency.

Water Oxidation, Sustainability, and the Catalyst Spin State: State of Play and Prospects

The water oxidation reaction is crucial in the fields of catalysis and sustainability. This review examines water oxidation through the lens of the catalysts’ spin state. Additionally, we delve into the quantum mechanical entanglement of the catalysts’ essential components and suggest exploring the connection between catalytic activity, spin state, and entanglement more broadly. This perspective could open new pathways for designing catalysts, not only for water oxidation but also for other significant reactions in sustainable chemistry.