Chemical Catalysis Research Articles

Synthesis and characterization of low-dimensional N-heterocyclic carbene lattices.

The covalent interaction of N-heterocyclic carbenes (NHCs) with transition metal atoms gives rise to distinctive frontier molecular orbitals (FMOs). These emergent electronic states have spurred the widespread adoption of NHC ligands in chemical catalysis and functional materials. Although formation of carbene-metal complexes in self-assembled monolayers on surfaces has been explored, design and electronic structure characterization of extended low-dimensional NHC-metal lattices remains elusive. Here we demonstrate a modular approach to engineering one-dimensional (1D) metal-organic chains and two-dimensional (2D) Kagome lattices using the FMOs of NHC-Au-NHC junctions to create low-dimensional molecular networks exhibiting intrinsic metallicity. Scanning tunneling spectroscopy and first-principles density functional theory reveal the contribution of C-Au-C π-bonding states to dispersive bands that imbue 1D- and 2D-NHC lattices with exceptionally small work functions.

Opinion — On a New Mechamistic Model Toward the Catalytic Reactions: From Hydrogen Combustion to Fischer-Tropsch Reaction

Mechanism research in catalytic chemistry is both fascinating and confusing, particularly when it comes to solid-state catalysts, the nature of catalytic behaviours has been unidentified so far. For a mechanistic model to be acceptable, it should have an ability to explain all unique aspects of a given catalytic reaction and provide an illuminating explanation to a widely range of catalytic reaction. In our recent reports, a new mechanistic model was suggested for catalytic CO<sub>2</sub> reduction reaction on Cu metal and hydrogen evolution reaction on various transition metals, which provides a reasonable interpretation to both catalytic reactions (from the diversity of product distribution and catalytic behaviour of various metals). Here, it is expected to extend this new mechanistic model to a wider range of catalytic reactions over various catalysts. Such as hydrogen combustion with Cu metal adding, oxidation of SO<sub>2</sub> by O<sub>2</sub> to give SO<sub>3</sub> with NO adding, conversion of CO and NO into CO<sub>2</sub> and N<sub>2</sub> with Ru metal adding, and hydrogeneration of propylene with Pt metal adding. Importantly, this model seems also to pertain to the mechanism of the Fischer-Tropsch (T-F) reaction, i.e. the conversion of CO and H<sub>2</sub> to hydrocarbons, principally a mixture of linear alkanes (including methane) and alkenes, by passage over various heterogeneous transition-metal catalysts (Fe, Co, Ni et.al.).

Recent advances in palladium‐catalyzed α‐arylation reactions

The indispensable role of α‐arylated compounds in chemistry can be accounted from its presence in various pharmaceuticals we use in our daily life. Chemists are establishing diverse methods for the synthesis of various α‐arylated compounds by considering their applications in different fields including biology, medicine, agrochemicals, material science, etc. Diverse pharmacologically active compounds, natural products, and drugs contain α‐arylated carbonyl groups in their structure. The impact of transition metal catalysis in chemistry is overwhelming, among which palladium is the predominant due to its high reactivity as well as catalytic potential. α‐Arylation reactions with palladium catalysts have been successful in producing a variety of desired chemicals. The formation of active pharmaceutical ingredients and total synthesis of natural products can now be achieved by the development of novel pathways through the α‐arylation of carbonyl compounds, catalyzed by palladium. Wide variety of simple arylating agents could be used under the condition of palladium catalysis. Syntheses that utilize α‐arylation methods often offer advanced ways that improve overall yields, expand the scope of the synthesis, and reduce the steps. One of the synthetic achievements is the increased selectivity obtained with lower amounts of the catalyst. Gentle reaction conditions were employed, and broad substrate scope was accomplished. Recent advances in the α‐arylation reactions of various compounds, catalyzed by palladium, is discussed in this review covering literature from 2016 to 2022.

Enhanced predictive optimization of methane dry reforming via ResponseSurface methodology and artificial neural network approaches: Insights using a novel nickel-strontium-zirconium-aluminum catalyst

This study investigates the molecular dynamics of methane dry reforming catalyzed by a novel nickel-strontium-zirconium-aluminum (5Ni+3Sr/10Zr+Al) catalyst, leveraging both Response Surface Methodology (RSM) and Radial Basis Function Neural Network (RBFNN) for predictive optimization. Focusing on the impact of operational parameters—hourly space velocity, reaction temperature, and CO2:CH4 mole ratio—on the conversion rates and formation of reaction components, we aim to predict optimal conditions and corresponding process variables. Through a comparison of a three-layer Feed Forward Neural Network, optimized at a 3:10:1 topology, with traditional RSM approaches, our findings highlight the superior predictive capabilities of ANN models. Notably, ANN demonstrated exceptional performance with Radj2and F_Ratio values significantly surpass those of RSM, alongside lower statistical error terms. This superiority is attributed to ANN's robust handling of nonlinear relationships between inputs and outputs, asserting its potential for enhancing predictive accuracy in chemical process optimization. At optimum predicted conditions like 1 CH4/CO2,750 °C reaction temperature, 12000 cm3g−1h−1 space velocity, NiSrZrAl outperformed with > 85 % CH4 and CO2 conversion with H2/CO ∼1 up to 20 h time on stream. Our research underscores the importance of integrating advanced modeling techniques for the efficient and accurate prediction of catalytic reactions, offering valuable insights for future applications in chemical engineering and catalysis.

Spatially selective catalysis of OSA starch for preparation of Pickering emulsions with high emulsification properties

The traditional strategies of chemical catalysis and biocatalysis for producing octenyl succinic anhydride modified starch can only randomly graft hydrophobic groups on the surface of starch, resulting in unsatisfactory emulsification performance. In this work, a lipase-inorganic hybrid catalytic system with multi-scale flower like structure is designed and applied to spatially selective catalytic preparation of ocenyl succinic anhydride modified starch. With the appropriate floral morphology and petal density, lipases distributed in the “flower center” can selectively catalyze the grafting of hydrophobic groups in a spatial manner, the hydrophobic groups are concentrated on one side of starch particles. The obtaining OSA starch exhibits excellent emulsifying property, and the pickering emulsion has good protective effect on the embedded curcumin. This work provides a direction for the development of high-performance starch-based emulsifiers for the food and pharmaceutical industries, which is of great significance for improving the preparation and emulsification theory research of modified starch.

Access to Enantioenriched Allylic Alcohols via Peptide‐Mimic Phosphonium Salt‐Catalyzed Asymmetric Aerobic Hydroxylation

Comprehensive SummaryThe development of catalytic asymmetric methods that enable access to value‐added functionalities or structures, exemplified by allylic alcohols, is a highly interesting yet challenging topic from both academic and industrial perspectives. However, before recent advances in chemical catalysis, there were scarce protocols toward constructing enantioenriched tertiary allylic alcohol scaffolds. In this context, peptide‐mimic phosphonium salts were found to be highly efficient in catalytic asymmetric α‐hydroxylation of α,β‐unsaturated and/or β,ϒ‐unsaturated compounds with satisfactory regio‐ and stereochemical outcomes (up to 97% yield and 95% ee). This methodology tolerates a broad array of substrates and thus provides an expeditious and unified platform for the assembly of enantioenriched tertiary allylic alcohols by avoiding the use of additional reductants and expensive metal catalysts. Furthermore, the power of this protocol is enlarged by simple conditions and the use of air as a source of hydroxyl functionality.

DszA Catalyzes C-S Bond Cleavage through N5-Hydroperoxyl Formation.

Due to its detrimental impact on human health and the environment, regulations demand ultralow sulfur levels on fossil fuels, in particular in diesel. However, current desulfurization techniques are expensive and cannot efficiently remove heteroaromatic sulfur compounds, which are abundant in crude oil and concentrate in the diesel fraction after distillation. Biodesulfurization via the four enzymes of the metabolic 4S pathway of the bacterium Rhodococcus erythropolis (DszA-D) is a possible solution. However, the 4S pathway needs to operate at least 500 times faster for industrial applicability, a goal currently pursued through enzyme engineering. In this work, we unveil the catalytic mechanism of the flavin monooxygenase DszA. Surprisingly, we found that this enzyme follows a recently proposed atypical mechanism that passes through the formation of an N5OOH intermediate at the re side of the cofactor, aided by a well-defined, predominantly hydrophobic O2 pocket. Besides clarifying the unusual chemical mechanism of the complex DszA enzyme, with obvious implications for understanding the puzzling chemistry of flavin-mediated catalysis, the result is crucial for the rational engineering of DszA, contributing to making biodesulfurization attractive for the oil refining industry.

Metal-organic polymer enables efficient organic photoelectrochemical transistor biosensing

The field of organic photoelectrochemical transistor (OPECT) is newly emerged, with increasing efforts attempting to utilize its properties in biological sensing. Advanced materials with new physicochemical properties have proven important to this end. Herein, we report a metal-organic polymers-gated OPECT biosensing exemplified by CuⅠ-arylacetylide polymers (CuAs)-modulated poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) channel. Both the photoelectrochemical properties and gating capability of CuAs are explored and optimized for high-efficacy photogating. Morever, based on its inherent structure, the specific reaction between CuAs and sulfur ions (S2−) is revealed and S2−-mediated microRNA-21 detection is realized by linking with nucleic acid amplification and alkaline phosphatase catalytic chemistry. This work introduces metal-organic polymers as gating materials for OPECT biosensing.

Halogen-powered static conversion chemistry.

Halogen-powered static conversion batteries (HSCBs) thrive in energy storage applications. They fall into the category of secondary non-flow batteries and operate by reversibly changing the chemical valence of halogens in the electrodes or/and electrolytes to transfer electrons, distinguishing them from the classic rocking-chair batteries. The active halide chemicals developed for these purposes include organic halides, halide salts, halogenated inorganics, organic-inorganic halides and the most widely studied elemental halogens. Aside from this, various redox mechanisms have been discovered based on multi-electron transfer and effective reaction pathways, contributing to improved electrochemical performances and stabilities of HSCBs. In this Review, we discuss the status of HSCBs and their electrochemical mechanism-performance correlations. We first provide a detailed exposition of the fundamental redox mechanisms, thermodynamics, conversion and catalysis chemistry, and mass or electron transfer modes involved in HSCBs. We conclude with a perspective on the challenges faced by the community and opportunities towards practical applications of high-energy halogen cathodes in energy-storage devices.

An overview of Metal–Organic Frameworks as potential platform: Sensing for detection environmental pollutants and drug delivery applications

Metal Organic Frameworks (MOFs) represent a novel class of materials, characterized by their ability to form extended porous crystalline structures through the linkage of inorganic clusters or metallic ions with organic ligands. The availability of broad range of metal centres and type of organic linkers gives us opportunity for tailoring physical and chemical properties of MOFs. These modified MOFs opens up new channels for the customization of new devices needed for specific purposes. Though MOFs have been explored for significant applications in different sectors such as gas storage, proton conduction, biotechnological, biomedical sciences, catalysis, and separation, but drug delivery and the sensing applications has been taken exclusively at the manuscript. So, this article entails an overview of various synthetic methodology of low dimensional MOFs such as 1D and 2-D MOFs, and also focuses on their applications in sensing and drug delivery. This stems from their remarkable catalytic chemistry and their compatibility with a broad spectrum of materials. Furthermore, the 2-D layered structure of MOFs and their distinctive coordination of metal ions with organic ligands have emerging interest in the recent years.

The discovery of novel noncoding RNAs in 50 bacterial genomes.

Structured noncoding RNAs (ncRNAs) contribute to many important cellular processes involving chemical catalysis, molecular recognitionand gene regulation. Few ncRNA classes are broadly distributed among organisms from all three domains of life, but the list of rarer classes that exhibit surprisingly diverse functions is growing. We previously developed a computational pipeline that enables the near-comprehensive identification of structured ncRNAs expressed from individual bacterial genomes. The regions between protein coding genes are first sorted based on length and the fraction of guanosine and cytidine nucleotides. Long, GC-rich intergenic regions are then examined for sequence and structural similarity to other bacterial genomes. Herein, we describe the implementation of this pipeline on 50 bacterial genomes from varied phyla. More than 4700 candidate intergenic regions with the desired characteristics were identified, which yielded 44 novel riboswitch candidates and numerous other putative ncRNA motifs. Although experimental validation studies have yet to be conducted, this rate of riboswitch candidate discovery is consistent with predictions that many hundreds of novel riboswitch classes remain to be discovered among the bacterial species whose genomes have already been sequenced. Thus, many thousands of additional novel ncRNA classes likely remain to be discovered in the bacterial domain of life.

Efficient hydrolysis of cellulose into sugars in aqueous systems using fibrous core-shell structure FS@C/HPW

Phosphotungstic acid hydrate (HPW)-doped hydroxyl-rich hydrothermal carbon-coated fibrous silica catalyst (FS@C/HPW) is fabricated to induce the highly efficient hydrolysis of cellulose to sugar in an ultra-low acid aqueous system. The obtained FS90@C/HPW12 owns good thermal stability under 200 °C and the highest specific surface area at 28 m2/g. Owing to its special fibrous microstructures, FS90@C/HPW12 can cause linear damage and structural fragmentation on the surface of cellulose during hydrolysis. Accordingly, rather highly efficient hydrolysis with the cellulose conversion of 100 %, total reducing sugar and glucose yields at 92.2 % and over 85 % is achieved in the aqueous system with FS90@C/HPW12 and 5 mmol/L H2SO4. FS90@C/HPW12 also exhibits good reusability in multiple hydrolysis. This research provides a particular way for the design and synthesis of solid catalysts to induce the highly efficient hydrolysis of cellulose to sugar by chemical catalysis in a full aqueous system.

Catalytic Conversion of Complex Reactant Systems Makes the World Greener, More Sustainable and Hopeful: Where and How to Go?

Catalysis plays vital roles in chemical industries, which brings out significant convenience to human life in many aspects. With the development of both science and technology, various advanced and multivariate technologies have been cultivated in catalysis. Herein, a brief introduction in the frontiers of catalysis chemistry including single-atom catalysts, single crystal-based model catalysts, molecular switches catalysis and metal-organic frameworks / covalent-organic frameworks based catalysts has been given. Complex reactant systems (Biomass, vehicle exhausted gases, plastic wastes, and waste water) that featured with complex compositions, chemical-bonding and interactions endow researchers huge challenges to convert them to value-added chemicals or treat them to less-toxic or even non-toxic chemicals. Successes on catalytic conversion and degradation of these complex reactant systems sheds light on constructing a greener and more sustainable Earth via using both traditional and advanced catalysts combined with rational strategies. Progresses that achieved on the catalytic degradation of these complex reactant systems have been summarized here. However, the remaining issues concerned with these complex reactant systems drive us to think about how to further deal with them to achieve higher sustainability. Herein, four prospectives are proposed. We truly believe that with the continuous efforts on developing new catalysts with high efficiency and exploring reaction mechanisms under actual conditions towards these complex reactant systems, clearer understanding and better results could be achieved ultimately.

Practical and efficient oxygenation of benzylic C-H bonds with dioxygen catalyzed by two-dimensional porous organic frameworks possessing porphyrin cobalt(II) units

Metalloporphyrin T(4-Br)PPCo was used in the construction of two-dimensional porous organic framework materials (2D POFs) in order to achieve the direct benzyl C-H bonds oxygenation. In order to prevent the disordered diffusion of free radicals in 2D POFs, a restricted reaction channel was constructed, and heterogeneous catalysis was applied to decrease the deep oxygenation of partial oxygenation products due to central metal sites. All 2D POFs were characterized as amorphous microporous materials containing highly and uniformly dispersed Co2+. It was used to partially oxygenate C-H bonds at benzyl position employing dioxygen in solvent-free condition, and the conversion and selectivity were improved at the same time, especially when residual -B(OH)2 and -Br were capped. Compared with T(4-Br)PPCo, the substrate conversion increased from 39 % to 66 %, and the selectivity for 4-nitroacetophenone increased from 66 % to 91 %. The reaction mechanism, apparent kinetics and substrate compatibility were also studied. In this work, it provided a guiding reference for the effective C-H bonds oxygenation and other free radical based chemical reactions. The use of POFs in catalytic chemistry was further broadened, and a successful method for improving the catalytic characteristics of POFs by capping the remaining active groups was suggested.

MOF/MXene Composites: Synthesis, Application and Future Perspectives

Abstract2D MXenes family creates an interest in environmental cleaning and energy conversion. It shows large surface functional groups, electronic transmission, and electrical conductivity. This research focuses on Metal Organic Framework‐based Ti3C2 heterojunctions, directing on surface morphology control, customizable electrical structure, high performance in Ti3C2‐based electrocatalytic devices, and energy storage as a supercapacitor. In addition, future development obstacles and viable research possibilities are presented. MXene detailed analysis reveals a fundamental study, structure‐activity connections, and potential research paths for environmental applications. Specially developed MOF/MXene nanoarchitectures with remarkable features are highlighted in several study fields, including the chemical sciences, environmental engineering, physics, catalysis, and nanotechnology. They represent a new class of cutting‐edge developing materials. Mainly, the presented review describes multiple synthesis approaches by adjusting conditions for MOF/MXene nanoarchitectures with varying morphologies, and intriguing properties can also be developed for electrochemical energy conversion and storage.

Unveiling Confinement Engineering for Achieving High-Performance Rechargeable Batteries.

The confinement effect, restricting materials within nano/sub-nano spaces, has emerged as an innovative approach for fundamental research in diverse application fields, including chemical engineering, membrane separation, and catalysis. This confinement principle recently presents fresh perspectives on addressing critical challenges in rechargeable batteries. Within spatial confinement, novel microstructures and physiochemical properties have been raised to promote the battery performance. Nevertheless, few clear definitions and specific reviews are available to offer a comprehensive understanding and guide for utilizing the confinement effect in batteries. This review aims to fill this gap by primarily summarizing the categorization of confinement effects across various scales and dimensions within battery systems. Subsequently, the strategic design of confinement environments is proposed to address existing challenges in rechargeable batteries. These solutions involve the manipulation of the physicochemical properties of electrolytes, the regulation of electrochemical activity, and stability of electrodes, and insights into ion transfer mechanisms. Furthermore, specific perspectives are provided to deepen the foundational understanding of the confinement effect for achieving high-performance rechargeable batteries. Overall, this review emphasizes the transformative potential of confinement effects in tailoring the microstructure and physiochemical properties of electrode materials, highlighting their crucial role in designing novel energy storage devices.

Electronic Structure and Ligand Effects on the Activation and Cleavage of N2 on a Molybdenum Center.

Dinitrogen fixation under ambient conditions remains a challenge in the field of catalytic chemistry due to the inertness of N2. Nitrogenases and heterogeneous solid catalysts have displayed remarkable performance in the catalytic conversion of dinitrogen to ammonia. By introduction of molybdenum centers in molecular complexes, one of the most azophilic metals of the transitional metal series, moderate ammonia yields have been attained. Here, we present a combined multiconfigurational/density functional theory study that addresses how ligand fields of different strengths affect the binding and activation of dinitrogen on molybdenum atoms. First, we explored with MRCI computations the diatomic Mo-N and triatomic Mo-N2 molecular systems. Then, we performed a systematic examination on the stabilization effects introduced by external NH3 ligands, before we explore model neutral and charged complexes with different types of ligands (H2O, NH3, and PH3) and their consequences on the N2 binding and activation.

Catalytic chemistry inspired hollow carbon nanofibers loaded with NiS/Ni as high-performance and safe Li+ reservoir

Transition metal sulfides (TMSs) based anodes hold a very broad application prospect in lithium ion batteries (LIBs). In this work, the catalytic effect of metallic nickel at high temperature was used to generate hollow carbon nanofibers loaded with NiS and Ni (denoted as NiS/Ni@HCNF). The heteroatoms doped carbon fibers buffer the huge volumetric change of NiS during the discharge/charge process, and enhance the ion transport efficiency and electrical conductivity. In addition, the high specific surface area brought by the hollow carbon nanofibers can accelerate the electrolyte penetration and speed up the transport of ions as well as electrons. When used as anode of half cell, this electrode gives 958.5 and 612.9 mAh/g after running 1000 cycles under 1 and 2 A/g, showing the extremely-low attenuation rates of 0.0483 % per cycle and 0.0643 % per cycle, respectively. Impressively, NCM//NiS/Ni@HCNF battery shows the discharge capacity of 187.6 mAh/g at 1st cycle. Regarding the next 100 cycles, the relatively-high discharge capacities (>110 mAh/g) and coulombic efficiency (CE) values (>96 %) are discerned. It is noted that the usage of NiS/Ni@HCNF electrode improves the activation energy for thermal runaway, corroborating the elevated thermal safety of battery.

C-H Bond Activation by a Seven-Coordinate Bipyridine-Bipyrazole Ruthenium(IV) Oxo Complex.

Ruthenium-oxo species with high coordination numbers have long been proposed as active intermediates in catalytic oxidation chemistry. By employing a tetradentate bipyridine-bipyrazole ligand, we herein reported the synthesis of a seven-coordinate (CN7) ruthenium(IV) oxo complex, [RuIV(tpz)(pic)2(O)]2+ (RuIVO) (tpz = 6,6'-di(1H-pyrazol-1-yl)-2,2'-bipyridine, pic = 4-picoline), which exhibits high activity toward the oxidation of alkylaromatic hydrocarbons. The large kinetic isotope effects (KIE) for the oxidation of DHA/DHA-d4 (KIE = 10.3 ± 0.1) and xanthene/xanthene-d2 (KIE = 17.2 ± 0.1), as well as the linear relationship between log (rate constants) and bond dissociation energies of alkylaromatics, confirmed a mechanism of hydrogen atom abstraction.

Laser direct overall water splitting for H2 and H2O2 production

Hydrogen (H2) and hydrogen peroxide (H2O2) play crucial roles as energy carriers and raw materials for industrial production. However, the current techniques for H2 and H2O2 production rely on complex catalysts and involve multiple intermediate steps. In this study, we present a straightforward, environmentally friendly, and highly efficient laser-induced conversion method for overall water splitting to simultaneously generate H2 and H2O2 at ambient conditions without any catalysts. The laser direct overall water splitting approach achieves an impressive light-to-hydrogen energy conversion efficiency of 2.1%, with H2 production rates of 2.2 mmol/h and H2O2 production rates of 65 µM/h in a limited reaction area (1 mm2) within a short real reaction time (0.36 ms/h). Furthermore, we elucidate the underlying physics and chemistry behind the laser-induced water splitting to produce H2 and H2O2. The laser-induced cavitation bubbles create an optimal microenvironment for water-splitting reactions because of the transient high temperatures (104 K) surpassing the chemical barrier required. Additionally, their rapid cooling rate (1010 K/s) hinders reverse reactions and facilitates H2O2 retention. Finally, upon bubble collapse, H2 is released while H2O2 remains dissolved in the water. Moreover, a preliminary amplification experiment demonstrates the potential industrial applications of this laser chemistry. These findings highlight that laser-based production of H2 and H2O2 from water holds promise as a straightforward, environmentally friendly, and efficient approach on an industrial scale beyond conventional chemical catalysis.