Transition Metal Catalysts Research Articles

Discovery of Alloy Catalysts for Ammonia Decomposition by Machine Learning-Based Prediction of Adsorption Energies

Ammonia decomposition has gained significant attention as an eco-friendly method for hydrogen production because it creates no carbon dioxide emissions. While Ru catalysts are known for their high activity in ammonia decomposition, their high cost makes them uneconomical for commercial use. Therefore, it is essential to explore novel alloy catalysts composed of inexpensive elements with high catalytic performance. Nitrogen adsorption energies serve as key descriptors indicating the catalytic performance for ammonia decomposition, and first-principle calculations can compute these energies. However, the screening of numerous alloy catalyst candidates through extensive first-principle calculations and experimental validations remains time-consuming due to the vast number of potential candidates. To address this, artificial intelligence and machine learning models are being developed to quickly predict catalyst performance, efficiently searching for promising catalyst candidates. In this study, we developed a machine-learning-based method to rapidly predict nitrogen adsorption energies using a graph-based artificial neural network, thereby efficiently searching for novel catalysts for ammonia decomposition. Our training dataset included the nitrogen adsorption energies of 30 pure transition metal catalyst candidates, as well as binary alloy catalyst candidates, including core-shell and intermetallic compounds. As a result, we successfully identified 12 catalyst candidates composed of inexpensive elements that are likely to exhibit catalytic performance comparable to Ru catalysts.

Uniform Polymer Microspheres by Photoinduced Metal-Free Atom Transfer Radical Precipitation Polymerization.

Herein, a photoinduced method is introduced for the synthesis of highly cross-linked and uniform polymer microspheres by atom transfer radical polymerization (ATRP) at room temperature and in the absence of stabilizers or surfactants. Uniform particles are obtained at monomer concentrations as high as 10% (by volume), with polymers being exempt from contamination by residual transition metal catalysts, thereby overcoming the two major longstanding problems associated with thermally initiated ATRP-mediated precipitation polymerization. Moreover, the obtained particles have also immobilized ATRP initiators on their surface, which directly enables the controlled growth of densely grafted polymer layers with adjustable thickness and a well-defined chemical composition. The method is then employed successfully for the synthesis of molecularly imprinted polymer microspheres.

Engineering Electrolytes with Transition Metal Ions for the Rapid Sulfur Redox and In Situ Solidification of Polysulfides in Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have been pursued due to their high theoretical energy density and superb cost-effectiveness. However, the dissolution-conversion mechanism of sulfur inevitably leads to shuttle effects and interface passivation issues, which impede Li-S battery practical application. Herein, the approach of adopting transition metal salts (CoI2) to engineering the electrolyte is proposed. Different from anchored transition metal catalysts in the cathode, soluble cobalt ions can chemically reduce and solidify polysulfides, alleviating the dependence of sulfur conversion on the conductive interface while suppressing the shuttle effect. Importantly, all elements in CoI2 are in the lowest valence state and solid complexes are formed after the redox reaction, which prevents the migration of high valent Co3+ to the anode, thus overcoming the poor compatibility between redox mediator and Li anode. Notably, I3- has the function of eliminating dead sulfur and dead lithium, which we apply to Li-S batteries. After activating I3- at a certain frequency, Li-S batteries indeed achieve a longer and more stable cycle life. By combining the regulatory behavior of anions and cations, the electrolyte is engineered for Li-S batteries with high capacity, long lifespan, and excellent rate performance.

Advances in Combined Asymmetric Catalysis of Transition Metal/Phase Transfer Catalysts

Phase‐transfer catalysts (PTCs) are chemical agents that facilitate the transfer of molecules or ions between different reaction phases, thereby accelerating heterogeneous reaction processes. Transition metal catalysts are renowned for their versatility in breaking inert chemical bonds and forming new carbon‐carbon bonds. Over the past two decades, integrating metal catalysts with phase‐transfer catalysts has emerged as a highly valuable and adaptable strategy in modern organic synthesis. This combined catalytic approach highlights the enhanced synthetic capabilities and demonstrates the benefits of merging these two catalytic systems. This review provides an overview of recent advancements in asymmetric catalysis that utilize the synergy between metal and phase‐transfer catalysts, focusing on their role in the rapid and efficient synthesis of complex organic molecules with precise stereochemistry.

Molecularly Imprinted Polymers for Highly Specific Bioorthogonal Catalysis Inside Cells.

Transition metal catalysts (TMCs) mediated bioorthogonal catalysis expand the chemical possibilities within cells. Developing synthetic TMCs tools that emulate the efficiency and specificity of natural metalloenzymes is a rewarding yet challenging endeavor. Here, we highlight the potential of molecularly imprinted enzyme mimics (MIEs) containing a Cu center and specific substrate binding domain, for conducing dimethylpropargyloxycarbonyl (DmProc) cleavage reactions within cells. Our studies reveal that the Cu-MIEs act as highly specific guides, precisely catalyzing target substrates, even in glutathione (GSH)-rich cellular environments. By adapting templates similar to the target substrates, we evolved Cu-MIEs activity to a high level and provided a method to broaden its scope to other unique substrates. This system was applied to a thyroid hormone (T3)-responsive gene switch model, inducing firefly luciferase expression by T3 in cells. This approach verifies that MIEs effectively rescue DmProc-bearing T3 prodrugs and seamlessly integrating themself into cellular biocatalytic networks.

Recent Advancements in Fe-Based Catalysts for the Efficient Reduction of NOx by CO.

The technology of CO selective catalytic reduction of NOx (CO-SCR) showcases the potential to simultaneously eliminate CO and NOx from industrial flue gas and automobile exhaust, making it a promising denitrification method. The development of cost-effective catalysts is crucial for the widespread implementation of this technology. Transition metal catalysts are more economically viable than noble metal catalysts. Among these, Fe emerges as a prominent choice due to its abundant availability and cost-effectiveness, exhibiting excellent catalytic performance at moderate reaction temperatures. However, a significant challenge lies in achieving high catalytic activity at low temperatures, particularly in the presence of O2, SO2, and H2O, which are prevalent in specific industrial flue gas streams. This review examines the use of Fe-based catalysts in the CO-SCR reaction and elucidates their catalytic mechanism. Furthermore, it also discusses various strategies devised to enhance low-temperature conversion, taking into account factors such as crystal phase, valence states, and oxygen vacancies. Subsequently, the review outlines the challenges encountered by Fe-based catalysts and offers recommendations to improve their catalytic efficiency for use in low-temperature and oxygen-rich environments.

Ornidazole degradation based on peroxymonosulfate activation induced by oxygen vacancies (OV)-enriched Cu-Co-TiO2: Coexistence of free-radical and non-radical pathways

Employing transition-metal catalysts in peroxymonosulfate (PMS) activation reactions to facilitate combined free-radical and non-radical interactions is regarded as a proficient approach for decomposing organic contaminants. However, the creation of active catalysts faces significant challenges due to low activation efficiency, inadequate action sites, and instability of current activation materials. Here, we successfully prepared bimetallic Cu and Co co-doped TiO2 (Cu-Co-TiO2) catalyst using the sol-gel technique. Excellent ornidazole (ONZ) removal efficiency (0.628 min−1) was demonstrated by the Cu-Co-TiO2/PMS system, which was applicable across a broad pH range (4−10) and unaffected by different water matrices. Moreover, the coexistence of free-radical (SO4•-, •OH and O2•−) and non-radical (1O2) routes in the Cu-Co-TiO2/PMS system, where SO4•- and 1O2 are the predominant active substances, was confirmed by quenching experiments and electron paramagnetic resonance (EPR) study. The synergistic impact of Cu/Co bimetal may hasten the redox cycles of Cu+/Cu2+ and Co2+/Co3+, causing plenty of oxygen vacancies (OV) and improving PMS activation efficiency. The quantitative structure-activity relationship (QSAR) examination of the intermediates showed a decrease in toxicity, and the potential pathways of ONZ degradation were illustrated using Liquid Chromatography Mass Spectrometry (LC-MS) technology. This work not only demonstrated the effectiveness and stability of Cu-Co-TiO2 as a PMS activator, but it also offered fresh information on how to remove organic pollutants from wastewater by using PMS activation via the radical and non-radical oxidation pathway.

Late Transition Metal Olefin Polymerization Catalysts Derived from 8-Arylnaphthylamines

Late transition metal catalysts represent a significant class of olefin polymerization catalysts that have played an essential role in advancing the polyolefin industry owing to their highly tunable ligands and low oxophilicity. A key feature for the design of late transition metal catalysts lies in the steric bulk of the o-aryl substituents. Bulky 8-arylnaphthylamines have emerged as a promising aniline candidate for conducting high-performance catalysts by introducing axially steric hindrance around the metal center. This review focuses on late transition metal (Ni, Pd, Fe) catalysts derived from 8-arylnaphthylamines, surveying their synthesis, structural features, and catalytic applications in olefin (co)polymerizations. Additionally, the relationship between catalyst structure and catalytic performance is discussed, highlighting how these unique ligand systems influence polymerization activity, molecular weight, and polymer branching.

Electrochemical N‐Centered Radical‐Triggered Intramolecular N−N Coupling for the Cyclization of o‐Aminyl Azobenzenes

AbstractAn electrochemical radical cyclization of o‐aminyl azobenzenes via N‐centered radical generation has been developed for the synthesis of benzotriazoles. The cyclization of o‐aminyl azobenzenes bearing a sulfonyl protection on amine readily proceeds in the absence of any external transition metal catalyst or chemical oxidant, and exhibits good tolerance towards functional groups.

Electricity-Driven Strain-Release Cascade Cyclization of Bicyclo[1.1.0]butane (BCB): Stereoselective Synthesis of Functionalized Spirocyclobutyl Oxindoles.

Spirocyclobutyl oxindoles, characterized by their unique three-dimensional structures, are valuable building blocks for many pharmacophores and drug units. However, stereoselective synthetic strategies for these scaffolds remain underdeveloped, with most existing methods relying on transition metal catalysts and stoichiometric redox reagents. In this work, we introduce an electrochemical strain-release driven cascade spirocyclization of bicyclo[1.1.0]butane (BCB) derivatives for the stereoselective synthesis of functionalized spirocyclobutyl oxindoles. Tetrabutylammonium bromide serves a dual purpose as both a supporting electrolyte and brominating agent.The method offers a broad substrate scope, high atom economy, and excellent diastereoselectivity. The stereoselectivity of the product is controlled by minimizing the dipolar repulsion between the amide C=O and the C-Br bonds. We also explored the methodology's versatility by applying it to various functionalizations and demonstrated its scalability for practical use. The efficient derivatization of the products allowed for for the rapid creation a diverse library of functionalized spirocyclobutyl oxindoles.

Silyl Ethers as Latent Pronucleophiles in Enantioselective Lewis Base Catalyzed Synthesis of Allylic Ethers from Allylic Fluorides

Allylic ethers are a common occurrence in natural products and are often used as intermediates in target-oriented synthesis. Their synthesis often relies on the use of transition metal catalysts. Here we report an organocatalytic method for allylation of O-centered nucleophiles: Lewis base catalyzed allylation of silyl ethers with allylic fluorides. The method relies on the concept of latent pronucleophiles in Lewis base catalysis to overcome common limitations in substrate scope even allowing for allylation of sterically congested O-pronucleophiles. When chiral Lewis base catalysts are used, the allyl ethers are produced in enantioenriched form via a kinetic resolution of fluorides where streoselectivity is determined by the chiral catalyst.

Hierarchically Structured Catalysts toward Sustainable Hydrogen Economy: Electro- and Thermo-chemical Pathways.

Hydrogen, as an important clean energy source, plays a more and more crucial role in decarbonizing the planet and meeting the global climate challenge due to its high energy density and zero-emission. The demand for sustainable hydrogen is increasing drastically worldwide as driven by the global shift towards low-carbon energy solutions. Hierarchically structured catalysts and devices have gradually taken the center stage toward replacing the traditional counterparts, especially with the rapid advancing of the design and manufacture of such ordered nanostructure assemblies toward high activity, efficient mass transport, and superb stability. In this review, the latest progress of the hierarchically structured catalysts for hydrogen production have been surveyed on electro- and thermo- chemical pathways comparatively. It covers the structure designs of atomic dispersion, nanoscale surfaces and interfaces for achieving highly active and durable catalysts, components, and devices. Both electrochemical and thermochemical approaches are reviewed in terms of the vast design details, engineered benefits, and understandings of various Pt-group metal (PGM) and non-PGM based transition metal catalysts for hydrogen production. As the growing trend, brief discussions are also presented toward the high-level assembly and manufacture of complexly structured components and devices at scale in the electrochemical and thermochemical energy systems.

Visible-Light-Driven Method for the Selective Synthesis of Amides and N-Acylureas from Carboxylic Acids and Thioureas.

In this work, we developed a visible-light-driven method for the selective synthesis of amides and N-acylureas from carboxylic acids and thioureas. This protocol was featured as avoidance of additional oxidants and transition metal catalysts, simple manipulations, low cost, broad substrate scope, and good functional group tolerance. As only oxygen serves as the oxidation reagent, this method provides a promising synthesis candidate for the formation of N-aryl amides and N-acylureas, including late-stage functionalization of complex pharmaceutical molecules and biologically active molecules.

In Situ Growth of MoN on Nickel Foam for Highly Efficient Hydrogen Evolution in Alkaline Solution.

Highly efficient, stable, and low-cost hydrogen evolution catalysts are urgently required for water electrolysis. Herein, a method for in situ growth of medium-nitrogen nanosheet MoN catalysts with a large electrochemical surface area on nickel foam (NF) is proposed. The results show that the morphology of the as-prepared catalysts greatly depends on the nitrogen sources and nitridation temperature. The MoN/NF catalyst nitride at 700 °C using melamine as a nitrogen source exhibits a spindle-like morphology consisting of stacked nanosheets, which is conducive to exposing more active sites, thereby increasing the catalyst activity. The N atoms in MoN could adjust the chemical environment of the metal by changing the density of the d-band electron state, which further improves the HER performance. Benefiting from the regulation of Mo charge distribution and exposure to more active sites through N doping and morphological control, the MoN/NF catalyst exhibits superior HER performance with an overpotential of 70 mV at a current density of 10 mA·cm-2, a Tafel slope of 44.3 mV dec-1, and an Rct of 1.83 Ω, indicating high HER catalytic activity, fast kinetics, and excellent conductivity. Theoretical calculations reveal that among the (002), (202), and (200) planes of MoN, the (202) plane exhibits the lowest value of |ΔGH*| (0.47 eV), which is close to that of Pt(111) (0.14 eV). More importantly, MoN(202) also has the smallest work function of 3.58 eV, indicating an enhanced capability to offer electrons. This work develops a strategy to design high-performance and low-cost transition-metal nitride HER catalysts.

Deuteration Degree Controllable Synthesis of Aryl Deuteromethyl Ethers Through Dual photoredox and Thiol Catalysis.

Herein, we report a facile and efficient deuteration degree controllable method for the preparation of aryl deuteromethyl ethers through dual photoredox and thiol catalysis using phenols as the starting materials and inexpensive D2O and CDCl3 as the deuterium sources. All aryl d1, d2, and d3 deuteromethyl ethers can be precisely prepared with good to excellent yields and deuteration ratios. The reaction operates under mild conditions without the need for high temperatures or high loading of transition metal catalysts, and a wide range of functional groups are well tolerated.

Highly Dispersed Pd@ZIF‐8 for Photo‐Assisted Cross‐Couplings and CO2 to Methanol: Activity and Selectivity Insights

AbstractOur study unveils a pioneering methodology that effectively distributes Pd species within a zeolitic imidazolate framework‐8 (ZIF‐8). We demonstrate that Pd can be encapsulated within ZIF‐8 as atomically dispersed Pd species that function as an excited‐state transition metal catalyst for promoting carbon–carbon (C−C) cross‐couplings at room temperature using visible light as the driving force. Furthermore, the same material can be reduced at 250 °C, forming Pd metal nanoparticles encapsulated in ZIF‐8. This catalyst shows high rates and selectivity for carbon dioxide hydrogenation to methanol under industrially relevant conditions (250 °C, 50 bar): 7.46 molmethanol molmetal−1 h−1 and >99 %. Our results demonstrate the correlations of the catalyst structure with the performances at experimental and theoretical levels.

In Situ Carbon Thermal Reduction to Enrich Sulfur-Vacancy in Nickel Disulfide Cathode for Efficient Synthesizing Hydrogen Peroxide.

Transition metal catalysts are widely used in the 2e- ORR due to their cost-effectiveness. However, they often encounter issues related to low activity. Defect engineering are used on developing highly active catalysts, which can effectively modify active sites and promote electron transfer. Here, carbon-coated Ni3S2 (Ni3S2@C), where the additional sulfur vacancies (VS) is prepared induced by the carbon layer is coupled with active nickel sites. Through in situ and ex situ experiments combined with DFT calculations, it is demonstrated that the carbon layer can regulate the quantity of VS in Ni3S2. Materials with a higher concentration of VS exhibit enhanced 2e- ORR activity and higher H2O2 selectivity. In situ Raman spectroscopy confirms that Ni serves as the key active site in this catalyst. DFT calculations indicate that the OOH binding energy (ΔG) decreases with an increase in the number of VS, favoring the protonation of *OOH to generate H2O2. Upon performance testing, the average H2O2 selectivity is 92.3%, with the highest yield reaching up to 3860mmolgcat-1h-1. It is noteworthy that Ni3S2@C exhibits high stability, with only a slight decrease in 2e- pathway selectivity after 5000 cycles of ADT.

FeNi3 alloy doped carbon spheres for improving hydrogen storage performance of MgH2

MgH2 is one of the ideal hydrogen storage materials because of its high hydrogen storage density, but the thermodynamic stability and slow kinetics of Mg/MgH2 system hinder its practical application. Transition metal catalyst doping has become an important strategy to improve the hydrogen storage kinetics of MgH2. In this work, FeNi3@CS was prepared by solvothermal method with carbon spheres (CS) as the support, and introduced into Mg/MgH2 system to prepare MgH2–FeNi3@CS composite. The initial dehydrogenation temperature of MgH2–FeNi3@CS composite is 565 K, which is 100 K lower than additive-free MgH2. At 423 K, MgH2–FeNi3@CS composite could absorb 4.5 wt% H2, while the hydrogen absorption capacity of MgH2 without additives is only 2.0 wt%. After 10 cycles, the hydrogenation and dehydrogenation capacity could be maintained at 5.6 wt% and 4.5 wt%, respectively. In addition, the activation energy of MgH2–FeNi3@CS composite decreased by 52 kJ/mol compared with MgH2. FeNi3 was in situ converted to Mg2NiH4 and Fe after hydrogenation-ball milling, which were considered as the catalytic active substances in Mg/MgH2 system. The synergistic catalysis of Mg2Ni/Mg2NiH4, Fe and carbon materials has a positive effect on improving the hydrogen storage performance of Mg/MgH2 system.

Enzymatic and Bio-Inspired Enantioselective Oxidation of Non-Activated C(sp 3)–H Bonds

AbstractThe enantioselective oxidation of C–H bonds relies on two different approaches: the use of enzymes or bio-inspired transition metal catalysts. Both are powerful tools, as they transform ubiquitous C(sp3)–H bonds into valuable oxygenated building blocks. However, the reaction remains a challenge in synthetic chemistry, continuously demanding efficient catalytic systems to improve substrate scopes. Optimization of site- and enantioselectivities in bio-catalytic systems is underpinned by protein engineering, while ligand design and medium effects play crucial roles in bio-inspired synthetic complexes. In this Short Review, recent advances in the field are described, focusing on reactions that target strong, non-activated C–H bonds.1 Introduction1.1 Enantioselective Catalytic C–H Oxidation in Nature and Bio-Inspired Systems1.2 Biological C–H Oxidation Mechanism and Challenges for the Implementation of Chirality with Synthetic Catalysts1.3 Bio-Catalytic C–H Oxidation Systems: From Microorganism to Engineered Enzymes1.4 Mimicking Nature: The Bio-Inspired C–H Oxidation Approach1.5 Origin of Enantioselectivity2 Enantioselective C–H Oxidation of Non-Activated C–H Bonds2.1 Hydroxylation at Non-Activated C–H Bonds by Bio-Catalytic Systems2.2 Enantioselective C–H Lactonization with Enzymatic Systems2.3 Oxidation at Non-Activated C–H Bonds by Synthetic Catalysts2.4 Enantioselective Lactonization with Small-Molecule Catalysts3 Conclusions

Vitreous silica supported metal catalysts for direct non-oxidative methane coupling

Direct non-oxidative methane coupling (NMC) transforms methane into valuable chemicals and hydrogen, which is a promising pathway to boost industrial decarbonization. The reaction, however, is challenged by high C-H bond activation temperature, catalyst coking, and low selectivity towards hydrocarbon products. Here we studied the efficacy of five vitreous silica supported 3d transition metal (Mn, Fe, Co, Ni, and Cu) catalysts (denoted as M/SiO2-v) for NMC. These catalysts were prepared by flame fusion of mixtures of quartz and metal silicate precursors. The metal species in the as-synthesized catalysts were fully or partially oxidized, with their stability following the order of Mn > Fe ≈ Co > Ni > Cu in the NMC reaction. The Cu species has low methane reaction rate, due to the high adsorption and dissociation energies of methane. The Mn and Ni species have high methane reaction and coke formation rates, which is supported by easy kinetics of methane deep dehydrogenation to carbon. In contrast, Fe and Co species showed the best hydrocarbon product selectivity. Particularly, the Co species emerged as the optimal catalyst for NMC, showcasing a balanced methane activation, hydrocarbon formation, and low coke yield. The relationship between the evolved metal species under reaction conditions and their NMC performance was discussed. The present study screens and provides effective catalyst formulations for NMC reactions.