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ChemCatChem: Volume 16, Issue 16
August 26, 2024
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Cover
Front Cover: Synthesis-Structure-Catalysis Relations in CHA Zeolites Applied for Selective Catalytic Reduction of NOx with Ammonia (ChemCatChem 16/2024)
- First Published: 27 August 2024
The Front Cover represents the three formation routes of zeolite from different starting materials. Zeolites are crucial industrial catalysts, whereas their crystallization mechanism is still unclear, limiting their rational functional design. Nao Tsunoji and co-workers present the synthesis–structure–catalysis relation of CHA zeolite to get fundamental knowledge for intentionally controlling the function of zeolites. Different starting materials provide three different formation pathways to form CHA zeolites with different properties in the presence of tetraethylammonium hydroxide as an inexpensive organic structure directing agent. The knowledge related to origin of the catalytic durability was obtained based on their structural character, crystallization mechanism, and exhaust gas purification ability. More information can be found in the Research Article by Nao Tsunoji and co-workers (DOI: 10.1002/cctc.202400459).
Cover Feature: Stabilizing Layered BiOBr Photoelectrocatalyst by Van Der Waals Heterojunction Strategy (ChemCatChem 16/2024)
- First Published: 27 August 2024
2D MoS2/BiOBr van der Waals heterojunctions can be used for photoelectrocatalytic hydrogen production. The Cover Feature shows a MoS2/BiOBr heterojunction working as a photocathode. The photogenerated electrons from BiOBr mainly flow into two directions: one is migrating towards the MoS2 surface, driving the hydrogen evolution reaction; the other is accumulating on BiOBr and reduces BiOBr to metallic Bi. However, in a heterojunction with small ratio of MoS2, the electrons are prone to transfer to MoS2, thus decreasing the accumulation of electrons on BiOBr and preventing it from deactivation. More information can be found in the Research Article by Mengjiao Wang, Francesco Lamberti, and co-workers (DOI: 10.1002/cctc.202400282).
Review
Crystalline to Amorphous: Unveiling the Potential of Transition Metal Oxide-based Electrocatalysts for Facile Oxygen Evolution Reaction in Alkaline Media
- First Published: 27 January 2024
The development of efficient metallic electrocatalysts is essential for realizing the potential of water splitting as a sustainable energy source. Compared with the early discovered electrodes with crystalline structure, the amorphous metallic glass-oxide assembly outperforms many transition and precision metal-based oxides and their composite forms regarding oxygen electroactivity and stability.
Pnictocatalysis
- First Published: 31 January 2024
In analogy with carbocatalysis, thermal catalysis on extended surfaces of Group 15 elements is coined here as “pnictocatalysis” (phospho-, arsene-, antimony- and bismuth-catalysis). We show the few examples reported so far, which however include C−C, C−O, C−S, C−N and C-halide bond-forming reactions, thus showcasing the synthetic potential of this new type of catalysis.
Carbon quantum dots for efficient hydrogen production: A critical review
- First Published: 17 February 2024
Carbon quantum dots (CQDs), or fluorescent carbon nanoparticles, have attracted a lot of attention due to their many uses in chemical sensing, biomedical imaging, nanotechnology, photovoltaics, LEDs, and hydrogen production. This review's main goal is to provide a detailed analysis and highlight the revolutionary potential of CQDs in advancing hydrogen-generating technology.
An Overview of Syntheses of Salvinorin A and its Analogues
- First Published: 26 February 2024
Salvinorin A, a potent human hallucinogen, uniquely activates the kappa-opioid receptor (κ-OR) with high efficacy and selectivity. Its novel structure lacks nitrogenous components, distinguishing it from other opioids. With a complex trans-decalin core and δ-lactone fused with a furan moiety, synthetic access to Salvinorin A remains challenging due to a sensitive epimerizable center. Despite considerable synthetic efforts, only nine syntheses have been produced. This review aims to offer insights into the primary strategies employed to accomplish the syntheses documented thus far.
Mechanism and Kinetics Guided Design of Catalysts for Functionalized Nitroarenes Hydrogenation
- First Published: 01 March 2024
This review describes the overview of mechanistic and kinetics insights for guiding the design of catalysts for selective hydrogenation of functionalized nitroarenes to produce anilines, and summarizes the strategies developed for controlling the selectivity to target product, including isolating active sites, constructing synergistic active sites and regulating local environments of active sites.
Electrocatalytic Applications of Carbon Dots and Their Composites
- First Published: 11 March 2024
CDs are promising electrocatalysis for HER, OER, ORR, CO2RR and other reactions. This review aims to help readers better understand the application of CDs in the field of electrocatalysis, reveal the reasons that affect electrocatalytic performance, and guide for further constructing more efficient, stable, and green electrocatalysts.
Advance of Single-Atom Catalysts Confined into Pristine Metal-Organic Frameworks and their Energy-Related Applications
- First Published: 19 March 2024
MOF supported single-atom catalysts (SACs) have been shown remarkable potential in the energy-related application. This review summaries the reported fabrication strategies, characterizations, and energy related applications of MOF-based SACs, and highlight the challenges and future directions of MOF-based SACs.
Recent Development in Synthesis of N-Methylamines with Amines and Methanol
- First Published: 22 March 2024
Carbon-Nitrogen bond formation plays a key role in the synthesis of functional organic intermediates. This review comprehensively summarized the N-methylation transformation of amine with methanol through the catalytic system of homogenous, heterogenous and photocatalyst, including that of mechanism study. Finally, the development direction of catalyst design for N-methylation was prospected.
Progress through Temporal Analysis of Products and Steady-state Isotopic Transient Kinetic Analysis to Elucidate Oxidation, CO2 Hydrogenation and Lower Olefins Production Reactions
- First Published: 25 March 2024
This review highlights the contributions Temporal Analysis of Products and Steady-State Isotopic Transient Kinetic Analysis have made for elucidating mechanistic and kinetic aspects of oxidative coupling of methane, CO/CO2 hydrogenation, metathesis of ethylene with 2-butenes, acrolein oxidation, methanol conversion, and non-oxidative propane dehydrogenation. We focus on clarifying individual reaction pathways including the kind, concentration, and lifetime of reactive surface intermediates.
Interface Engineering of Electrocatalysts for Efficient and Selective Oxygen Evolution in Alkaline/Seawater
- First Published: 25 March 2024
This review unravels the recent achievements in electrocatalysts for alkaline seawater oxidation through interface engineering. We define the interface types and classify them based on the interfacial configurations. Then, we summarize the recent studies on electrocatalysts developed through interface engineering to elaborate the interfacial effects on promoting the OER processes in both alkaline electrolyte and seawater.
Concept
The Construction of Helical Carbon-Based Skeletons for Enhanced Electrocatalytic Performance
- First Published: 07 March 2024
The helical structure is adopted to achieve the periodic surface curvature for carbon-based skeleton to regulate the electronic structure of electrocatalyst, which endows carbon-based materials with special catalytic properties. In this Concept, synthesis strategies of different characteristics, and further corresponding heteroatom load for helical carbon-based skeleton are summarized.
One-Pot Reactions in Different Sites: A New Approach in Hydroformylation-Based Processes
- First Published: 26 March 2024
Integrated Electrolytic Hydrogen Production for Boosting Energy Utilization
- First Published: 04 April 2024
Hydrogen shows promise for a sustainable energy future, but current electrolysis faces challenges due to the high energy demand of the anode oxygen evolution reaction (OER). This study focuses on integrated electrolysis that replaces OER with specific anodic oxidations and offers insights for cost-effective and highly efficient hydrogen production systems.
Cobalt/Photoredox Cooperative Catalysis-Enabled Cycloaddition Reactions of 1,6-Diynes and Related Compounds
- First Published: 08 April 2024
The combination of cobalt and photoredox catalysis displays high activity in the cycloaddition reactions of unsaturated substrates bearing a 1,6-diyne motif. This Concept outlines recent progress in the study of cycloaddition reactions mediated by Co/photoredox cooperative catalysis. Versatile polycyclic products can be obtained via metallole intermediates, which can facilitate the activation of σ-bonds such as C−O and C−H bonds.
Novel Alkane Dehydrogenation Routes via Tailored Catalysts
- First Published: 10 April 2024
Novel alkane dehydrogenation routes, including CO2 assisted dehydrogenation, chemical looping oxidative dehydrogenation, dual-path dehydrogenation and auto-accelerated multiple alkane dehydrogenation routes, are highlighted in this Concept. Rational design of corresponding catalysts, proper choice of reaction conditions and the in depth understandings on the reaction mechanism and structure-function relations are summarized as the key in these reaction routes.
Research Article
Synthesis-Structure-Catalysis Relations in CHA Zeolites Applied for Selective Catalytic Reduction of NOx with Ammonia
- First Published: 07 May 2024
The selective catalytic reduction of NOx with NH3 was tested using CHA zeolites synthesized from different starting materials in the presence of tetraethylammonium hydroxide. Stepwise gel preparation (SGP) promoted the formation of abundant paired aluminum sites, which resulted in the high catalytic performance and high hydrothermal stability of the obtained CHA zeolite.
Stabilizing Layered BiOBr Photoelectrocatalyst by Van Der Waals Heterojunction Strategy
- First Published: 06 May 2024
In MoS2/BiOBr photocathode, the active electrons from both UV light and electric field can either reduce the adsorbed H* on the edge of MoS2 to H2 or reduce BiOBr to Bi. Varying the MoS2 content in the HJ impacts the stability of BiOBr in PEC HER. HJs with 1 % MoS2 enhance BiOBr stability, while those with 50 % accelerate BiOBr reduction.
Dehydrogenative Oxidation of Alcohols by Reusable Iridium Catalysts with a Cooperative Polymer Ligand
- First Published: 27 February 2024
High catalytic performance of the iridium-polymer complex for the dehydrogenative oxidation of alcohols was demonstrated. Bipyridonate moiety in the polymer structure acts as a cooperative “functional ligand”, realizing the enhancement of dehydrogenation of various alcohols. Further, recovered catalyst could be reused without loss of catalytic efficiency at least ten times.
Impact of the Potential Dependent Surface Adlayer Composition on the ORR Activity and H2O2 Formation on Ru(0001) in Acid Electrolytes
- First Published: 29 February 2024
Classical mechanisms for the oxygen reduction reaction on metal electrodes require an adsobrate free surface. On the example of Ru single crystal electrodes, which are never free from adsorbates, we show that depending on the potential and electrolyte the reaction is either inhibited or can even lead to the formation of significant amounts of hydrogen peroxide.
Vicinal Diones and α-Keto Esters as Electrophiles of Aldolases for Stereoselective Construction of Tertiary Alcohols
- First Published: 07 March 2024
First Insight into the Catalytic Activity of Stereolithographically 3D-Printed Tannin-Based Carbon Architectures
- First Published: 11 March 2024
Honeycomb carbon monoliths with different textural properties and surface chemistry were obtained from by stereolithography 3D printing of tannin-based resins. These new, architected materials have shown interesting performance as catalysts for the ozonation of oxalic acid and as catalyst supports for the hydrogenation of bromate ions in solution. They thus highlight the potential of 3D carbons for heterogeneous catalysis as an alternative to macro-structured carbonaceous catalysts.
Diamine-Assistant Synthesis of Cu@MFI Catalysts for Ethanol Dehydrogenation
- First Published: 21 March 2024
Stable Cu catalysts for ethanol dehydrogenation: Low-cost diamines of ethylenediamine and propanediamine were effective chelators to encapsulate Cu species into the framework of MFI under basic and thermal conditions, resulting in >96 % ethanol conversion and 98 % acetaldehyde selectivity in the 300 h time on stream for the ethanol direct dehydrogenation reaction.
Confinement Effects in Catalysis: Steering the Product Selectivity in Cannabidiol Isomerization by the Resorcinarene Supramolecular Capsule
- First Published: 21 March 2024
The confinement effect provided by the resorcinarene hydrogen bonded capsule in the presence of HCl accelerates the isomerization of cannabidiol leading to cyclic and hydrated products that are uncommon compared to the same reaction with traditional strong Brønsted acids, thus widening the chemical scenario provided by the capsule.
Synthesis and Characterization of Co(II) Substituted Keggin-Type Polyoxometalates as Novel Catalysts for the Hydroformylation of 1-Hexene in a Thermomorphic Solvent System
- First Published: 21 March 2024
Donor-Acceptor Pyrene-Based Covalent Organic Framework for Blue Light Photocatalytic Oxidative Coupling of Amines
- First Published: 26 March 2024
Donor-Acceptor Covalent Organic Frameworks (COFs) are excellent photocatalysts with tunable band positions and good charge mobility. Three pyrene-based COFs are synthesized for the aerobic coupling of amines with blue-LED irradiation. The selective amine coupling proceeds with an apparent quantum yield of 11.3 % at 420 nm. All COFs are stable and recyclable.
Scalable Bioreactor Production of an O2-Protected [FeFe]-Hydrogenase Enables Simple Aerobic Handling for Clean Chemical Synthesis
- First Published: 28 March 2024
The enzyme CbA5H from Clostridium beijerinckii, the only known [FeFe]-hydrogenase able to survive exposure to oxygen, was evaluated here in biotechnologies for sustainable chemical synthesis. Enzyme production was optimized in a scalable bioreactor. CbA5H was purified aerobically, characterized using benchtop activity assays, and used to drive biocatalytic hydrogenations for example in the preparation of pharmaceutical fragment (3)-quinuclidinol at 0.4 g scale.
Engineering Tauriopine Dehydrogenase for Efficient Catalytic Synthesis of (R)-Alpha-Ethyl-2-Oxo-1-Pyrrolidineacetic Acid
- First Published: 28 March 2024
The synthetic pathway for (R)-Etiracetam critically hinges on (R)-alpha-ethyl-2-oxo-1-pyrrolidineacetic acid ((R)-AEOPA). We divided the synthesis of (R)-AEOPA into two steps of enzymatic and chemical synthesis, and focused on enzymatic synthesis of intermediates (R)-4-(carboxypropylamino) butyric acid ((R)-4-CPAB), The strains with high yield of (R)-CPAB were obtained by structural mechanism analysis and protein engineering.
Cobalt-Catalyzed Wacker-Type Aerobic Oxidation of Olefins into Ketones Enabled by PMHS: Giving Value to a Chemical Waste with Optimal Atom-Economy
- First Published: 02 April 2024
The first example of using polymethylhydrosiloxane (PMHS), a major chemical waste from the silicon industry, as stoichiometric hydrosilane source for the aerobic Wacker-type oxidation of olefins into ketones is reported thanks to an Earth-abundant-based cobalt catalyst. The catalysis occurs at industrially-relevant conditions, namely 70 °C and one bar of oxygen pressure with ethanol as a relatively green solvent.
NiFe Catalysts for Oxygen Evolution Reaction: Is There an Optimal Thickness for Generating a Dynamically Stable Active Interface?
- First Published: 01 April 2024
A Non-Macrocycle Thiolate-Based Cobalt Catalyst for Selective O2 Reduction into H2O
- First Published: 03 April 2024
Co-based catalysts, recognized for preferentially converting O2 to H2O2, shift selectivity to H2O production in the presence of thiolate donors in the first coordination sphere. Transitioning from Mn or Fe to Co, using the same N2S2 ligand, also alters selectivity, highlighting the impact of the nature of the metal ion.
On the Mechanism of the Lysosomal Enzyme Iduronate-2-sulfatase. A Multiscale Approach
- First Published: 02 April 2024
Molecular dynamics and QM/MM calculations are carried out to provide mechanistic insights on the hydrolysis of dermatan sulfate by the Ca2+-dependent iduronate-2-sulfatase, an enzyme is involved in the occurrence of Hunter disease. The computations highlight the role played by the amino acids in the substrate binding as well as in the catalytic reaction.
Magnetically Reusable Carbon Nanotube Coated Co-based Catalysts towards Highly Efficient Transfer Hydrogenation of Nitroarenes
- First Published: 02 April 2024
Tri-reforming of Methane over a Hydroxyapatite Supported Nickel Catalyst
- First Published: 07 April 2024
Synthesis, Characterization and Reactivity Studies of Cobalt(III) Porphyrin-Iodosylarene Adduct and Cobalt(III) Porphyrin π-Cation Radical Species
- First Published: 03 April 2024
Cobalt(III) porphyrin-ArIO adduct complexes have been synthesized and characterized. The O−I bond cleavage of cobalt(III) porphyrin-ArIO adduct is promoted in the presence of acid, forming cobalt(III) porphyrin π-cation radical species, which is much more reactive than the corresponding adduct species in electron transfer reactions. While the oxidation of metal centre is inhibited due to the “oxo-wall” for late transition metals.
Catalytic Asymmetric Approach to 1,3,4,5-Tetrahydro-1,4-benzodiazepin-2-ones in One-Pot
- First Published: 03 April 2024
A first catalytic and asymmetric synthesis of medicinally relevant tetrahydro-1,4-benzodiazepin-2-ones and unprecedented 1,5-dihydro-4,1-benzoxazepin-3(2H)-ones, has been developed. The telescoped approach relies on the use of commercially available reagents, recyclable organocatalyst and a single solvent. The heterocycles were isolated in good overall yield (30-69 %) and satisfactory to high enantioselectivity (up to 98 % ee).
P and O Co-Doped Pt−Co Octahedral Nanocrystals as Highly Active and Stable Electrocatalysts for Oxygen Reduction Reaction
- First Published: 08 April 2024
The co-doping of P and O in Oct PtCo/C has been found to significantly enhance ORR (oxygen reduction reaction) activity through strain and ligand effects. Simultaneously, the robust interaction between Co and O effectively impedes Co dissolution, thereby markedly improving the stability of the catalyst.
Uniformly Distributed Palladium Nanoparticles on NH2-MIL-53 Fabricated by an Equilibrium Adsorption Method for Reduction of Nitrite in Water
- First Published: 07 April 2024
Pd nanoparticles (about 2 nm) with uniform distribution were formed on NH2-MIL-53 despite of high loading, by a facile equilibrium adsorption method. The obtained catalysts showed high activity for catalytic reduction of nitrite in water, due to the preferential exposure of Pd(111) facets on Pd nanoparticles.
Improving Oxidative Catalytic Efficiency for Fuels Desulfurization Using Hybrid Materials Based in MOF-808@SBA-15
- First Published: 11 April 2024
An unprecedented tri-hybrid material, PMo12@MOF-808@SBA-15, revealed a notable catalytic performance and robustness to desulfurize a multicomponent model fuel containing approximately 1500 ppm of sulfur. It demonstrated an enhanced activity and recyclability relatively to the parent's composites, PMo12@MOF-808 and PMo12@SBA-15.
Molecular Electrocatalysis under Finite Diffusive Mass Transport Conditions. An Analytical Approach
- First Published: 08 April 2024
A significant gap exists in the theoretical understanding of the interplay between different kinetics and mass transport in molecular electrocatalysis within confined spatial domains. Here, an expression for the current-potential-time response of a catalytic reaction occurring under these conditions is presented. From this approach, the effects of finite diffusion on the efficiency of these processes can be quantified.
In-Situ Investigations of Polyoxometalate-Catalysed Biomass Oxidation to Formic Acid by Using Multinuclear High Resolution Flow NMR Spectroscopy
- First Published: 10 April 2024
Influence of Ylide Functionalization on the Catalytic Performance of Ferrocenyldiphosphines in Au(I)-Catalyzed Hydroaminations and Hydrohydrazinations
- First Published: 10 April 2024
The catalytic performance of a series of gold complexes based on ferrocenyldiphosphines with or without ylide substituents was compared in the hydroamination and hydrohydrazination of alkynes. Each introduction of a ylide group resulted in a significant increase in activity, resulting in highly active catalysts for a variety of substrates.
Ionic Liquid-Silver Catalysts for Acetylene Acetoxylation at Low-Temperature
- First Published: 14 April 2024
In this work, Ag-IL/AC catalysts were synthesized by loaded ILs phase dispersion technique, the presence of ILs stabilized the Ag species to maintain the Ag+ state and improved the dispersion of the Ag species. As a result, the catalytic performance of the Ag-IL/AC catalysts was 2.5 times higher than that of the conventional Zn/AC catalysts at a low-temperature of 180 °C.
Highly Stereoselective Synthesis of 1,3-Enynes via Aryl to Vinyl 1,4-Palladium Migration/Sonogashira Coupling Sequence
- First Published: 11 April 2024
Transient In situ DRIFTS Investigation of CO2 Hydrogenation to Methanol over Unsupported CuGa Catalysts
- First Published: 15 April 2024
Transient in situ DRIFTS investigation of CO2 hydrogenation to methanol over unsupported CuGa and CuGaN (with N doping) catalysts was conducted. N doping could possibly promote the formation of Cu+ sites and weak the CO interaction on catalyst surface, while prohibited the reduction of Ga2O3 to oxygen-deficient Ga2O3-x. H2/D2 isotope exchange SSITKA results confirm that the Cu+-bound formates could possibly serve as key intermediates for methanol synthesis.
In Situ Formation of Suspended Graphene Windows for Lab-Based XPS in Liquid and Gas Environments
- First Published: 21 April 2024
In situ X-ray photoelectron spectroscopy (XPS) of a reaction at the solid-liquid interface is performed in a lab-based system under ultra-high vacuum conditions (UHV). To enable this, a PDMS/Au-supported transfer process is demonstrated that reliably produces continuous, high-quality and contamination-free suspended graphene windows which successfully seal liquids and high pressure (~1 bar) gases.
Addressing the Activity and Selectivity Challenges for CO2 Reduction via Transition-Metal-Free Homo- and Hetero-Biatomic Catalysts Embedded in Two-Dimensional Networks
- First Published: 15 April 2024
Regioselective Ring Opening of Epoxide with Alcohols: A Selective Route to α-Alkylated Ketones and β-Alkylated Secondary Alcohols
- First Published: 17 April 2024
A tandem catalytic protocol for the selective synthesis of α-alkylated ketones and β-alkylated secondary alcohols directly from epoxide and alcohol coupling is developed by employing a phosphine-free, air and moisture stable Ir(III) complex bearing 2-(2-benzimidazolyl)-6-hydroxypyridine ligand using considerably lower base at lower temperature. Several control experiments are carried out to understand the catalytic process.
Corrigendum
Corrigendum: Corrigendum to “A Hydride Migration Mechanism for the Mo-Catalyzed Z-2-Selective Isomerization of Terminal Alkenes”
- First Published: 25 April 2024