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Reaction barriers for molecules dissociating on metal surfaces (as relevant to heterogeneous catalysis) are often difficult to predict accurately with density functional theory (DFT). Although the results obtained for several dissociative chemisorption reactions via DFT in the generalized gradient approximation (GGA), in meta-GGA, and for GGA exchange + van der Waals correlation scatter around the true reaction barrier, there is an entire class of dissociative chemisorption reactions for which GGA-type functionals collectively underestimate the reaction barrier. Little is known why GGA-DFT collectively fails in some cases and not in others, and we do not know whether other methods suffer from the same inconsistency. Here, we present barrier heights for dissociative chemisorption reactions obtained from the random phase approximation in the adiabatic-connection fluctuation-dissipation theorem (ACFDT-RPA) and from hybrid functionals with different amounts of exact exchange. By comparing the results obtained for the dissociative chemisorption reaction of H2 on Al(110) (where GGA-DFT collectively underestimates the barrier) and H2 on Cu(111) (where GGA-DFT scatters around the true barrier), we can gauge whether the inconsistent description of the systems persists for hybrid functionals and ACFDT-RPA. We find hybrid functionals to improve the relative description of the two systems, but to fall short of chemical accuracy. ACFDT-RPA improves the results further and leads to chemically accurate barriers for both systems. Together with an analysis of the density of states and the results from selected GGA, meta-GGA, and GGA exchange + van der Waals correlation functionals, these results allow us to discuss possible origins for the inconsistent behavior of GGA-based functionals for molecule–metal reaction barriers. [ABSTRACT FROM AUTHOR]

The random phase approximation (RPA) as a means of treating electron correlation recently has been shown to outperform standard density functional theory (DFT) approximations in a variety of cases. However, the computational cost of the RPA is substantially more than DFT, especially when aiming to study extended surfaces. Properly accounting for sufficient surface ensemble size, Brillouin zone sampling, and vacuum separation of periodic images in standard periodic-planewave-based DFT code raises the cost to achieve converged results. Here, we show that sub-system embedding schemes enable use of the RPA for modeling heterogeneous reactions at reduced computational cost. We explore two different embedded RPA (emb-RPA) approaches, periodic emb-RPA and cluster emb-RPA. We use the (experimentally and theoretically) well-studied H2 dissociative adsorption on Cu(111) as our exemplar, and first perform full periodic RPA calculations as a benchmark. The full RPA results match well the semi-empirical barrier fit to experimental observables and others derived from high-level computations, e.g., from recent embedded n-electron valence second order perturbation theory [Zhao et al., J. Chem. Theory Comput. 16(11), 7078–7088 (2020)] and quantum Monte Carlo [Doblhoff-Dier et al., J. Chem. Theory Comput. 13(7), 3208–3219 (2017)] simulations. Among the two emb-RPA approaches tested, the cluster emb-RPA accurately reproduces the energy profile (maximum error of 50 meV along the reaction pathway) while reducing the computational cost by approximately two orders of magnitude. We therefore expect that the embedded cluster approach will enable wider RPA implementation in heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

The propensity of water to remain in a metastable liquid state at temperatures below its equilibrium melting point holds significant potential for cryopreserving biological material such as tissues and organs. The benefits conferred are a direct result of progressively reducing metabolic expenditure due to colder temperatures while simultaneously avoiding the irreversible damage caused by the crystallization of ice. Unfortunately, the freezing of water in bulk systems of clinical relevance is dominated by random heterogeneous nucleation initiated by uncharacterized trace impurities, and the marked unpredictability of this behavior has prevented the implementation of supercooling outside of controlled laboratory settings and in volumes larger than a few milliliters. Here, we develop a statistical model that jointly captures both the inherent stochastic nature of nucleation using conventional Poisson statistics as well as the random variability of heterogeneous nucleation catalysis through bivariate extreme value statistics. Individually, these two classes of models cannot account for both the time-dependent nature of nucleation and the sample-to-sample variability associated with heterogeneous catalysis, and traditional extreme value models have only considered variations of the characteristic nucleation temperature. We conduct a series of constant cooling rate and isothermal nucleation experiments with physiological saline solutions and leverage the statistical model to evaluate the natural variability of kinetic and thermodynamic nucleation parameters. By quantifying freezing probability as a function of temperature, supercooled duration, and system volume while accounting for nucleation site variability, this study also provides a basis for the rational design of stable supercooled biopreservation protocols. [ABSTRACT FROM AUTHOR]

The niobium-based nanocomposite (Nb-CP), inspired by MOF-based synthesis, was developed utilizing the ligands 4-benzenedicarboxylic acid (BDC) and 1,3,5-benzenetricarboxylic acid (BTC). This material was decorated with bimetallic nanoparticles (Ni 2 /Pt 8 NPs-Nb-CP) and applied for the first time for hydrogen evolution from sodium borohydride (NaBH 4). Characterization results indicated successful synthesis. The FT-IR analysis revealed the presence of functional groups such as -C-H, –C O, and -O-H from ligands in the composite. Thermogravimetric analysis confirmed the thermal stability of the niobium composite (Nb-CP). Through X-ray diffraction (XRD), peaks associated with sodium niobate were detected. Additionally, the material was functionalized with bimetallic Ni/Pt nanoparticles, whose presence was also identified by XRD. The cubic morphology of the material was observed, with the decoration of bimetallic nanoparticles (Ni 2 /Pt 8 NPs-Nb-CP) with an average size of 7.80 ± 0.10 nm, uniformly distributed in Nb-CP. The catalytic performance of the material was evaluated in hydrogen evolution from NaBH 4. Various reaction parameters were investigated, such as nanoparticle composition, variation in NaBH 4 concentration, catalyst dose, NaOH concentration, and temperature. Remarkably, the material exhibited a hydrogen generation rate (HGR) of 1782 mL min−1 g−1 cat and an activation energy of 23.1 kJ mol−1. Furthermore, it demonstrated efficiency close to 100% over 16 consecutive reaction cycles, indicating its promising stability and reusability. This study highlights the potential of Ni 2 /Pt 8 NPs-Nb-CP as an efficient and durable catalyst for hydrogen production through borohydride hydrolysis, providing insights into the design and application of advanced heterogeneous catalytic materials. [Display omitted] • Ni/Pt nanoparticles were decorated in a novel niobium-based composite. • The material synthesis was inspired by Metal Organic Framework (MOF) synthesis. • The material was employed in NaBH 4 hydrolysis, yielding an HGR of 1782 mL min−1 g−1 cat. • H 2 evolution exhibits an activation energy of 23.1 kJ mol−1. • The material was reused in up to 16 cycles. [ABSTRACT FROM AUTHOR]

A novel type of oxide material, high entropy oxide (Mn0.2Fe0.2Co0.2Ni0.2Cu0.2)3O4 (MFO) composites with spinel structure were successfully synthesized by a simple solution combustion in this paper, and it was first applied to the degradation of antibiotic organic pollutants in water by photo-Fenton. SEM and BET characterization showed that the composite was porous and had a large specific surface area. XPS results showed that Fe, Mn, Cu, Co and Ni all participated in the redox reaction of the catalytic process. The redox pairs of Mn2+/Mn3+, Cu+/Cu2+, Co2+/Co3+, Ni2+/Ni3+ can accelerate the Fe2+/Fe3+ redox cycling in MFO to activate H2O2 and produce more reactive oxygen species. The catalytic performance of MFO composite was investigated using tetracycline hydrochloride (TC-HCl) as a model pollutant. The results displayed that the degradation rate of TC-HCl by MFO was 92.9% when the initial pH was 4, the dose of H2O2 was 50 mM, and the irradiation time was 60 min. The high entropy oxide MFO composites could build up an internal electric field, which restrains electron–hole recombination, improves the transfer of photogenerated charge carriers and maximize photocatalytic property. In addition, the free radical capture experiment determined that the main active species of the degradation reaction were e−, •O2− and •OH. The synergistic effect of the five components in the high entropy oxide strengthens lattice distortion and defects, increases oxygen vacancies, and thus has enhanced catalytic effect for TC-HCl degradation. This work shows that high entropy oxides have excellent catalytic performance for tetracycline organic pollutants, and it is speculated that high entropy oxides have good application prospects in the field of advanced oxidation technology for the degradation of organic pollutants. [ABSTRACT FROM AUTHOR]

ABSTRACT Palladium nanoparticles immobilized on ZIF 67‐derived porous CoOx were prepared by wet‐impregnation method, followed by calcination at different temperatures. The calcination temperature has been employed to effectively manipulate the size of metal nanoparticles, where higher calcination temperatures resulted in larger sizes. The experimental results revealed that by manipulating the calcination temperature, the synthesis of palladium nanoparticles with varying sizes could be effectively controlled. Increasing the calcination temperature resulted in larger particle sizes. At a calcination temperature of 350°C, the synthesis process produced the smallest palladium nanoparticles, averaging 1.35 nm in size, facilitating the reaction between aryl halides and arylboronic acids with yields ranging from 83% to 99%. Furthermore, these nanoparticles demonstrated superior catalytic activity and recyclability. [ABSTRACT FROM AUTHOR]

AbstractZSM-5, an efficient and reusable heterogeneous catalyst, is employed for the one-pot, three-component synthesis of 2,4,6-triarylpyridines from substituted benzaldehydes, acetophenones and ammonium acetate using a simple, efficient, and green method. Both electron-releasing and withdrawing aldehydes and ketones went smoothly into substituted 2,4,6-triarylpyridines. Notably, the present reaction was carried out in the solvent-fee condition. The key merits of the present protocol are the milder reaction condition, easy workup protocol, high yield of desired pyridines and recyclability and reusability of the catalyst. The developed protocol offers a broad scope of substrate applicability and good sustainability. [ABSTRACT FROM AUTHOR]

The valorization of native lignin to functionalized aromatic compounds under visible light is appealing yet challenging. In this communication, colloidal mercaptoalkanoic acid capped ultrathin ZnIn2S4 (ZIS) microbelts was successfully fabricated, which was used as a superior catalyst for depolymerization of native lignin in birch woodmeal under visible light, with an optimum yield of 28.8 wt % to functionalized aromatic monomers achieved in 8 h. The capped mercaptoalkanoic acid not only enables a solvent modulated reversible interchange of ZIS between the colloidal state for efficient reaction and the aggregated state for facile separation, but also serves as a precursor for light initiated generation of reactive thiyl radical for highly selective cleavage of β‐O‐4 bond in native lignin. This work provides a green and efficient strategy for the depolymerization of native lignin to functionalized aromatic monomers under mild conditions, which involves a new mechanism for the cleavage of β‐O‐4 bonds in native lignin. The capability of cleavage of β‐O‐4 bonds in native lignin by photogenerated thiyl radicals also demonstrates the great potential of using photogenerated thiyl radicals in organics transformations. [ABSTRACT FROM AUTHOR]

The Cu‐glutathione (GSH) redox system, essential in biology, is designed here as a supramacromolecular assembly in which the tetrahedral 18e Cu(I) center loses a thiol ligand upon adsorption onto ZIF‐8, as shown by EXAFS and DFT calculation, to generate a very robust 16e planar trigonal single‐atom Cu(I) catalyst. Synergy between Cu(I) and ZIF‐8, revealed by catalytic experiments and DFT calculation, affords CO2 conversion into high‐value‐added chemicals with a wide scope of substrates by reaction with terminal alkynes or propargyl amines in excellent yields under mild conditions and reuse at least 10 times without significant decrease in catalytic efficiency. [ABSTRACT FROM AUTHOR]

Here, we report CdS quantum dot (QD) gels, a three‐dimensional network of interconnected CdS QDs, as a new type of direct hydrogen atom transfer (d‐HAT) photocatalyst for C−H activation. We discovered that the photoexcited CdS QD gel could generate various neutral radicals, including α‐amido, heterocyclic, acyl, and benzylic radicals, from their corresponding stable molecular substrates, including amides, thio/ethers, aldehydes, and benzylic compounds. Its C−H activation ability imparts a broad substrate and reaction scope. The mechanistic study reveals that this reactivity is intrinsic to CdS materials, and the neutral radical generation did not proceed via the conventional sequential electron transfer and proton transfer pathway. Instead, the C−H bonds are activated by the photoexcited CdS QD gel via a d‐HAT mechanism. This d‐HAT mechanism is supported by the linear correlation between the logarithm of the C−H bond activation rate constant and the C−H bond dissociation energy (BDE) with a Brønsted slope α=0.5. Our findings expand the currently limited direct hydrogen atom transfer photocatalysis toolbox and provide new possibilities for photocatalytic C−H activation. [ABSTRACT FROM AUTHOR]

To understand the nature of heterogeneous catalytic processes and improve their efficiency, it is necessary to conduct both experimental and theoretical studies. At the same time, there is no unified approach to obtaining the necessary data using quantum chemistry methods. In this work, problems of the existing calculational approaches are analyzed. The obtained information is used to develop the original three‐layer embedded cluster model approach, which is shown to be the most effective. The general algorithm for obtaining such models for various oxides is formulated. The sufficient accuracy of the proposed models in predicting geometric and energy characteristics, vibrational frequencies, activation barriers, and thermodynamic characteristics is verified. The specifics of calculating the thermodynamic characteristics of heterogeneous processes using the proposed cluster models is studied in detail. The developed approach is an effective tool for studying the mechanism of heterogeneous catalytic processes both by itself and in combination with experiment. [ABSTRACT FROM AUTHOR]

AbstractGiven the abundance of functional groups, meso- and macro-pores, and a high surface area, the piperazine-based poly(amic acid) was employed as a heterogeneous catalyst in the multicomponent reaction to prepare pyrrolidinone scaffolds in a green solvent, acting as a medium for mass transfer and crystallization solvent. The important parameters of the reaction were investigated to find the optimal reaction conditions. A conversion of 100% was obtained at reflux conditions within 30–100 min using a catalytic amount of 200 mg of piperazine-based poly(amic acid) per 2 mmol of reactants (100 mg of cat./1 mmol of reactant). The piperazine-based poly(amic acid) exhibited high recyclability and the recovered catalyst could be used in successive runs without worthy loss in its activity. This work revealed the catalytic activity of the piperazine-based poly(amic acid) as a promising functional polymeric heterogeneous catalyst for organic synthesis. [ABSTRACT FROM AUTHOR]

Herein, we present an efficient, one‐pot reaction for accessing 3‐benzylated indoles via the coupling of benzyl alcohols with indoles under heterogeneous catalysis by manganese ferrite (MnFe2O4) nanoparticles. Notably, this reaction, for the first time, employs MnFe2O4 nanoparticles prepared using a simple grinding method. The high compatibility of MnFe2O4 nanoparticles enables a broad substrate scope and high regioselectivity. Moreover, this approach offers several attractive highlights including the use of a recyclable oxide catalyst and green and cost‐effective alkylating reagents under solvent‐free conditions. [ABSTRACT FROM AUTHOR]

The present article includes systematic update information with recent developments in nanocatalyzed organic transformations with the special emphasis on the use of nanostructured heterogeneous catalysts in multi‐component syntheses of structurally diverse drug‐like small molecules incorporating medicinally privileged heterocyclic systems. Moreover, the nanocatalyzed transformations included in the article are environmentally sustainable and will provide an access to a diverse range of heterocyclic scaffolds with the use of combinatorial chemistry in the presence of heterogeneous catalysts. The reaction mechanisms involving catalytic facilitation with the interaction of nanostructured catalysts with the reacting molecules have also been included. The nanocatalyzed multi‐component reactions included in the article will be important significantly for designing synthetic protocols to synthesize natural product mimetic scaffolds with privileged heterocyclic ring systems. Thus, the present review article will contribute considerably not only to the chemical research, especially organometallics, organic syntheses and catalyses, but also to the drug discovery research with the emphasis on pharmaceutical and medicinal research. The present review article presents a thorough and balanced view of the subject. [ABSTRACT FROM AUTHOR]

Using halloysite clay and vitamin B1 hydrochloride, a novel acidic halloysite-dendrimer catalytic composite has been developed for conversion of fructose to 5-hydroxymthylfurfural. To grow the dendritic moiety on halloysite, it was first functionalized and then reacted with melamine, epichlorohydrin and vitamin B1 hydrochloride respectively. Then, the resulting composite was treated with ZnCl2 to furnish Lewis acid sites. Use of vitamin B1 as the cationic moiety of ionic liquid obviated use of toxic chemicals and resulted in more environmentally friendly composite. Similarly, dendritic moiety of generation 2 was also grafted on halloysite and the activity of both catalysts for conversion of fructose to 5-hydroxymthylfurfural was investigated to disclose the role of dendrimer generation. For the best catalytic composite, the reaction variables were optimized via RSM and it was revealed that use of 0.035 g catalyst per 0.1 g fructose at 95 °C furnished HMF in 96% yield in 105 min. Turnover numbers (TONs) and frequencies (TOFs) were estimated to be 10,130 and 5788 h−1, respectively. Kinetic studies also underlined that Ea was 22.85 kJ/mol. The thermodynamic parameters of Δ H ≠ , Δ S ≠ and Δ G ≠ , were calculated to be 23 kJ/mol, − 129.2 J/mol and 72.14 kJ/mol, respectively. Notably, the catalyst exhibited good recyclability and hot filtration approved heterogeneous nature of catalysis. [ABSTRACT FROM AUTHOR]

ABSTRACT One‐pot synthesis of acetamides, benzimidazoles, and benzothiazoles are central reactions for synthesizing pharmaceuticals and fine chemicals. Despite tremendous progress in heterogeneous catalysis, the synthesis of these nitrogen‐containing compounds still remains challenging. Here, we report an efficient, simple, and cost‐effective nitrogen‐doped CeO2‐supported Co single‐atom catalyst (SAC) (Co/N‐CeO2) enabled synthesis of acetamides, benzimidazoles, and benzothiazoles. As far as we know, this is the first to report that SACs catalyze the synthesis of acetamides, benzimidazoles, and benzothiazoles. Detailed spectroscopic characterization revealed the structure of catalytic center. Harnessing the catalytic activity of SACs, the work offers promising routes for future synthesis of heterocycles. [ABSTRACT FROM AUTHOR]

The electronic structure of active metal centers plays an indispensable role in regulating catalytic reactivity in heterogeneous catalysis, developing other metals as promoters to decorate electronic state is a common strategy, while non‐metal component of carbon as electronic additives to regulate d‐band center has rarely been studied in thermal‐catalysis field. Herein, we report electron‐deficient tetrahedral Co(II) (Td‐cobalt(II)) centers through carbon‐layer modulation for propane dehydrogenation (PDH). It is indicated that bifunctional sites of both Td‐cobalt(II) and metallic‐cobalt are designed, and the in situ generated carbon through the disproportionation of CO on metallic‐cobalt can cover the inactive metallic‐cobalt and tailor d‐band of active Td‐cobalt(II) simultaneously. More importantly, the pre‐deposited carbon‐layer is proposed to decrease electron density of Td‐cobalt(II) and make d‐band center closer to Fermi level, consequently promotes C−H activation in PDH reaction. This study provides new perspective for the utilization of inactive carbon as electronic promoters and unlocks new opportunity to fabricate efficient PDH and other heterogeneous catalysts. [ABSTRACT FROM AUTHOR]

Metal-oxide interfaces with poor coherency have specific properties comparing to bulk materials and offer broad applications in heterogeneous catalysis, battery, and electronics. However, current understanding of the three-dimensional (3D) atomic metal-oxide interfaces remains limited because of their inherent structural complexity and the limitations of conventional two-dimensional imaging techniques. Here, we determine the 3D atomic structure of metal-oxide interfaces in zirconium-zirconia nanoparticles using atomic-resolution electron tomography. We quantitatively analyze the atomic concentration and the degree of oxidation, and find the coherency and translational symmetry of the interfaces are broken. Atoms at the interface have low structural ordering, low coordination, and elongated bond length. Moreover, we observe porous structures such as Zr vacancies and nano-pores, and investigate their distribution. Our findings provide a clear 3D atomic picture of metal-oxide interface with direct experimental evidence. We anticipate this work could encourage future studies on fundamental problems of oxides, such as interfacial structures in semiconductor and atomic motion during oxidation process. A detailed understanding of metal-oxide interfaces is essential for uncovering their intrinsic properties. Here, the authors investigate the 3D atomic structure of metal-oxide interfaces in Zr-ZrO2 nanoparticles using atomic-resolution electron tomography. [ABSTRACT FROM AUTHOR]

This study systematically evaluates fluorine‐containing materials with varying compositions of K, Al, Co, Cu, Mg, and Zn as catalysts for glycerol oligomerization. Comprehensive analyses were conducted for all of the catalysts, considering their structural, compositional, morphological characteristics, and basicity, to understand them in greater depth. Among these analyses, gas chromatography was employed to examine the composition of the reaction products. The investigation extended to a recycling study under optimized conditions. Thermogravimetric analysis and X‐ray photoelectron spectroscopy were used to characterize the spent catalysts. Catalytic activity was found to be influenced strongly by the fluorine content, demonstrating remarkable performance for the materials containing fluoroperovskites such as KMgF3 in the catalyst KMgAFC, and K2ZnF6 in KZAFC. Remarkably, KZAFC with 20% fluorine exhibited superior glycerol conversion (68%) and selectivity for diglycerol (27%). Comparative analysis with ZnAl‐layered double hydroxide highlighted the positive impact of fluorine on catalytic activity. Introducing a calcination step in the catalyst recovery process also demonstrated improved activity during recycling. Interestingly, KZAFC exhibited stability over four reaction cycles, presenting an economic advantage over homogeneous catalysts. The study also shed light on the potential fluorine loss at the surface and potassium leaching into reaction products, correlating these phenomena with the observed decline in activity. These comprehensive findings contribute significantly to advancing sustainable glycerol valorization through heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Catechol‐formaldehyde resin (CFR) is very attractive for H2O2 production via the catalytic process. However, the H2O2 formation is accompanied by the oxidation of catechol groups to o‐benzoquinone groups on CFR, which will cause irreversible damage to CFR and greatly limit its long‐term stable catalytic activity. Herein, CdS/CFR composite photocatalyst with a core‐shell structure was synthesized by hydrothermal method. The photogenerated electrons of CdS are used as a powerful driving force for the reversible redox conversion between catechol groups and o‐benzoquinone groups on the CFR, which not only achieves the long‐term stability of CFR‐catalyzed production of H2O2, but also promotes the separation efficiency of photogenerated e– and h+ in CdS, greatly inhibiting their recombination, so as to maintain CdS stability. The H2O2 yield of CdS/CFR can accumulate to 1.65 mmol·L–1 under visible light for 6 h without sacrificial agent, which is about 3.1 and 2 times that of CdS and CFR, respectively, and CdS/CFR can persist for 10 cycles of photocatalysis (60 h). CdS/CFR also improves the yield of photocatalytic H2O2 by increasing the selectivity of H2O2 and inhibiting its decomposition. This work offers a novel tactic for expanding the application of CFR in photocatalytic generation of H2O2. [ABSTRACT FROM AUTHOR]

1-Butanol, primarily sourced from petroleum, is currently being considered as a viable alternative to gasoline. Various pathways for synthesizing 1-butanol from renewable raw materials have been explored, with a particular focus on the Guerbet reactions. This study aimed to investigate the synthesis of 1-butanol from ethanol using Mg/Al mixed oxides derived from layered double hydroxides with Mg/Al molar ratios of 3:1, 5:1, 8:1, and 10:1. The catalysts were analyzed through X-ray diffraction, X-ray fluorescence, N2 adsorption, scanning electron microscope and energy-dispersive X-ray spectroscopy. Catalytic reaction tests were performed according to a Central Composite Rotatable Design (CCRD) with three replicates at the central point (CP). Among the catalysts tested at CP, the mixed oxides with Mg/Al molar ratios of 3:1 and 5:1 exhibited the most promising results, displaying similar ethanol conversion, and 1-butanol selectivity. This similarity underscores their well-balanced combination of both acidic and basic sites. However, further assessment through a deactivation test revealed that the mixed oxides with Mg/Al molar ratio of 5:1 held the most potential for long-term 1-butanol synthesis from ethanol, thanks to its superior stability and sustained activity. Using this catalyst, other reaction tests were carried out following the CCRD, varying N2 feed flowrate, ethanol molar content in feed flowrate, and temperature. The results indicated that an increase in ethanol conversion directly correlated with higher temperatures, while the 1-butanol selectivity depended on both the N2 feed flowrate, ethanol molar content in feed flowrate, highlighting the importance of a well-balanced combination of both acidic and basic sites. [ABSTRACT FROM AUTHOR]

In PMS catalytic oxidation studies, we design and prepare a Mn3O4/CuO (CMO-2) composite catalyst using metal–organic frameworks (MOFs) as precursors. Compared with Mn3O4, its activated per-oxy-monosulfate activation catalyzed the degradation of pollutants with nearly six times higher activity efficiency. The experimental findings demonstrate that CMO-2 derived from metal–organic frameworks offer the advantages of wide adaptability to solution pH, along with improved versatility, stability, and recyclability. Further experiments involving radical scavenging, electrochemistry, and electron spin resonance (EPR) techniques confirm that the CMO-2 derived from MOF structures exhibit more significant interfacial engineering effects. This leads to an expansion of active interfaces, enhancing the accessibility and dispersion of active sites. Consequently, it significantly improves the efficiency of electron-transfer reactions and promotes a wide range of reactive oxygen species (ROSs), including SO4•− •OH and1O2. Based on the synergistic effect of copper-manganese bimetallic, the copper-manganese composite catalyst (CMO-2) prepared by doping 0.5 g of Cu-MOF showed the best catalytic activity in activating PMS, and the resulting ROSS could efficiently degrade organic pollutants. [ABSTRACT FROM AUTHOR]

Camelina sativa plant residue was used as feedstock for the production of biogasoline (a mixture of paraffinic and olefinic hydrocarbons) by catalytic hydrothermal liquefaction (cHTL) process. The experiments were conducted at temperature range 200–375°C and pressure range 10–19 MPa. Molecular hydrogen was added for the hydro-deoxygenation processes. Various experiments were performed to understand the contributions of process parameters such as temperature, pressure, hydrogen, and retention time on reaction conversion and products distribution. This was followed by screening of different catalyst supports – γ-Al2O3, HZSM-5, SiO2-Al2O3, SBA-15, and Al2O3-HZSM-5 to understand their impacts as well as catalytic activities. The Al2O3/HZSM-5 exhibited the best properties and was impregnated with a varying range of cobalt metal for the HTL of Camelina sativa. The 5%Co/γ-Al2O3-HZSM-5 catalyst exhibited highest liquefaction conversion (79%) and biogasoline yield (43%) at optimized reaction conditions due to the presence of strong brønsted acidity on the catalyst were that enhanced both the hydrocarbon cracking and hydrogenation leading to the production of low boiling point and low molecular weight hydrocarbon within the boiling point range of fossil gasoline. Across all the data point used in the work, the average deviation was within ± 3%, these are mostly indicated by the error bars. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Catechol‐formaldehyde resin (CFR) is very attractive for H2O2 production via the catalytic process. However, the H2O2 formation is accompanied by the oxidation of catechol groups to o‐benzoquinone groups on CFR, which will cause irreversible damage to CFR and greatly limit its long‐term stable catalytic activity. Herein, CdS/CFR composite photocatalyst with a core‐shell structure was synthesized by hydrothermal method. The photogenerated electrons of CdS are used as a powerful driving force for the reversible redox conversion between catechol groups and o‐benzoquinone groups on the CFR, which not only achieves the long‐term stability of CFR‐catalyzed production of H2O2, but also promotes the separation efficiency of photogenerated e– and h+ in CdS, greatly inhibiting their recombination, so as to maintain CdS stability. The H2O2 yield of CdS/CFR can accumulate to 1.65 mmol·L–1 under visible light for 6 h without sacrificial agent, which is about 3.1 and 2 times that of CdS and CFR, respectively, and CdS/CFR can persist for 10 cycles of photocatalysis (60 h). CdS/CFR also improves the yield of photocatalytic H2O2 by increasing the selectivity of H2O2 and inhibiting its decomposition. This work offers a novel tactic for expanding the application of CFR in photocatalytic generation of H2O2. [ABSTRACT FROM AUTHOR]

Symmetrical biaryl compounds are vital chemical feedstocks in the fine chemical industry. Homocoupling, which produces aryl‐aryl reagents, remains the predominant method for their synthesis. Previously, Yaghi et al. reported a patent demonstrating the high performance of HKUST‐1 in homocoupling reactions involving arylboronic acids with electron‐withdrawing substituents. However, reactions with electron‐donating substituents yielded lower results. In this study, we introduce optimized protocols for HKUST‐1 catalyzed homocoupling of arylboronic acids with electron‐donating substituents, achieving symmetrical biaryl products with yields up to 93 %. We also observed significant hydroxylation byproducts competing with homocoupling products when the reaction was exposed to air, especially for arylboronic acids with electron‐donating substituents. This heterogeneous HKUST‐1 catalyst demonstrated recyclability for up to three cycles without a significant decline in catalytic activity. [ABSTRACT FROM AUTHOR]

Plasmon-driven chemical conversion is gaining burgeoning interest in the field of heterogeneous catalysis. Herein, we study the reactivity of N-methyl-4-sulfanylbenzamide (NMSB) at nanocavities of gold and silver nanoparticle aggregates under plasmonic excitation to gain understanding of the respective reaction mechanism. NMSB is a secondary amide, which is a frequent binding motive found in peptides and a common coupling product of organic molecules and biomolecules. Surface-enhanced Raman scattering (SERS) is used as a two-in-one in-situ spectroscopic tool to initiate the molecular transformation process and simultaneously monitor and analyze the reaction products. Supported by dissociative electron attachment (DEA) studies with the gas phase molecule, a hot electron-mediated conversion of NMSB to p-mercaptobenzamide and p-mercaptobenzonitrile is proposed at the plasmonic nanocavities. The reaction rate showed negligible dependence on the external temperature, ruling out the dominant role of heat in the chemical transformation at the plasmonic interface. This is reflected in the absence of a superlinear relationship between the reaction rate constant and the laser power density, and DEA and SERS studies indicate a hot-electron mediated pathway. We conclude that the overall reaction rate is limited by the availability of energetic hot electrons to the NMSB molecule. Photocatalysis driven by surface plasmons is a promising approach for light-driven chemical conversions of molecules under mild conditions. Here, the authors study the reactivity of N-methyl-4-sulfanylbenzamide (NMSB) at the nanocavities of gold and silver nanoparticle aggregates under plasmonic excitation and propose a hot electron-mediated conversion of NMSB to p-mercaptobenzamide and p-mercaptobenzonitrile. [ABSTRACT FROM AUTHOR]

Developing a desirable ethanol dehydrogenation process necessitates a highly efficient and selective catalyst with low cost. Herein, we show that the "complex active site" consisting of atomically dispersed Au atoms with the neighboring oxygen vacancies (Vo) and undercoordinated cation on oxide supports can be prepared and display unique catalytic properties for ethanol dehydrogenation. The "complex active site" Au−Vo−Zr3+ on Au1/ZrO2 exhibits the highest H2 production rate, with above 37,964 mol H2 per mol Au per hour (385 g H2 gAu-1 ${{\rm{g}}_{{\rm{Au}}}^{ - 1} }$ h−1) at 350 °C, which is 3.32, 2.94 and 15.0 times higher than Au1/CeO2, Au1/TiO2, and Au1/Al2O3, respectively. Combining experimental and theoretical studies, we demonstrate the structural sensitivity of these complex sites by assessing their selectivity and activity in ethanol dehydrogenation. Our study sheds new light on the design and development of cost‐effective and highly efficient catalysts for ethanol dehydrogenation. Fundamentally, atomic‐level catalyst design by colocalizing catalytically active metal atoms forming a structure‐sensitive "complex site", is a crucial way to advance from heterogeneous catalysis to molecular catalysis. Our study advanced the understanding of the structure sensitivity of the active site in atomically dispersed catalysts. [ABSTRACT FROM AUTHOR]

CeO2‐supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2‐Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5 wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

The N‐methylation reaction of amines with methanol via the borrowing‐hydrogen strategy is an important method for the construction of C−N bonds. Compared with other C1 sources, such as toxic formaldehyde or expensive formic acid, methanol is more suitable for N‐methylation reactions due to its eco‐friendliness and low price. Using this strategy, various types N‐methylated products, including biological and pharmaceutical molecules have been prepared. Here, we present a thorough survey of decades of articles showing current developments in N‐methylation reactions with methanol. We discuss homogenous, heterogenous and light‐driven catalytic systems for both N‐methylation and N,N‐dimethylation reactions. This review presents the shortcomings of current developments and provides future development progress in N‐methylation reactions with methanol. [ABSTRACT FROM AUTHOR]

A prerequisite for the development or optimization of heterogeneous catalysts is a comprehensive understanding of the reaction mechanism and kinetics at the level as elementary as possible. In comparison with steady‐state catalytic tests typically used for this purpose, non‐steady‐state (transient) studies provide deeper insights due to higher time resolution. For several decades, temporal analysis of products (TAP) and steady‐state isotopic transient kinetic analysis (SSITKA) have been successfully applied to the analysis of various heterogeneous reactions. In this review, we highlight the contributions made by TAP and SSITKA studies between 2017 and 2023 to the understanding of reaction mechanisms and to the derivation of microkinetics. The versatility of these methods is illustrated by the examples of oxidative coupling of methane, CO/CO2 hydrogenation to hydrocarbons or methanol, metathesis of ethylene with 2‐butenes to propene, acrolein oxidation to acrylic acid, methanol conversion to olefins and non‐oxidative propane dehydrogenation to propene. We also provide our personal views on possible developments in this area. [ABSTRACT FROM AUTHOR]

The remediation of polluted water is a major concern for public health and the environment. Catalytic removal of model organic and inorganic pollutants in water using carbon catalysts has shown promising results. In the present work, stereolithographically 3D‐printed bio‐based carbon monoliths with different textural and surface chemistry properties were used as catalysts for oxalic acid oxidation and catalyst supports for bromate reduction in continuous systems. A significant synergistic effect between ozone or dihydrogen and carbon catalyst was evidenced by mineralization of 14–25 % of oxalic acid or reduction of 15–45 % of bromates in the steady state, respectively. The best results were achieved with samples with the highest mesoporous surface area or, in the case of lower surface area, with samples having the strongest basic character. As materials with great potential, optimizing the textural properties of architected carbon monoliths will enable them to compete with other macro‐structured carbon catalysts. [ABSTRACT FROM AUTHOR]

The isomerization of glucose to fructose plays a crucial role in the food industry and the production of biomass‐derived chemicals in biorefineries. However, the catalyst used in this reaction suffers from low selectivity and catalyst deactivation due to carbon or by‐product deposition. In this study, MgSnO3 catalyst, synthesized via a facile two‐step process involving hydrothermal treatment and calcination, was used for glucose isomerization to fructose. The catalyst demonstrated outstanding catalytic performance, achieving a fructose equilibrium yield of 29.8 % with a selectivity exceeding 90 % under mild conditions owing to its acid‐base interaction. Notably, spent catalysts can be regenerated by photoirradiation to remove surface carbon, thereby avoiding the changes in properties and subsequent loss of activity associated with conventional calcination regeneration method. This novel approach eliminates the energy consumption and potential structural aggregation associated with traditional calcination regeneration methods. The acid‐base active sites of the catalyst, along with their corresponding catalytic reaction mechanism and photoregeneration mechanism were investigated. This study presents a demonstration of the comprehensive utilization of catalytic material properties, i. e. acid‐base and photocatalytic functionalities, for the development of a green and sustainable biomass thermochemical conversion system. [ABSTRACT FROM AUTHOR]

Photocatalytic synthesis of value‐added chemicals has gained increasing attention in recent years owing to its versatility in driving many important reactions under ambient conditions. Selective hydrogenation, oxidation, coupling, and halogenation with a high conversion of the reactants have been realized using designed photocatalysts in batch reactors with small volumes at a laboratory scale; however, scaling‐up remains a critical challenge due to inefficient utilization of incident light and active sites of the photocatalysts, resulting in poor catalytic performance that hinders its practical applications. Flow systems are considered one of the solutions for practical applications of light‐driven reactions and have experienced great success in photolytic and homogeneous photocatalysis, yet their applications in heterogeneous photocatalysis are still under development. In this perspective, we have summarized recent progress in photolytic and photocatalytic synthetic chemistry performed in flow systems from the view of reactor design with a special focus on heterogeneous photocatalysis. The advantages and limitations of different flow systems, as well as some practical considerations of design strategies are discussed. [ABSTRACT FROM AUTHOR]

Atomic‐level tailoring of active sites is an efficient strategy for designing high‐performance photocatalysts for clean energy. Asymmetric atomic sites (AAS) like MSA‐Ov‐M2 created through hetero‐metal single atoms (MSA) doping on defect‐rich metal oxides (M2‐Ov‐M2) are favored for better activation of targeted molecules. However, creating AAS typically demands high energy input, hindering their widespread use in photocatalytic H2 production. Furthermore, precise control over surface defects to create AAS remains challenging. Here, CuSA‐Ov‐Ti3c highly asymmetric atomic sites catalyst (HAASC) is constructed by strategically trapping Cu single atoms on high‐index (111) faceted TiO2. This material combines single‐atom catalysis and facet engineering, achieving unprecedented H2 production rates (8.3 mmol h−1 g−1 in pure water and 784.5 mmol h−1 g−1 in water/methanol mixture). Experimental and theoretical analyses reveal CuSA substituting five‐coordinated Ti atoms (Ti5c) next to three‐coordinated (Ti3c) ones, forming CuSA‐Ov‐Ti3c HAAS. HAAS plays multiple roles in i) improving light harvesting, charge‐transfer dynamics, and redox capability of photoexcited electrons; ii) enhanced adsorption and polarization of H2O molecules; iii) facilitating electron transfer from CuSA‐Ov‐Ti3c to H2O molecules, and iv) raising d‐band center toward Fermi level resulting in ≈250‐fold enhanced H2 production than Ti5c‐O‐Ti3c AASC. This work opens new avenues for future structural designs in heterogeneous catalysis for energy‐related applications. [ABSTRACT FROM AUTHOR]

In the pursuit of enhancing the applications of hydrogen as an energy carrier, this research delved into the utilization of a singular hybrid catalyst capable of performing both dehydrogenation and hydrogenation processes for Liquid Organic Hydrogen Carriers (LOHCs). This study presents the synthesis and characterization of a hybrid catalyst, combining an organometallic pincer complex with Pd−Ru heterostructures supported on γ‐alumina. Unlike conventional transition and noble metal nanoparticles, the use of a pincer complex offers exceptional thermal stability due to its aryl backbone, which is advantageous for various endothermic dehydrogenation reactions of hydrocarbons in LOHCs. This pioneering hybrid catalyst is a novel approach, demonstrating a proof of concept. In this study, we utilized the hybrid catalyst to investigate the dehydrogenation and hydrogenation of a lower enthalpic system, specifically the cyclooctane−cyclooctene system. The dehydrogenation of cyclooctane was conducted at 443 K using tertiary butyl ethylene as a sacrificial hydrogen acceptor, while the hydrogenation of cyclooctene reaction catalyzed by Pd−Ru nanostructures occurred at 298 K and 1 atm H2. The results showed successful tandem dehydrogenation‐hydrogenation reactions. However, challenges were noted in terms of catalytic activity and recyclability, providing valuable insights for further refinement and optimization. [ABSTRACT FROM AUTHOR]

Referring to selected examples of reproducible green syntheses using hybrid sol‐gel catalysts of the SiliaCat series from different doctoral theses and research works published between 2015 and early 2024, this study briefly illustrates how said catalysts have been applied in a number of green synthetic methods of significant industrial relevance. This shows evidence that the nanochemistry “bottom‐up” sol‐gel approach based on catalytic species entrapped in organically modified silicas as effective and versatile heterogeneous catalysts developed between the late 1990s and 2010 has succeeded. Subsequent developments will show how the use of said materials in automated syntheses, supplying data to machine learning algorithms actually leads to faster and cheaper optimization of the reaction conditions. Said progress ultimately will further accelerate industrial uptake of heterogeneous catalysis under flow in the fine chemical industry whose reluctance to change processes was due to the need to replace financially amortized (and expensive) production plants. [ABSTRACT FROM AUTHOR]

Comprehensive Summary The direct oxidation of methane (CH4) into high‐valued C1 oxygenates production has garnered increased attention in effectively using vast CH4 and alleviating the global energy crisis. However, due to the high cleavage energy of C—H bond and low polarity of CH4 molecule, it is difficult to activate the first C—H bond. Furthermore, C1 oxygenates are readily inclined to be oxidized to CO2, because their weaker C—H bond comparing with CH4 molecule, resulting in poor selectivity. Herein, we designed ultrathin PdxAuy alloy NWs supported on ZSM‐5 (Z‐5) to investigate the direct oxidation of CH4 to high value‐added oxygenate under mild conditions. By precisely adjusting the molar ratio of Pd/Au and alloying degree, Pd9Au1NWs/Z‐5 showed an excellent yield of 11.57 mmol·g–l·h–1 and the outstanding selectivity of 95.1% for C1 oxygenates (CH3OH, CH3OOH and HCOOH). The in‐situ spectroscopic and mechanism analysis proved that the enhanced catalytic performance of Pd9Au1NWs/Z‐5 was ascribed to the stable one‐dimensional nanostructure and the strong synergy effect with high alloying PdAu, which could increase the adsorption capacity of CH4 molecules on Pd atoms to promote the CH4 conversion. This work offers valuable insights into the design concept of high‐efficient catalysts and the structure‐activity relationship for the direct oxidation of CH4. [ABSTRACT FROM AUTHOR]

Comprehensive Summary The conversion of aniline to nitrosobenzene (NSB), a key step in the synthesis of important chemicals, demands the development of environmentally friendly photocatalysts that operate under mild conditions. This process is driven by the need for sustainable methods, given toxic nature of aniline and its central role in the production of dyes, pharmaceuticals, and agricultural chemicals. This study reports on the synthesis of three reduced phosphomolybdate compounds with Co(II) centers and polypyridine ligands, which show great potential as photocatalysts for the mild oxidation of aniline to NSB. The synthesis uses 30% H2O2 as the oxidant and the compounds as the sole catalysts, achieving high conversion rates and selectivity without additional additives or photosensitizers. The integration of multidentate ligands with {P4Mo6} clusters significantly reduces the band gap, facilitating visible‐light‐driven photocatalysis. The adsorption interaction between coordinated water molecules and Co ions and H2O2 is found to enhance the conversion rate of aniline, a finding supported by DFT analyses. [ABSTRACT FROM AUTHOR]

Covalent immobilization of chiral dienes in mesoporous solids for asymmetric heterogeneous catalysis is highly attractive. In order to study confinement effects in bimolecular vs monomolecular reactions, a series of pseudo‐C2‐symmetrical tetrahydropentalenes was synthesized and immobilized via click reaction on different mesoporous solids (silica, carbon, covalent organic frameworks) and compared with homogeneous conditions. Two types of Rh‐catalyzed reactions were studied: (a) bimolecular nucleophilic 1,2‐additions of phenylboroxine to N‐tosylimine and (b) monomolecular isomerization of isoxazole to 2H‐azirne. Polar support materials performed better than non‐polar ones. Under confinement, bimolecular reactions showed decreased yields, whereas yields in monomolecular reactions were only little affected. Regarding enantioselectivity the opposite trend was observed, i. e. effective enantiocontrol for bimolecular reactions but only little control for monomolecular reactions was found. [ABSTRACT FROM AUTHOR]

A novel method for the production of a biofuel precursor and additive (γ-valerolactone) using in-situ generated hydrogen is reported. Firstly, a potential non-carbon fuel as hydrogen is generated from water through a photoelectrochemical approach employing a set of TiO 2 nanostructures synthesized by hydrodynamic anodization. Secondly, this system was coupled with a reactor in a way that the hydrogen produced reacts with levulinic acid in the presence of a ruthenium catalyst to yield γ-valerolactone. The preparation procedure of TiO 2 nanostructures was optimized and the influence of factors such as the rotation speed and the anodization media was investigated. The best photoelectrochemical performance corresponds to the nanostructure synthesized in lactic acid and using hydrodynamic conditions at a rotation speed of 1000 rpm. The optimal nanostructure was used as a photocatalyst for hydrogen production by water splitting, with the generated hydrogen being directly used for the transformation of levulinic acid into γ-valerolactone in the presence of a ruthenium catalyst supported on alumina. Using this optimal TiO 2 and the ruthenium catalyst, a yield to γ-valerolactone of 93 % was obtained in only 5 h at 60 °C and atmospheric pressure. [Display omitted] • Optimization of photoelectrochemical water splitting with titania nanostructures. • Tandem process: photoelectrocatalysis and conventional heterogeneous catalysis. • In-situ generated hydrogen for biofuel production. • Clean fuels: hydrogen and γ-valerolactone. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Localized surface plasmon resonance has been demonstrated to provide effective photophysical enhancement mechanisms in plasmonic photocatalysis. However, it remains highly challenging for distinct mechanisms to function in synergy for a collective gain in catalysis due to the lack of spatiotemporal control of their effect. Herein, the anisotropic plasmon resonance nature of Au nanorods was exploited to achieve distinct functionality towards synergistic photocatalysis. Photothermal and photochemical effects were enabled by the longitudinal and transverse plasmon resonance modes, respectively, and were enhanced by partial coating of silica nanoshells and epitaxial growth of a reactor component. Resonant excitation leads to a synergistic gain in photothermal‐mediated hot carrier‐driven hydrogen evolution catalysis. Our approach provides important design principles for plasmonic photocatalysts in achieving spatiotemporal modulation of distinct photophysical enhancement mechanisms. It also effectively broadens the sunlight response range and increases the efficacy of distinct plasmonic enhancement pathways towards solar energy harvesting and conversion. [ABSTRACT FROM AUTHOR]

The production of ethylene glycol (EG) from cellulose has garnered significant attention in recent years as an attractive alternative to fossil fuels due to the potential of cellulose as a renewable and sustainable feedstock. In this work, to the best of our knowledge, a series of low-cost Ni-W bimetallic catalysts supported on glucose/carbon nanotube hybrid carbons were synthesised for the first time and employed to transform cellulose into EG. Two different strategies were combined for the preparation of the carbons: the activation and addition of carbon nanotubes (CNTs) to obtain a hybrid material (AG-CNT). The catalytic conversion process proceeded through cellulose hydrolysis to glucose, followed by glucose retro-aldol condensation to glycolaldehyde and its subsequent hydrogenation to EG. Through the optimisation of the catalyst's properties, particularly the metals' content, a good synergistic effect of C-C bond cleavage and hydrogenation capabilities was assured, resulting in the highly selective production of EG. The balance between Ni and W active sites was confirmed to be a crucial parameter. Thus, total cellulose conversion (100%) was achieved with EG yields of 60–62%, which are amongst the best yields ever reported for the catalytic conversion of cellulose into EG via carbon-supported catalysts. [ABSTRACT FROM AUTHOR]

Lignin, a phenolic‐rich biomass component, holds promise for producing value‐added products. However, its complex structure and recalcitrance present challenges for its effective utilization. To overcome this, a AuPd/Li−Al layered double hydroxide (LDH) catalyst was developed to facilitate lignin depolymerization. Various AuPd bimetallic nanoparticle compositions were supported on a basic Li−Al LDH support via a sol‐immobilization method and characterized using N2‐physisorption, X‐ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The catalysts were then evaluated in the oxidation of several benzylic alcohols using O2 as the oxidant, from which Au7Pd3/Li−Al LDH and Au1Pd1/Li−Al LDH were identified as possessing promising catalytic activity. Further investigations focused on the aerobic oxidation of β‐O‐4 linked lignin model dimers under atmospheric pressure. The tested catalysts demonstrated sequential oxidation of the model compounds, leading to cleavage of the β‐O‐4 linkage. Finally, the catalysts were applied to the oxidative deconstruction of γ‐valerolactone (GVL) extracted maple lignin at 120 °C. Au1Pd1/Li−Al LDH emerged as the most effective catalyst, yielding a range of aromatic monomers with a total monomer yield of 27 %. These results highlight the potential of the Au1Pd1/Li−Al LDH catalyst system as an eco‐friendly approach for lignin depolymerization under mild conditions. [ABSTRACT FROM AUTHOR]

We investigate the interaction of CO2 with metallic and oxidized Cu(110) surfaces using a combination of near‐ambient pressure scanning tunneling microscopy (NAP‐STM) and theoretical calculations. While the Cu(110) and full CuO films are inert, the interface between bare Cu(110) and the CuO film is observed to react instantly with CO2 at a 10 mbar pressure. The reaction is observed to proceed from the interfacial sites of CuO/Cu(110). During reaction with CO2, the CuO/Cu(110) interface releases Cu adatoms which combine with CO3 to produce a variety of added Cu−CO3 structures, whose stability depends on the gas pressure of CO2. A main implication for the reactivity of Cu(110) is that Cu adatoms and highly undercoordinated CuO segments are created on the Cu(110) surface through the interaction with CO2, which may act as reaction‐induced active sites. In the case of CO2 hydrogenation to methanol, our theoretical assessment of such sites indicates that their presence may significantly promote CH3OH formation. Our study thus implies that the CuO/Cu(110) interfacial system is highly dynamic in the presence of CO2, and it suggests a possible strong importance of reaction‐induced Cu and CuO sites for the surface chemistry of Cu(110) in CO2‐related catalysis. [ABSTRACT FROM AUTHOR]

α‐Amino phosphonates are bio‐isosteres of amino acids and have numerous biochemical activities. While they are generally prepared via carbon–phosphorus bond formation using a plethora of methods but using recyclable photo‐catalysts and readily accessible amine and phosphites are not commonly used in synthesis. Herein, we used organo‐soluble MoS2 Quantum Dots (QDs) as an exceptionally efficient nano‐photocatalyst for the synthesis of α‐amino phosphonates. Our approach emphasizes on photocatalysis within organic media, providing a facile and effective method for conducting these intricate organic conversions under mild conditions. This straightforward process harnesses the power of molecular oxygen (O2) as an oxidizing agent. To elaborate, our method is intricately guided by the inherent capability of MoS2 QDs to enter an excited state upon absorption of blue light. This excited state bears appropriate potential energy to initiate the formation of reactive iminium ion species from N‐phenyl benzylamine, thus driving the desired product formation. Mechanistic analysis has also unveiled the pivotal role of MoS2 QDs in generating reactive superoxide radicals from O2 through single electron transfer (SET), underscoring their significance in the process. Remarkably, this photocatalytic transformation furnishes a diverse array of functionalized products, expanding its applicability and potential implications in various contexts. [ABSTRACT FROM AUTHOR]

Over the past few decades, a significant amount of research effort has focused on investigating the active site requirements and reaction mechanisms for partial methane oxidation (PMO) to methanol over copper–exchanged zeolites during stoichiometric and stepwise chemical looping routes. More recently, research efforts have expanded to include investigating the PMO reaction in a continuous catalytic regime, primarily focusing on determining the influence of catalyst composition on Cu speciation and structure and, in turn, on PMO rate and selectivity. The structures of candidate Cu active sites are commonly studied using a combination of ex situ and in situ spectroscopic approaches. In this perspective, we critically examine the prior literature on catalytic PMO over Cu–zeolites to identify key knowledge gaps that remain in our understanding as motivation for future research efforts. We identify opportunities for future research to address these gaps by adapting analogous interrogation techniques that have been successfully used to elucidate the active site requirements and mechanistic details of another catalytic redox reaction cycle on Cu–zeolites, the selective catalytic reduction (SCR) of nitrogen oxides (NOx). [ABSTRACT FROM AUTHOR]

Strong metal‐support interactions (SMSI) featuring the formation of encapsulation overlayer around metal nanoparticles has drawn much attention in heterogeneous catalysis. Recent years, various novel SMSI phenomena have been observed and the nature of SMSI also has been revealed with the improvement of characterization techniques. Understanding the SMSI effect could deepen the insight into the structure‐activity relationship of metal‐supported catalysts, and rationally guide the design of special metal‐interface sites to manipulate catalytic behavior in chemical reaction. In this review, the research progress of SMSI and its application in heterogeneous COx hydrogenation are briefly surveyed, with emphasis on the advanced characterization, manipulation strategy and specific role of SMSI in Fischer‐Tropsch synthesis process, CO2 methanation and Reverse Water Gas Shift reaction. The current challenges and perspectives for the development of SMSI are also discussed. [ABSTRACT FROM AUTHOR]

Molecular catalysts represent an exceptional class of materials in the realm of electrochemical carbon dioxide reduction (CO2RR), offering distinct advantages owing to their adaptable structure, which enables precise control of electronic configurations and outstanding performance in CO2RR. This study introduces an innovative approach to heterogeneous electrochemical CO2RR in an aqueous environment, utilizing a newly synthesized N4‐macrocyclic cobalt complex generated through a dimerization coupling reaction. By incorporating the quaterpyridine moiety, this cobalt complex exhibits the capability to catalyze CO2RR at low overpotentials and reaches near‐unity CO production across a wide potential range, as verified by the online mass spectrometry and in situ attenuated total reflectance‐Fourier transform infrared spectroscopy. Comprehensive computational models demonstrate the superiority of utilizing quarterpyridine moiety in mediating CO2 conversion compared to the counterpart. This work not only propels the field of electrochemical CO2RR but also underscores the promising potential of cobalt complexes featuring quaterpyridine moieties in advancing sustainable CO2 conversion technologies within aqueous environments. [ABSTRACT FROM AUTHOR]

In this paper, we discuss reaction-diffusion processes in porous catalyst granules of spherical, cylindrical, and lamellar forms for various types of chemical reactions. We obtain approximate solutions of the quasi-homogeneous model for general catalytic reactions. Also, we analyze necessary conditions for the appearance of a "dead zone" in the central domain of a porous catalyst granule in the case of a general catalytic reaction. [ABSTRACT FROM AUTHOR]

A magnetically isolable iron oxide nanoparticles is introduced as an efficient heterogeneous photocatalyst for non‐directed C−H arylation employing aryl diazonium salts as the aryl precursors. This first‐row transition metal‐based photocatalyst revealed versatile activities and is applicable to a wide range of substrates, demonstrating brilliant efficacy and superior recyclability. Detailed catalytic characterization describes the physical properties and redox behavior of the Fe‐catalyst. Adequate control experiments helped to establish the radical‐based mechanism for the C−H arylation. [ABSTRACT FROM AUTHOR]