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Plasmonic coupling among nanocavities creates a significant collective response of near-field enhancement, leading to numerous applications such as extraordinary optical transmittance, enhanced spectroscopy, energy harvesting, photo-enhanced catalysis, meta-lens, etc. We report here a perturbation theory based on the two-body interaction potential to clarify the plasmonic coupling between/among nanocavities. With this theory, we demonstrated that one can calculate the near-field distribution of a cluster of nanocavities and that the results are in agreement with simulations by the finite element method and those measured by a scanning near-field optical microscope. The perturbation theory offers an effective way in dealing with the plasmonic coupling behavior of nanocavities. [ABSTRACT FROM AUTHOR]

Heterojunction catalysts in the field of hydrogen evolution reaction (HER) from electrocatalytic water splitting have recently become a hot research topic. In this paper, we systematically calculated the HER catalytic performance of a MoS2/CoS2 heterojunction for the first time, considering the effect of edge sites regulation, strain and electric field. The results indicate that the MoS2/CoS2 heterojunction exhibits synergistic catalytic performance compared to MoS2 and CoS2, the HER catalytic activity of which can be improved by exposing more edge sites or regulating the S content on the edges, with an optimized ratio of 25%. Surprisingly, applying strain has a slight effect on the catalytic activity of the edge, however, an obvious effect on the basal plane. For example, applying 2% tensile strain on the MoS2/CoS2 heterojunction can improve the edge catalytic performance by 13%, and for the basal plane, this value can reach 92%. In this case, the catalytic performance of the basal plane is better than that of the edge with 2% and without strain. Since the basal plane accounts for the majority of the two-dimensional catalysts, the catalytic performance of the basal plane is generally much lower than that of the edge. This discovery is of great significance, which means by adjusting strain, the catalytic performance of the heterojunction catalyst is likely to be improved by orders of magnitude. Moreover, considering the actual experimental process, we also calculated the effect of the electric field and found that 0.7 V/Å electric field can enhance the HER catalytic activity of the MoS2/CoS2 heterojunction by 23%. [ABSTRACT FROM AUTHOR]

The photochemical generation of nicotinamide cofactor 1,4-NADH, facilitated by inorganic photosensitizers, emerges as a promising model system for investigating charge transfer phenomena at the interface of semiconductors and bacteria, with implications for enhancing photosynthetic biohybrid systems (PBSs). However, extant semiconductor nanocrystal model systems suffer from achieving optimal conversion efficiency under visible light. This study investigates quasi-one-dimensional CdS nanorods as superior light absorbers, surface modified with catalyst Cp*Rh(4,4'-COOH-bpy)Cl2 to produce enzymatically active NADH. This model subsystem facilitates easy product isolation and achieves a turnover frequency (TOF) of 175 h-1, one of the highest efficiencies reported for inorganic photosensitizer-based nicotinamide cofactor generation. Charge transfer kinetics, fundamental for catalytic solar energy conversion, range from 106 to 108 s-1 for this system highlighting the superior electron transfer capabilities of NRs. This model ensures efficient cofactor production and offers critical insights into advancing systems that mimic natural photosynthesis for sustainable solar-to-chemical synthesis.

In pharmaceutical discovery, the "magic methyl" effect describes a substantial improvement in the pharmacological properties of a drug candidate with the incorporation of methyl groups. Therefore, to expedite the synthesis of methylated drug analogs, late-stage, undirected methylations of C(sp3)-H bonds in complex molecules would be valuable. However, current methods for site-selective methylations are limited to activated C(sp3)-H bonds. Here we describe a site-selective, undirected methylation of unactivated C(sp3)-H bonds, enabled by photochemically activated peroxides and a nickel(II) complex whose turnover is enhanced by an ancillary ligand. The methodology displays compatibility with a wide range of functional groups and a high selectivity for tertiary C-H bonds, making it suitable for the late-stage methylation of complex organic compounds that contain multiple alkyl C-H bonds, such as terpene natural products, peptides, and active pharmaceutical ingredients. Overall, this method provides a synthetic tool to explore the "magic methyl" effect in drug discovery.

Pt-based alloys, such as Pt3Ni, are among the best electrocatalysts for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells. Doping of PtNi alloys with Zr was shown to enhance the durability of the operating ORR catalysts. Rationalizing these observations is hindered by the absence of atomic-level data for these tri-metallic materials, even when not exposed to the fuel cell operation conditions. This study aims at understanding structure–property relations in Zr-doped PtNi nanoparticles as a key to their ORR function. In particular, we calculated, using a method based on density functional theory, the most stable chemical orderings of pristine and Zr-doped Pt3Ni particles containing over 400 atoms. We thus clarify (i) preferential location and charge states of Zr atoms in the Pt3Ni NPs; (ii) effect of doping Zr atoms on the stability of the Pt skin of the Pt3Ni NPs; (iii) charge redistribution induced by Zr dopants; (iv) layer-by-layer atomic ordering in the Pt3Ni/Zr NPs with the increasing Zr content; and (v) effect of Zr atoms on the adsorption energies of O and OH species as indicators of the ORR activity. [ABSTRACT FROM AUTHOR]

Effective synthesis and application of single-atom catalysts on supports lacking enough defects remain a significant challenge in environmental catalysis. Herein, we present a universal defect-enrichment strategy to increase the surface defects of CeO2-based supports through H2 reduction pretreatment. The Pt catalysts supported by defective CeO2-based supports, including CeO2, CeZrOx, and CeO2/Al2O3 (CA), exhibit much higher Pt dispersion and CO oxidation activity upon reduction activation compared to their counterpart catalysts without defect enrichment. Specifically, Pt is present as embedded single atoms on the CA support with enriched surface defects (CA-HD) based on which the highly active catalyst showing embedded Pt clusters (PtC) with the bottom layer of Pt atoms substituting the Ce cations in the CeO2 surface lattice can be obtained through reduction activation. Embedded PtC can better facilitate CO adsorption and promote O2 activation at PtC-CeO2 interfaces, thereby contributing to the superior low-temperature CO oxidation activity of the Pt/CA-HD catalyst after activation.

Rapid and precise detection of hydrogen peroxide (H2O2) holds great significance since it is linked to numerous physiological and inorganic catalytic processes. We herein developed a label-free and washing-free strategy to detect H2O2 by employing a hand-held personal glucose meter (PGM) as a signal readout device. By focusing on the fact that the reduced redox mediator ([Fe(CN)6]4-) itself is responsible for the final PGM signal, we developed a new PGM-based strategy to detect H2O2 by utilizing the target H2O2-mediated oxidation of [Fe(CN)6]4- to [Fe(CN)6]3- in the presence of horseradish peroxidase (HRP) and monitoring the reduced PGM signal in response to the target amount. Based on this straightforward and facile design principle, H2O2 was successfully determined down to 3.63 μM with high specificity against various non-target molecules. We further demonstrated that this strategy could be expanded to identify another model target choline by detecting H2O2 produced through its oxidation promoted by choline oxidase. Moreover, we verified its practical applicability by reliably determining extracellular H2O2 released from the breast cancer cell line, MDA-MB-231. This work could evolve into versatile PGM-based platform technology to identify various non-glucose target molecules by employing their corresponding oxidase enzymes, greatly advancing the portable biosensing technologies.

This year's Emerging Leader in Molecular Spectroscopy Award recipient is Joseph P. Smith of Merck, whose research is significantly influencing pharmaceutical process development through his work in various spectroscopic techniques, [...]

C4F7N [2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanenitrile]/CO2 gas mixtures are being developed as an eco-friendly electrical insulator to replace SF6, the most potent greenhouse industrial gaseous dielectric. However, recent studies have reported complicated and often conflicting decomposition pathways for C4F7N/CO2 gas mixtures, which has raised concerns. In this work, the decomposition characteristics of C4F7N/CO2 gas mixtures were studied comprehensively by both designed computations and experiments. Computations were performed starting from fundamental propositions of C4F7N/CO2 decompositions, which were further experimentally verified by pyrolysis, long-term thermal aging with/without catalytic materials (industrial-grade molecular sieves 4A), and electrical decomposition by spark discharge. The results of both computations and experiments suggest that in an ideal thermal decomposition, C4F7N is likely to decompose into C2F6 and small fluoronitriles first at high temperatures. The generation of C3F6 and C2N2 from C4F7N thermal decomposition at lower temperatures appears because of the catalytic effect of incompatible materials, for example, the industrial-grade molecular sieves 4A that we tested. The electron impact dissociation of C4F7N plays an important role in C4F7N electrical decomposition, leading to additional formation of distinctive small molecules of CF4 and C2N2 of low concentrations. It was pointed out based on a real arcing test in a load disconnector that the decomposition of C4F7N gas mixtures in real applications will be at a much moderate and manageable rate than what was obtained from the highly accelerated laboratory tests presented in this work. The signatures of decomposition products extracted in this study provide invaluable guidance for developing decomposition-based diagnosis and fixation of decomposition byproducts toward SF6-free power grids. [ABSTRACT FROM AUTHOR]

The ability to sense chemical gradients and respond with directional motility and chemical activity is a defining feature of complex living systems. There is a strong interest among scientists to design synthetic systems that emulate these properties. Here, we realize and control such behaviors in a synthetic system by tailoring multivalent interactions of adenosine nucleotides with catalytic microbeads. We first show that multivalent interactions of the bead with gradients of adenosine mono-, di- and trinucleotides (AM/D/TP) control both the phoretic motion and a proton-transfer catalytic reaction, and find that both effects are diminished greatly with increasing valence of phosphates. We exploit this behavior by using enzymatic hydrolysis of ATP to AMP, which downregulates multivalent interactivity in situ. This produces a sudden increase in transport of the catalytic microbeads (a phoretic jump), which is accompanied by increased catalytic activity. Finally, we show how this enzymatic activity can be systematically tuned, leading to simultaneous in situ spatial and temporal control of the location of the microbeads, as well as the products of the reaction that they catalyze. These findings open up new avenues for utilizing multivalent interaction-mediated programming of complex chemo-mechanical behaviors into active systems.

Electrochemical CO2 reduction (CO2R) using heterogenized molecular catalysts usually yields 2-electron reduction products (CO, formate). Recently, it has been reported that certain preparations of immobilized cobalt phthalocyanine (CoPc) produce methanol (MeOH), a 6-electron reduction product. Here, we demonstrate the significant role of intermediate mass transport in CoPc selectivity to methanol. We first developed a simple, physically mixed, polymer (and polyfluoroalkyl, PFAS)-free preparation of CoPc on multiwalled carbon nanotubes (MWCNTs) which can be integrated onto Au electrodes using a poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) adhesion layer. After optimization of catalyst preparation and loading, methanol Faradaic efficiencies and partial current densities of 36% (±3%) and 3.8 (±0.5) mA cm-2, respectively, are achieved in the CO2-saturated aqueous electrolyte. The electrolyte flow rate has a large effect. A linear flow velocity of 8.5 cm/min produces the highest MeOH selectivity, with higher flow rates increasing CO selectivity and lower flow rates increasing the hydrogen evolution reaction, suggesting that CO is an unbound intermediate. Using a continuum multiphysics model assuming CO is the intermediate, we show qualitative agreement with the optimal inlet flow rate. Polymer binders were not required to achieve a high Faradaic efficiency for methanol using CoPc and MWCNTs. We also investigated the role of formaldehyde as an intermediate and the role of strain, but definitive conclusions could not be established.

Enzymes populate ensembles of structures necessary for catalysis that are difficult to experimentally characterize. We use time-resolved mix-and-inject serial crystallography at an x-ray free electron laser to observe catalysis in a designed mutant isocyanide hydratase (ICH) enzyme that enhances sampling of important minor conformations. The active site exists in a mixture of conformations, and formation of the thioimidate intermediate selects for catalytically competent substates. The influence of cysteine ionization on the ICH ensemble is validated by determining structures of the enzyme at multiple pH values. Large molecular dynamics simulations in crystallo and time-resolved electron density maps show that Asp17 ionizes during catalysis and causes conformational changes that propagate across the dimer, permitting water to enter the active site for intermediate hydrolysis. ICH exhibits a tight coupling between ionization of active site residues and catalysis-activated protein motions, exemplifying a mechanism of electrostatic control of enzyme dynamics.

Methods to access chiral sulfur(VI) pharmacophores are of interest in medicinal and synthetic chemistry. We report the desymmetrization of unprotected sulfonimidamides via asymmetric acylation with a cinchona-phosphinate catalyst. The desired products are formed in excellent yield and enantioselectivity with no observed bis-acylation. A data-science-driven approach to substrate scope evaluation was coupled to high throughput experimentation (HTE) to facilitate statistical modeling in order to inform mechanistic studies. Reaction kinetics, catalyst structural studies, and density functional theory (DFT) transition state analysis elucidated the turnover-limiting step to be the collapse of the tetrahedral intermediate and provided key insights into the catalyst-substrate structure-activity relationships responsible for the origin of the enantioselectivity. This study offers a reliable method for accessing enantioenriched sulfonimidamides to propel their application as pharmacophores and serves as an example of the mechanistic insight that can be gleaned from integrating data science and traditional physical organic techniques.

The high-fidelity (HF1), hyper-accurate (Hypa), and evolved (Evo) variants of the CRISPR-associated protein 9 (Cas9) endonuclease are critical tools to mitigate off-target effects in the application of CRISPR-Cas9 technology. The mechanisms by which mutations in recognition subdomain 3 (Rec3) mediate specificity in these variants are poorly understood. Here, solution nuclear magnetic resonance and molecular dynamics simulations establish the structural and dynamic effects of high-specificity mutations in Rec3, and how they propagate the allosteric signal of Cas9. We reveal conserved structural changes and dynamic differences at regions of Rec3 that interface with the RNA:DNA hybrid, transducing chemical signals from Rec3 to the catalytic His-Asn-His (HNH) domain. The variants remodel the communication sourcing from the Rec3 α helix 37, previously shown to sense target DNA complementarity, either directly or allosterically. This mechanism increases communication between the DNA mismatch recognition helix and the HNH active site, shedding light on the structure and dynamics underlying Cas9 specificity and providing insight for future engineering principles.

Enzymes accelerate the rates of biomolecular reactions by many orders of magnitude compared to bulk solution, and it is widely understood that this catalytic effect arises from a combination of polar pre-organization and electrostatic transition state stabilization. A number of recent reports have also implicated ultrafast (femtosecond-picosecond) timescale motions in enzymatic activity. However, complications arising from spatially-distributed disorder, the occurrence of multiple substrate binding modes, and the influence of hydration dynamics on solvent-exposed active sites still confound many experimental studies. Here we use ultrafast two-dimensional infrared (2D IR) spectroscopy and covalently-tethered substrate analogs to examine dynamical properties of the promiscuous Pyrococcus horikoshii ene-reductase (PhENR) active site in two binding configurations mimicking proposed "inactive" and "reactive" Michaelis complexes. Spectral diffusion measurements of aryl-nitrile substrate analogs reveal an end-to-end tradeoff between fast (sub-ps) and slow (>5 ps) motions. Fermi resonant aryl-azide analogs that sense interactions of coupled oscillators are described. Lineshape and quantum beat analyses of these probes reveal characteristics that correlate with aryl-nitrile frequency fluctuation correlation functions parameters, demonstrating that this anisotropy is an intrinsic property of the water-exposed active site, where countervailing gradients of fast dynamics and disorder in the reactant ground state are maintained near the hydration interface. Our results suggest several plausible factors leading to state-selective rate enhancement and promiscuity in PhENR. This study also highlights a strategy to detect perturbations to vibrational modes outside the transparent window of the mid-IR spectrum, which may be extended to other macromolecular systems. [ABSTRACT FROM AUTHOR]

CRISPR-Cas12a is a powerful RNA-guided genome-editing system that generates double-strand DNA breaks using its single RuvC nuclease domain by a sequential mechanism in which initial cleavage of the non-target strand is followed by target strand cleavage. How the spatially distant DNA target strand traverses toward the RuvC catalytic core is presently not understood. Here, continuous tens of microsecond-long molecular dynamics and free-energy simulations reveal that an α-helical lid, located within the RuvC domain, plays a pivotal role in the traversal of the DNA target strand by anchoring the crRNA:target strand duplex and guiding the target strand toward the RuvC core, as also corroborated by DNA cleavage experiments. In this mechanism, the REC2 domain pushes the crRNA:target strand duplex toward the core of the enzyme, while the Nuc domain aids the bending and accommodation of the target strand within the RuvC core by bending inward. Understanding of this critical process underlying Cas12a activity will enrich fundamental knowledge and facilitate further engineering strategies for genome editing.

Electron bifurcation (BF) is an evolutionarily ancient energy coupling mechanism in anaerobes, whose associated enzymatic machinery remains enigmatic. In BF-flavoenzymes, a chemically high-potential electron forms in a thermodynamically favorable fashion by simultaneously dropping the potential of a second electron before its donation to physiological acceptors. The cryo-EM and spectroscopic analyses of the BF-enzyme Fix/EtfABCX from Thermotoga maritima suggest that the BF-site contains a special flavin-adenine dinucleotide and, upon its reduction with NADH, a low-potential electron transfers to ferredoxin and a high-potential electron reduces menaquinone. The transfer of energy from high-energy intermediates must be carefully orchestrated conformationally to avoid equilibration. Herein, anaerobic size exclusion-coupled small-angle X-ray scattering (SEC-SAXS) shows that the Fix/EtfAB heterodimer subcomplex, which houses BF- and electron transfer (ET)-flavins, exists in a conformational equilibrium of compacted and extended states between flavin-binding domains, the abundance of which is impacted by reduction and NAD(H) binding. The conformations identify dynamics associated with the T. maritima enzyme and also recapitulate states identified in static structures of homologous BF-flavoenzymes. Reduction of Fix/EtfABCX's flavins alone is insufficient to elicit domain movements conducive to ET but requires a structural "trigger" induced by NAD(H) binding. Models show that Fix/EtfABCX's superdimer exists in a combination of states with respect to its BF-subcomplexes, suggesting a cooperative mechanism between supermonomers for optimizing catalysis. The correlation of conformational states with pathway steps suggests a structural means with which Fix/EtfABCX may progress through its catalytic cycle. Collectively, these observations provide a structural framework for tracing Fix/EtfABCX's catalysis.

Calcium carbonate (CaCO3) is an incredibly abundant mineral on Earth, with over 90% of it being found in the lithosphere. To address the CO2 crisis and combat ocean acidification, it is essential to produce more CaCO3 using various synthetic methods. Additionally, this approach can serve as a substitute for energy-intensive processes like cement production. By doing so, we have the potential to not only reverse the damage caused by climate change but also protect biological ecosystems and the overall environment. The key lies in maximizing the utilization of CaCO3 in various human activities, paving the way for a more sustainable future for our planet.

With the rise of machine learning (ML), the modeling of chemical systems has reached a new era and has the potential to revolutionize how we understand and predict chemical reactions. Here, we probe the historic dependence on utilizing enantiomeric excess (ee) as a target variable and discuss the benefits of using relative Gibbs free activation energies (ΔΔG≠), grounded firmly in transition‐state theory, emphasizing practical benefits for chemists. This perspective is intended to discuss best practices that enhance modeling efforts especially for chemists with an experimental background in asymmetric catalysis that wish to explore modelling of their data. We outline the enhanced modeling performance using ΔΔG≠, escaping physical limitations, addressing temperature effects, managing non‐linear error propagation, adjusting for data distributions and how to deal with unphysical predictions,in order to streamline modeling for the practical chemist and provide simple guidelines to strong statistical tools. For this endeavor, we gathered ten datasets from the literature covering very different reaction types. We evaluated the datasets using fingerprint‐, descriptor‐, and graph neural network‐based models. Our results highlight the distinction in performance among varying model complexities with respect to the target representation, emphasizing practical benefits for chemists. [ABSTRACT FROM AUTHOR]

The low‐temperature liquid metals Ga‐In and Ga‐Sn have previously showcased >95 % selectivity towards the electrochemical reduction of CO2 to formate, occuring only when the alloys are melted, not solid. Here, density functional theory molecular dynamics and metadynamics simulations reveal that CO2 does not directly adsorb to the Ga‐alloy surface, but instead is reduced indirectly by reaction with an adsorbed hydrogen. The reaction barrier is vastly more favourable when this process occurs at In or Sn sites (average: 0.26 eV), than when it occurs on Ga (average: 0.47 eV). However, there is no difference in barrier between solid and liquid surfaces. Instead, we find that Hads is mobile only on the liquid surface, travelling due to the motion of the liquid beneath. This process drives Hads to In/Sn sites, allowing low‐barrier CO2 reduction to occur only on the liquid. Therefore, the dynamic motion of liquid metal catalysts can underpin their unique reactivity. The result has far reaching implications for any protonation reaction conducted with a liquid metal catalyst. [ABSTRACT FROM AUTHOR]

Organic–inorganic hybrid porous materials (OIHMs) inherit the unique properties from both organic and inorganic components, and the flexibility in the incorporation of functional groups renders the OIHMs an ideal platform for the construction of catalytic materials with multiple active sites. The preparation of OIHMs with precise locations of organic–inorganic components and tunable structures is one of the important topics for the catalytic application of OIHMs, but it is still very challenging. In this feature article, we describe our work related to the preparation of OIHMs via confining active sites in the nanostructure and a layer-by-layer assembly method and their applications in acid–base catalysis, catalytic hydrogenation and photocatalysis with a focus on the elucidation of the synergistic effects of different active sites and the unique properties of OIHMs in catalysis. [ABSTRACT FROM AUTHOR]

Photo-thermo catalysis that combines photo- and thermo-catalysis has emerged as an attractive approach for effective and economical elimination of pollutants. Herein, we fabricated a robust, highly water stable 2D Co(II)-MOF photo-thermo catalyst towards the decomposition of permanganate anions. It has been demonstrated that Co(II)-MOF exhibits excellent catalytic capacity, good selectivity and incredible reusability for degrading MnO4-. The reaction rate of the process was investigated for thermo-photo vs. thermo/photo processes to provide conclusive evidence that Co(II)-MOF shows a strong synergistic use as both an energy source and Lewis acid. [ABSTRACT FROM AUTHOR]

As a new type of artificial enzyme, a nanozyme is an ideal substitute for natural enzymes and has been successfully applied in many fields. However, in the application of biomolecular detection, most nanozymes have the disadvantages of long reaction times or high detection limits, prompting researchers to search for new efficient nanozymes. In this work, the enzyme-like activities of three polyoxometalate-based iron-organic complexes ([Fe(bpp)2](Mo6O19), [Fe(bpp)2]2(Mo8O26)·2CH3OH, and [Fe(bpp)2]4H[Na(Mo8O26)]3), namely, FeMo6, Fe2Mo8, and Fe4Mo8Na, were analyzed. All three polyoxometalate-based iron-organic complexes were found to be capable of catalyzing hydrogen peroxide (H2O2) to oxidize 3,3′,5,5′-tetramethylbenzidine and o-phenylenediamine, resulting in visible color changes, further exhibiting peroxidase-like activity. Results showed that Fe4Mo8Na had more active sites due to its long chain structure, endowing more prominent peroxidase-like activity compared with Fe2Mo8 and FeMo6. A colorimetric sensing platform for H2O2 and ascorbic acid detection based on Fe4Mo8Na was established. The linear response range for H2O2 detection was 0.5–100 μM, and the detection limit was 0.143 μM. The linear response for ascorbic acid detection ranges from 0 to 750 μM with a detection limit of 1.07 μM. This study provides a new perspective for developing new nanozymes and expanding the sensing and detection application of nanozymes. [ABSTRACT FROM AUTHOR]

In this work, star-shaped heterostructures of Ag 2 O/BaTiO 3 /ZnO were proposed as resistive-type gas sensors. Through combined analyzes of XRD, SEM, and EDS, the structure, surface morphology, and the elemental composition of the synthesized materials were confirmed. The star-shaped morphology of BaTiO 3 /ZnO was found to be intact even after loading with different quantities of Ag 2 O, as revealed by the SEM analysis. The impact of loading different amounts of Ag 2 O (ranging from 1 % to 3 %) on the sensors' ability to detect volatile organic compounds (VOCs) and carbon dioxide (CO 2) was concretely gauged by their response, response/recovery times, selectivity, and long-term stability. For the detection of ethanol/acetone, CO 2 , and methanol, a 1:2 M ratio of BaTiO 3 /ZnO with 1 % and 2 % Ag 2 O, and a 1:3 M ratio of BaTiO 3 /ZnO with 1 % Ag 2 O were determined as the optimum content, respectively. From the gas sensing analysis, Ag 2 O/BaTiO 3 /ZnO sensors with different amounts of Ag 2 O additive gave different optimal temperatures for different target gases. Lower operating temperatures, i.e. 180 °C, and 260 °C for CO 2 and VOCs, respectively, rapid responsivity with a response time of <1 s for VOCs, and fast recovery times (as low as 10, 13, and 6 s for ethanol, acetone, and methanol vapors, respectively) were observed. More importantly, the sensor exhibited good selectivity for several possible interferences. The underlying reasons for the acceleration of the gas molecules adsorption, hence the fast sensor response, are the high specific surface area established by the star-shaped morphology, and compatible energy band alignment at the p/n interface coupled with the catalytic effect induced by Ag 2 O. [ABSTRACT FROM AUTHOR]

Persistent phosphors possess unique afterglow optical properties. In this paper, a class of ultra-violet (UV) persistent luminescence nanoparticles were developed for catalytic photodegradation applications. UV persistent luminescence nanoparticles of SiO 2 -Zn 2 SiO 4 :Ga and SiO 2 -Zn 2 SiO 4 :Ga,Pb were successfully synthesized by using a mesoporous template method. The UV persistent luminescence intensity of SiO 2 -Zn 2 SiO 4 :Ga at 405 nm was enhanced up to ca. 3.5 times by co-doping with Pb2+ (396 nm), along with longer persistent luminescence duration. The photodegradation results indicate that it is useful to introduce UV persistent luminescence property into SiO 2 -Zn 2 SiO 4 :Ga,Pb to obtain enhanced catalytic activity of SiO 2 -Zn 2 SiO 4 with a bigger catalytic oxidation reaction kinetic constant (up to ∼4 times). This kind of UV persistent catalysis strategy may become a potential feasible method for better catalytic photodegradation activity. The UV persistent photocatalyst has potential applications in the photooxidation of organic molecules in high chroma and/or turbidity aqueous systems. [ABSTRACT FROM AUTHOR]

Herein, we disclose the first report on gold‐catalyzed C(sp2)‐CN cross‐coupling reaction by employing a ligand‐enabled Au(I)/Au(III) redox catalysis. This transformation utilizes acetone cyanohydrin as a nucleophilic cyanide source to convert simple aryl and alkenyl iodides into the corresponding nitriles. Combined experimental and computational studies highlighted the crucial role of cationic silver salts in activating the stable (P,N)‐AuCN complex towards the oxidative addition of aryl iodides to subsequently generate key aryl‐Au(III) cyanide complexes. [ABSTRACT FROM AUTHOR]

While significant progress has been made in the area of transition metal‐catalyzed ring‐opening and formal cycloaddition reactions of 1,1‐disubstituted silacyclobutanes (SCBs), synthesizing these SCBs—particularly those bearing additional functional groups—continues to present synthetic challenges. In this context, we present a novel Ni‐catalyzed reductive coupling reaction that combines 1‐chloro‐substituted silacyclobutanes with aryl or vinyl halides and pseudohalides, thereby obviating the need for organometallic reagents. This method facilitates the generation of 1,1‐disubstituted silacyclobutanes with a remarkable tolerance for various functional groups. This approach serves as a complementary and more step‐economical alternative to the commonly used yet moisture‐ and air‐sensitive nucleophilic substitution reactions involving Grignard or lithium reagents. Our initial mechanistic studies indicate that this reaction is initiated by oxidative cleavage of the Si−Cl bond in 1‐chlorosilacyclobutanes, which represents a distinct mechanism from the previously documented reductive coupling processes involving carbon electrophiles and chlorosilanes. [ABSTRACT FROM AUTHOR]

Herein, we report the first example of Rh-catalyzed C(sp²)-H difluoroallylation of α,β-unsaturated amides with 3-bromo-3, 3-difluoropropene under mild conditions. The features of this protocol for difluoroallylation are unprecedented vinylic substrates, ethanol as a green solvent, good functional group and air compatibility, and scale-up synthesis with low catalyst loading. [ABSTRACT FROM AUTHOR]

Heterogeneous photocatalysts based on polyoxovanadates with Keggin structure (POV) supported onto zeolite (NH4ZSM‐5) were developed. The amount of POV incorporated was varied from 5% to 30% wt. Catalysts were characterized by N2 adsorption–desorption isotherms, FT‐IR, XRD, DRS UV–vis, TGA, and 31P MAS‐NMR techniques; and the catalytic activity was evaluated in azo dye degradation. The specific surface area decreased as the POV content increased because of zeolite pore blocking. The XRD patters presented the characteristic peaks of NH4ZSM‐5 and POV, with no additional diffraction peaks, assigned to a well dispersed POV. FT‐IR and 31P MAS‐NMR results confirm that the Keggin structure of [PVW11O40]4− anions remain unaltered after their inclusion in the zeolite. The incorporation of POV generated a redshift at the absorption border, determined by DRS UV–vis, which promotes its activity in the visible range. Moreover, while POV content increase the bandgap energy diminishes and the photocatalytic activity increased. The higher photoactivity was 80% of discoloration when 30% wt of POV was incorporated. The characterization and catalytic evaluation indicated that these materials present suitable properties to be used as catalysts in the photocatalytic treatment of wastewater, being the main advantage their easy separation and reuse without significant decrease of the photoactivity. [ABSTRACT FROM AUTHOR]

Metallacycloprop-1-ene and metallacycloprop-2-ene complexes are the smallest unsaturated metallacycles, and have attracted continuing attention for their importance in organometallic synthesis and catalysis. This feature article summarizes the syntheses of monocyclic and fused metallacycloprop-2-enes, and monocyclic, spiro, and fused metallacycloprop-1-enes, all with crystallographically characterized structures. The aromatic properties of mononuclear metallacyclopropene complexes are also described. [ABSTRACT FROM AUTHOR]

This Short Review summarizes the synthesis and applications of triarylboranes (BAr3), including both homoleptic and heteroleptic species, with a focus on the modification of their electronic and structural properties via the introduction of meta -substituents with respect to the B atoms to their Ar groups. This approach constitutes a complementary alternative to conventional strategies for the design of BAr3 , which are usually based on a modification of their ortho - and/or para -substituents. An initial analysis revealed that CH3 and F are the most common meta -substituents in hitherto reported BAr3 (apart from the H atom). Thus, an extensive exploration of other substituents, e.g., heavier halogens, longer or functionalized alkyl groups, and aryl groups, will increase our knowledge of the structure and reactivity of BAr3 and eventually lead to a range of new applications. 1 Introduction 2 Scope of this Review 2.1 The Electronic and Steric Influence of meta -Substituents 2.2 Molecular Transformations Mediated by meta -Substituted Boranes 2.3 Other Examples of meta -Functionalization of BAr3 3 Conclusions and Perspectives [ABSTRACT FROM AUTHOR]

Vicinal stereogenic centers represent prevalent structural motifs in organic synthetic chemistry, and their construction poses a longstanding challenge. Transition-metal-catalyzed asymmetric allylic substitution has become a well-established enantioselective C–C bond-forming reaction. When these reactions involve a prochiral nucleophile and an allylic electrophile with a terminal substituent, the creation of vicinal stereogenic centers becomes feasible. However, despite remarkable achievements having been accomplished, realizing this transformation with precise control over both the enantio- and diastereoselectivity remains a significant challenge. To address the stereoselective challenges, the introduction of a second catalyst to the transition-metal-catalyzed asymmetric allylic alkylation to control the diastereoselectivity during C–C bond formation has proven particularly fruitful. In this short review, we aim to highlight recent advances in dual catalysis that enable diastereo- and enantioselective allylic substitutions. 1 Introduction 2 Construction of Vicinal Stereogenic Centers by Organo and Metal Dual Catalysis 2.1 Chiral Phase-Transfer Catalysis and Transition-Metal Dual Catalysis 2.2 Chiral Amine and Transition-Metal Dual Catalysis 2.3 NHC and Transition-Metal Dual Catalysis 2.4 Chiral Aldehyde and Transition-Metal Dual Catalysis 2.5 Chiral Lewis Base and Transition-Metal Dual Catalysis 3 Construction of Vicinal Stereogenic Centers by Metal and Metal Dual Catalysis 3.1 Lewis Acidic Metal and Iridium Dual Catalysis 3.2 Lewis Acidic Metal and Palladium Dual Catalysis 3.3 Palladium and Ruthenium Dual Catalysis 3.4 Other Advancements in the Construction of Vicinal Stereogenic Centers through Synergistic Bimetallic Catalysis Enabling Asymmetric Allylic Alkylation 4 Conclusions and Future Outlook [ABSTRACT FROM AUTHOR]

A relay catalytic system is developed for the asymmetric hydrogenative coupling of indoles with α,β-unsaturated ketones, affording enantioenriched chiral γ-indole alcohols with broad substrate scope and excellent enantioselectivities (32 examples, up to >99% ee). Mechanistic studies suggest that the relay catalytic system consists of copper-catalyzed alkylation and ruthenium-catalyzed asymmetric hydrogenation. [ABSTRACT FROM AUTHOR]

Nickel catalysis is a well-established and powerful tool for C–C cross-coupling reactions, and its versatility has expanded significantly over past decades by its combination with visible-light photocatalysis in metallaphotoredox chemistry. Photocatalysis enables the activation of traditionally inert substrates and turnover of the Ni catalyst through a single-electron transfer processes. In recent years, dual catalysis has been further empowered by photoactive Ni intermediates, which exhibit distinct reactivity profiles from their ground states and complement existing protocols. This short review focuses on the emergent subclass of metallaphotoredox catalysis in which the synergy of a photoactive Ni catalyst and a typical photocatalyst (e.g., a polypyridyl Ir complex) provide solutions to challenging C–C bond formation. 1 Introduction 2 Photoactive Nickel Complexes 3 HAT-Mediated C–C Cross-Coupling 4 Halofunctionalization of π-Systems 5 Photoelimination of an Aryl Radical 6 Conclusion [ABSTRACT FROM AUTHOR]

We report an HN-ZIF-67 catalyst with a large hollow structure and well-dispersed active sites by a facile diffusion-controlled strategy. Compared with the pristine ZIF-67 and semi-sealed ZIF-67, HN-ZIF-67 shows remarkable catalytic activity in the hydrogenation of nitro-compounds due to its highly dispersed active sites that are exposed to the substrate, and long cycle life. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A greener and more convenient alternative to traditional methods for the generation of thiyl radical as hydrogen atom transfer (HAT) catalyst is developed, using molecular oxygen to oxidize thiol without the need for chemical initiators or light irradiation. The thiol/oxygen catalysis enables selective and efficient difunctionalization of borane. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Amorphous nanomaterials are metastable nanomaterials which only have short‐range order within a few neighboring atoms, based on the local chemical bondings. Different from crystalline materials, the amorphous nanomaterials lack of long‐range order exhibit many intriguing and unique structu ral features, such as abundant active sites, structural flexibility, intrinsic isotropy and fast ionic transport. However, due to the unco nventional structural complexity, the systematic study and understanding of amorphous nanomaterials are still in the early stage. In this review, we will describe our journey to the synthesis, characterization and applications of amorphous nanomaterials, including catalysis, energy storage, optics and mechanics. What is the most favorite and original chemistry developed in your research group? Our group developed a variety of universal methods, such as "coordination etching" method, "self‐hydrolytic etch‐precipitation" method, photoetching method, co‐precipitation method, etc., to achieve the controllable preparation of amorphous nanomaterials with different morphology, size and dimension, and the catalytic, mechanical and optical properties of the materials and their potential applications were also studied. Moreover, the relevant mechanisms were proposed, the structure‐activity relationship was established, and the development and application of amorphous micro‐nanomaterials were promoted. How do you get into this specific field? Could you please share some experiences with our readers? My journey into the field of amorphous nanomaterials began 20 years ago when I developed a fascination for materials science and nanotechnology. During my early research experiences, I encountered the intriguing world of amorphous nanomaterials. These materials, lacking a long‐range crystalline order, presented both challenges and opportunities in terms of their synthesis and understanding their properties. It's a field where creativity and precision intersect, driving me to continually seek innovative solutions and deepen my understanding of nanoscale phenomena. How do you supervise your students? As a professor, I supervise students by setting clear expectations, holding regular meetings for feedback and guidance, and encouraging independent thinking. I support their career development by identifying opportunities and creating a collaborative environment. Adapting to individual needs, I foster a fair and consistent approach to help students grow professionally and academically. What is the most important personality for scientific research? One of the most important traits for scientific research is curiosity. It drives researchers to ask questions, explore new ideas, and seek innovative solutions. Curiosity fuels the desire to understand the unknown, propelling scientific discovery and breakthroughs. Additionally, persistence is crucial as research often involves challenges and setbacks that require perseverance to overcome. Clear communication skills are also vital for sharing findings and collaborating effectively within the scientific community. Who influences you mostly in your life? As a researcher, my greatest influences come from my mentors, Prof. Hesun Zhu, Qianshu Li and Shihe Yang who guide my academic journey and collaborators who inspire new ideas and perspectives. My mentors, who provide guidance and expertise play a crucial role in shaping my approach to research and career development. Their insights and support empower me to navigate challenges and continuously strive for excellence in my scientific endeavors. What are your hobbies? My hobbies are a blend of activities that complement and enrich my professional life. I enjoy participating in discussions and workshops within my academic community, where I can exchange ideas and learn from peers outside of formal research settings. Key Scientists: [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Advanced functionalization‐decorated porous organic polymers (POPs) are emerging as a prominent research focus, spanning from their construction to applications in gas storage and separation, catalysis, energy storage, electrochemistry, and other areas. Furthermore, the inherent organic nature, tailored pore structures, and adjustable chemical components of POPs offer a versatile platform for the incorporation of various metal active sites. Meticulously designed molecular building blocks can serve as organic ligands uniformly distributed throughout POPs, leading to the effective isolation of inorganic metal active sites at the molecular level. In this manner, POPs containing active metal centers bridge the gap between organic and inorganic scaffolds. This review aims to provide an overview of recent research progress on metal‐decorated POPs, focusing on strategies for incorporating metal active sites into POPs and their applications in adsorption, separation, catalysis, and photoelectrochemistry. Finally, current challenges and future prospects are discussed for further research. Key Scientists: Advanced functionalized porous organic polymers have become a new research hotspot, ranging from their construction to their use in gas storage and separation, catalysis, energy storage, electrochemistry, and other applications. In 2002, the McKeown group was the first to report phthalocyanine‐based MPOPs with permanent porosity and a moderate surface area. In 2010, the Yu group prepared nanoporous polyporphyrin materials P(Fe‐TTPP) from the metallated porphyrin with functionalized thiophenyl groups by the FeCl3 catalyzed oxidation couple reaction showing the surface area of 1522 m2·g–1. Subsequently, in 2013, the Deng group was the first to use metalated salens as the original building blocks for preparing MPOPs. The Morin group was the first to produce a series of ferrocene‐based nanoporous frameworks via radical polymerization, with surface areas ranging from 385 to 899 m2·g–1. In 2016, the Han group synthesized two N‐pyridinylphenylcarbazole (PPC) ligands to produce a series of metalized polycarbazole networks. Recently, the Tan group reported a solvent‐knitting hyper‐cross‐linking reaction to produce HUST‐1, which contains a porphyrin unit. The porphyrin moiety provides a centered square‐planar metal post‐coordination site, resulting in the metalated HUST‐1‐Co, which exhibits high efficiency in the catalytic conversion of CO2. Additionally, the Kegnæs group combined the decomposition of the palladium complex with an in situ catalyzed polymerization reaction, enabling the confinement of nascent Pd particles in the developing polymer network. This review focuses on recent research progress in metal‐decorated POPs, emphasizing strategies for incorporating metal active sites into POPs and their applications. [ABSTRACT FROM AUTHOR]

Noble metal nanoparticles (NMNPs) are crucial for catalytic processes, but their recycling and aggregation present challenges. Immobilizing NMNPs on substrates often reduces their catalytic activity due to hindered diffusion and decreased surface area. This study presents a novel approach using silver (N-Isopropylacrylamide Co methyl acrylic acid) (Ag@PNM) nanoparticles, characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), dynamic light scattering transmission (DLS), transmission electron microscopy (TEM) and UV–visible spectroscopy. A catalytic membrane with silver nanoparticles (Ag NPs) embedded in a three-dimensional (3D) network of hybrid microgels was fabricated. The microgels are filtered into a microporous membrane and expanded to secure the Ag NPs, enhancing catalytic efficiency for 4-nitrophenol reduction through improved mass transfer and exposure of the nanoparticles. The membrane shows high stability and performance, with a turnover frequency of 77.5 h−1 and an apparent rate constant (kapp) of 0.15 s−1. Additionally, the PES/Ag@PNM membrane demonstrated effective reduction of 4-nitrophenol. The straightforward synthesis and stability of this approach make it a promising and cost-effective solution for industrial applications. [ABSTRACT FROM AUTHOR]

[Display omitted] The present paper reports the fabrication of novel types of hybrid fibrous photocatalysts by combining block copolymer (BCP) templating, sol–gel processing, and coaxial electrospinning techniques. Coaxial electrospinning produces core–shell nanofibers (NFs), which are converted into hollow porous TiO 2 NFs using an oxidative calcination step. Hybrid BCP micelles comprising a single plasmonic nanoparticle (NP) in their core and thereof derived silica-coated core–shell particles are utilized as precursors to generate yolk-shell type particulate inclusions in photocatalytically active NFs. The catalytic and photocatalytic activity of calcined NFs comprising different types of yolk-shell particles is systematically investigated and compared. Interestingly, calcined NFs comprising silica-coated yolk-shells demonstrate enhanced catalytic and photocatalytic performance despite the presence of silica shell separating plasmonic NP from the TiO 2 matrix. Electromagnetic simulations indicate that this enhancement is caused by a localized surface plasmon resonance and a confinement effect in silica-coated yolk-shells embedded in porous TiO 2 NFs. Utilization of the coaxially electrospun TiO 2 NFs in combination with yolk-shells comprising plasmonic NPs reveals to be a potent method for the photocatalytic decomposition of numerous pollutants. It is worth noting that this study stands as the first occurrence of combining yolk-shells (Au@void@SiO 2) with porous electrospun NFs (TiO 2) for photocatalytic purposes and gaining an understanding of plasmon and confinement effects for photocatalytic performance. This approach represents a promising route for fabricating highly active and up-scalable fibrous photocatalytic systems. [ABSTRACT FROM AUTHOR]

Axially chiral furan‐based scaffolds have been recognized as a class of important five‐membered heteroaryl atropisomers, and developing catalytic atroposelective reactions for constructing this class of scaffolds is highly desirable. However, the catalytic atroposelective construction of such scaffolds is rather underdeveloped due to the existence of great challenges such as remote ortho‐substituents and weak configurational stability. To overcome these challenges, synthetic chemists have recently paid great attention to this research field, and a number of axially chiral furan‐based scaffolds have been constructed via catalytic atroposelective reactions using different strategies. This concept summarized these advances in this field and pointed out the remaining challenges, which will promote the further development of this emerging field. [ABSTRACT FROM AUTHOR]

The combined use of O2 and CO2 as oxidizing agents in the oxidative coupling of methane (OCM) has been assessed over two representative OCM catalysts, i. e., La−Sr/CaO and NaMnW/SiO2, under a wide range of inlet O2 and CO2 concentrations. The overall impact of CO2 was found to depend on the operating conditions and the catalyst used. At O2‐rich conditions, a negative effect of CO2 was observed on C2 selectivity. At O2‐lean conditions, a positive effect of CO2 on both catalysts was observed, likely originating from an enhanced dehydrogenation of C2H6 to C2H4 and limited deep oxidation of the involving hydrocarbons and reaction intermediates. The behavior induced by CO2 is attributed to its mild oxidizing ability and interactions with the catalysts. The enhanced dehydrogenation of C2H6 was observed and confirmed by specific tests with a CO2 and C2H6 feed. Well‐controlled CO2 addition improved the value of the OCM product mixture, mainly due to a 9 % increase in C2H4 and a 19 % increase in CO selectivity, resulting in a 25 % reduction of CO2 at the outlet over the La−Sr/CaO catalyst. These findings provide new insight into the CO2 effect on OCM and the data to translate this research into OCM process alternatives. [ABSTRACT FROM AUTHOR]

Oxygen Evolution Reaction (OER) is a fundamental process, with gold standards like RuO2 and IrO2. Recently, it was suggested that OER could go through unconventional intermediates, −O−H, −OO−H. −O−H is formed by the direct interaction of an adsorbed O species to a metal surface atom and a proton bound to a surface oxygen. Similarly, in −OO−H, an adsorbed −OO adduct interacts with a proton on a surface oxygen. This work compares the nature of key intermediates of OER on TiO2, RuO2, and IrO2(110) surfaces by Density Functional Theory (DFT) calculations and Ab‐Initio Molecular Dynamics (AIMD). We rationalized the nature, the relative stability trends in vacuum and the effect of water solvation of the species. −OO−H is preferred than −OOH. −OH is preferred than −O−H except for RuO2. We investigated the nature of the catalyst/water interfaces and the interaction of intermediates with water based on AIMD. On RuO2, −OH and −O−H display a different interaction with water. −OO−H is quite rigid on RuO2, while it is dynamic on IrO2 as the proton is shared between −OO and a surface oxygen atom. This study provides insights on the role of solvation to the nature of OER intermediates, that may help future studies. [ABSTRACT FROM AUTHOR]

Chiral aziridines are important motifs in natural products and biologically significant compounds, as well as one of the most valuable and versatile building blocks for the construction of diverse chiral functionalized amines. Because of the importance of chiral aziridines, various novel transition‐metal‐based catalytic systems and synthetic strategies have been established to investigate the highly effective and enantioselective aziridination process. This review outlined the recent significant advances made in the transition‐metal catalyzed enantioselective aziridination reactions, as well as the challenges and potential of the field at the current stage. [ABSTRACT FROM AUTHOR]

The direct conversion of syngas into hydrocarbons, catalyzed by a combination of metal oxide and acidic zeolite, has garnered increasing attention in the scientific community. The remarkable hydrocarbon selectivity achieved in the OX‐ZEO process is a key factor in this growing interest. This process involves two distinct steps: CO activation over the oxide and subsequent C−C coupling within the zeolite pores, connected by an unidentified oxygenate intermediate. In this study, we explored three proposed oxygenates as potential intermediates and compared their conversion within the OX‐ZEO process. Using a bifunctional ZnCr2O4/H‐MOR catalyst in a syngas‐fed batch reactor, we found that methanol (MeOH) and dimethyl ether (DME) produced a hydrocarbon distribution similar to syngas conversion. However, the conversion of acetic acid (AcOH) resulted in a notably distinct range of hydrocarbons, including short olefins not detected with other reagents. Our findings suggest that methanol/DME might serve as active intermediates in the OX‐ZEO process over the ZnCr2O4/H‐MOR catalyst. This study provides a deeper insight into the transformation of proposed intermediates, contributing to the identification of the bridging intermediate that links the two catalytic functions. [ABSTRACT FROM AUTHOR]

Dialkoxymethane (DAM) ethers, so‐called oxymethylene ethers (OMEs), are compounds constituted by a CH2‐unit bound to two identical alkoxy substituents. These compounds have showcased interesting technological applications as fuel additives or fuels, as a consequence of their interesting properties such as their low vapor pressure, high viscosity, cetane number and oxygen content. Moreover, they are also employed as environmentally‐benign solvents and bulk compounds useful in fine‐chemical industry. In addition, DAM ethers are considered formaldehyde surrogates. Industrially, dimethoxymethane (DMM) is still produced via two‐step protocol involving toxic formaldehyde that consists of a first step of methanol oxidation (Formox process). Hence, the development of more sustainable protocols for their synthesis is highly desired. Among the different strategies reported for DAM synthesis, its production from CO2/H2 and alcohols constitutes a practical, green and attractive alternative route. In this concept, a careful discussion of the developed catalytic protocols for synthesizing DAM from CO2/H2 or formic acid/H2 and alcohols/diols will be summarized. A special emphasis will be performed on the reaction mechanisms involved and the catalyst nature design and characterization. [ABSTRACT FROM AUTHOR]

ABSTRACT A novel ZnO‐Co3O4‐CuO nanocomposite (NC) has been explored as a heterogeneous catalyst for synthesizing a library of polyhydroquinolines (PHQ 1–10) via microwave‐assisted multicomponent reaction of various aromatic aldehydes, ethyl acetoacetate or ethyl cyanoacetate, dimedone, and ammonium acetate at 400 W in polyethylene glycol (10 mL) as a solvent. The NC showed a characteristic weak ferromagnetic behavior with a particle size of 10.3 ± 0.1 nm and surface area of 45.67 m2/g was easily prepared through a straightforward chemical coprecipitation method and was systematically characterized using XRD, FTIR, FESEM, HRTEM, EDS, BET, and VSM. The NC has an agglomerated particle cluster having a nearly spherical shape exhibiting brilliant catalytic performance, over +12.94 mV zeta potential value, hydrodynamic diameter of 267 nm, best dispersion stability, and reusability for up to six runs. This method of synthesizing PHQs has notable advantages of producing higher yields in a shorter reaction time (20 min), using simple, low‐cost catalyst, and microwave irradiation as a non‐conventional energy source. The highest TON of 37.76 and TOF of 113.29 h−1 also indicate that this is the best atom‐efficient and green design for the synthesis of polyhydroquinolines. Some novel polyhydroquinolines were also synthesized with excellent yield. [ABSTRACT FROM AUTHOR]