Using renewable biomass to synthesize valuable chemicals can reduce fossil fuel dependence and achieve carbon neutrality. Here, for the first time an infrared light-driven catalyst, Cu/Fe2O3, was designed to convert bioethanol to valuable acetaldehyde, accompanied by green hydrogen as a by-product, under both indoor IR light and natural sunlight. It achieves an initial acetaldehyde yield of 237 mmol g-1 h-1 under indoor IR irradiation and 205 mmol g-1 h-1 under real sunlight, with exceptional selectivity (97.7%) and nearly stoichiometric H2 byproduct production. Notably, the turnover number and initial turnover frequency surpass those of IR-driven systems by at least one order of magnitude and perform competitively with leading energy-intensive UV-vis-driven and thermocatalytic ethanol conversion processes operated up to 573 K. This high performance is attributed to: i) the construction of an efficient IR photons-to-phonons energy conversion channel within the ps timescale to drive localized thermocatalysis; and ii) the synergistic effect on the in situ formed of Cu/Fe2O3 interface, where Fe3+ sites promote dissociative ethanol adsorption, and Cu0 sites facilitates C─H bond cleavage.

Operating nanometal catalysts under harsh reaction conditions often leads to their disintegration into less active single atoms or clusters, which is considered as a primary cause of catalyst deactivation and loss of active components. In the current work, our theoretical calculations on CeO₂-supported Rh catalysts first reveal that pre-filling surface vacancies with suitable single metal atoms renders the subsequent anchoring of Rh atoms on supports energetically unfavorable. Guided by this insight, we propose a simple strategy that pre-anchored guest atoms to generate a high-potential confinement field, which thermodynamically suppresses the release of atoms from nanoparticles and their subsequent deposition onto the support, thereby stabilizing Rh nanocatalysts across a wide temperature range during methane oxidation while maintaining high activity. Catalytic tests of simulated engine methane emissions, coupled with environmental scanning transmission electron microscopy characterizations, reveal that both supported Rh nanoparticles with and without pre-anchored single atoms demonstrate initial methane oxidation activity at temperatures below 200 °C, while only single-atom-confined nanoparticles retain structural integrity and full activity after 800 °C aging, whereas unprotected ones degrade into single atoms and lose low-temperature reactivity, thereby confirming the effectiveness of our confinement strategy. Further theoretical calculations unveil that the low-temperature activity is driven by Rh nanoparticles with pronounced electron delocalization, rather than Rh single-atom interacting with the CeO₂ support. This work offers a new design strategy based on a novel energy confinement effect for dynamically stabilizing supported metal nanoparticle catalysts even under severe conditions while maintaining exceptional catalytic activity, opening up new avenues for catalyst design through alternative approaches beyond conventional metal-support interactions to regulate and enhance nanoparticle behavior and reactivity.

In this study, we report a remote C-H sulfenylation of 5,10-dihydrophenazasilines enabled by a cooperative catalytic system comprising a chiral Lewis base and an achiral Brønsted acid for the first time. The synergistic use of a chiral phosphoric triamide sulfide catalyst featuring a bis((S)-1-phenylpropyl)amine structural motif and an achiral sulfonic acid co-catalyst with precisely tuned acidity is essential for achieving efficient remote stereocontrol. This methodology provides efficient access to chiral silicon-stereogenic sulfur-containing organosilanes. A broad substrate scope is demonstrated, affording the desired products in moderate to excellent yields (up to 94%) and with moderate to excellent enantioselectivities (up to >99% ee). Mechanistic investigations through control experiments suggest that the reaction proceeds via sequential desymmetrization and kinetic resolution processes. Density functional theory (DFT) calculations further demonstrate that multiple weak C-H⋯π interactions, together with the torsional distortion of the substrate, are crucial for the observed enantioselectivity.

ABSTRACT Acetic acid represents a pivotal target for CO 2 reduction due to its dual function as a carbon‐utilization product and industrial feedstock. However, photocatalytic CO 2 reduction (PCCR) to acetic acid typically suffers from low acetic acid yields and selectivity, constrained by competing reactions from ethanol and inefficient C–C coupling. Herein, we report a chiral mesostructured ZnIn 2 S 4 (CMZI) photocatalyst that achieves a remarkable acetic acid yield of 962 µmol g −1 h −1 with a high selectivity of 97.3%. This performance stems from synergistic chirality‐induced spin polarization and sulfur site catalysis. Spin polarization stabilizes the triplet OCCO intermediate to enhance C–C coupling, while sulfur sites on ZnIn 2 S 4 {102} facets thermodynamically and kinetically favor acetic acid formation. This work offers critical insights into catalytic strategies of the efficient synthesis of high‐value multicarbon products and expanding the variety of synthetic products from CO 2 reduction.

Light-driven dry reforming of methane (LDRM) provides a feasible route for converting methane (CH4) and carbon dioxide (CO2) into synthesis gas, yet most reported systems require ultraviolet light or a high photon flux, limiting their practical deployment. Here, we show that interfacial oxygen vacancy dynamics can be regulated under mild broadband irradiation through engineered metal-support electronic coupling. In this way, Rh nanoparticles (NPs) supported on two-dimensional CeO2 nanosheets (NS) exhibit record-high Rh-specific activity under low-intensity broadband irradiation (1.20 W & centerdot;cm-2, 200-800 nm) without external heating, delivering H2 and CO production rates of 681 and 832 mmol & centerdot;gRh -1 & centerdot;h-1, respectively, together with the highest light-to-chemical energy conversion efficiency (LTCEE) reported for Rh-based LDRM catalysts under low-intensity irradiation (<= 3.0 W & centerdot;cm-2). In-situ characterizations, combined with density functional theory calculations, reveal a photochemical Mars-van Krevelen mechanism driven by interfacial charge separation. Photoexcited electrons transfer from CeO2-NS to Rh NPs across the Schottky junction, generating electron-rich Rh delta- species, while holes remain on CeO2-NS to induce interfacial oxygen vacancies (Ov). These vacancies serve as dynamic active sites that lower the energy barrier for CO2 dissociation, promote *CH3O oxidation, and facilitate *CO desorption. The ultrathin nanosheet architecture further lowers the Ov formation energy and improves charge separation efficiency, enabling dynamic vacancy generation under a low photon flux. This work establishes a general strategy for integrating light-induced charge separation with defect-mediated thermal chemistry to overcome kinetic limitations in thermodynamically demanding reactions, offering a pathway toward efficient solar-driven reforming.

Methacrylonitrile (MAN) serves as a key precursor for the synthesis of many important functional materials, but its efficient production via isobutylene ammoxidation is still constrained by the limited surface activity and stability of the conventional MoVTeNbO catalysts. Herein, we employ density functional theory calculations with on-site Coulomb interaction correction to elucidate at the atomic scale how Ce doping can regulate the electronic structure and catalytic performance of MoVTeNbO for ammoxidation. Our calculated results reveal that Ce readily substitutes for a surface Te site to form the thermodynamically most stable configuration (MoVTe(Ce)NbO), and this substitution introduces an unoccupied Ce 4f state and significantly promotes the initial activation of NH3 and isobutylene. By mapping the full reaction pathway for isobutylene ammoxidation to MAN, we further identify a synergetic dual role of Ce: (i) the distinctive empty Ce 4f states facilitate NH3 dissociation; (ii) the flexible coordination environment of Ce stabilizes the key oxygenated intermediates (e.g., OOH*, and OH*), thereby promoting subsequent oxidative dehydrogenation steps and boosting MAN formation. These findings establish clear design principles for engineering redox-active dopants into mixed-metal oxide catalysts and offer a theoretical foundation for developing high-performance and selective ammoxidation catalysts.

The electrochemical synthesis of hydrogen peroxide (H2O2) through the oxygen reduction reaction (ORR) functions as a sustainable alternative to the energy-intensive anthraquinone process, offering compatibility with renewable energy systems. Nevertheless, there are still critical challenges in attaining high selectivity and superior yield of H2O2. In this work, a CeO2/C composite catalyst is rationally designed through synergistic integration of ceria with surface-oxygen-rich carbon, which establishes an optimized microenvironment for efficient H2O2 generation. The CeO2/C catalyst achieves exceptional H2O2 selectivity of 92 % with an extended potential range from 0.7 to 0.2 V, together with 7.66 mol gcat stability, outperforming pristine ceria. Comprehensive characterizations reveal that the outstanding performances originate form dual-functional electronic modulation and defect-mediated intermediate optimization. The integration of oxygen-rich carbon with CeO2 induces interfacial electron transfer, simultaneously generating abundant oxygen vacancies and Ce3+ sites while preserving the oxygen-containing functional groups in amorphous carbon. The synergistic interplay between charge redistribution and defect engineering optimizes OOH* intermediate adsorption, thereby steering the ORR pathway toward H2O2 generation. This study provides fundamental insights into heterointerface engineering for sustainable peroxide synthesis.

Understanding charge transfer at semiconductor-metal interfaces is central to advancing photoelectronic materials, yet real-time monitoring of such ultrafast processes remains elusive. Here, we introduce a hybrid nanoarray-enhanced laser desorption/ionization mass spectrometry (HyNA-LDI-MS) strategy that enables direct and rapid tracking of photoelectrons and hot carriers at hybrid interfaces. Using juglone as an electron scavenger and representative analytes as hole probes, we provide mass spectrometric evidence of interfacial charge generation and reveal markedly higher transfer efficiency at conductive interfaces compared with insulating ones. Incorporating 4-methylbenzylpyridinium as a chemical thermometer uncovers a competition between charge transfer and photothermal heating: conductive interfaces favor efficient electron transfer that suppresses heat generation, while insulating ones convert excited electrons predominantly into thermal energy. These insights, supported by complementary optoelectronic studies and density functional theory-calculations, establish HyNA-LDI-MS as a powerful tool to unravel charge-energy dynamics at complex interfaces. This study provides fundamental insights into interfacial processes, guiding the design of high-performance analytical platforms such as LDI-MS systems and offering significant implications for related biomedical applications.

NH3-selective catalytic reduction (NH3-SCR) is a key technology for efficient NOx removal, yet its performance remains fundamentally limited by sluggish NH3 activation and redox kinetics over conventional catalysts. Although heterovalent doping (e.g., La) is widely employed to enhance the NH3-SCR activity of ceria-based catalysts, the underlying electronic mechanism remains elusive. Herein, spin-polarized density functional theory calculations corrected by on-site Coulomb interactions reveal that La doping induces delocalized O 2p holes on WO3/La-CeO2(111), which serve as the primary electron reservoir during the NH3-SCR reaction. These delocalized O 2p holes can work synergistically with the localized Ce 4f states to accommodate the redistributed charges, lowering the activation barrier for NH3 dissociation. This synergistic effect also affects the N-N coupling stage, where dynamic electron transfer between Ce 4f states and O 2p holes stabilizes the migration of NH2 species. As a result, such La-induced O 2p holes provide a significant thermodynamic driving force for the overall reaction. Our work establishes the synergy between delocalized O 2p holes and localized Ce 4f states as the origin of La-promoted NH3-SCR activity, providing a rational strategy for designing high-performance catalysts via electronic structure engineering. These insights highlight that heterovalent doping can effectively tune the redox properties of lattice oxygen in ceria-based catalysts and may provide theoretical guidance for the development of efficient vanadium-free NH3-SCR systems.

Abstract Light-driven dry reforming of methane (LDRM) provides a feasible route for converting methane (CH4) and carbon dioxide (CO2) into synthesis gas, yet most reported systems require ultraviolet light or a high photon flux, limiting their practical deployment. Here, we show that interfacial oxygen vacancy dynamics can be regulated under mild broadband irradiation through engineered metal–support electronic coupling. In this way, Rh nanoparticles (NPs) supported on two-dimensional CeO2 nanosheets (NS) exhibit record-high Rh-specific activity under low-intensity broadband irradiation (1.20 W·cm–2, 200–800 nm) without external heating, delivering H2 and CO production rates of 681 and 832 mmol·gRh–1·h–1, respectively, together with the highest light-to-chemical energy conversion efficiency (LTCEE) reported for Rh-based LDRM catalysts under low-intensity irradiation (≤3.0 W·cm–2). In-situ characterizations, combined with density functional theory calculations, reveal a photochemical Mars–van Krevelen mechanism driven by interfacial charge separation. Photoexcited electrons transfer from CeO2-NS to Rh NPs across the Schottky junction, generating electron-rich Rhδ– species, while holes remain on CeO2-NS to induce interfacial oxygen vacancies (Ov). These vacancies serve as dynamic active sites that lower the energy barrier for CO2 dissociation, promote *CH3O oxidation, and facilitate *CO desorption. The ultrathin nanosheet architecture further lowers the Ov formation energy and improves charge separation efficiency, enabling dynamic vacancy generation under a low photon flux. This work establishes a general strategy for integrating light-induced charge separation with defect-mediated thermal chemistry to overcome kinetic limitations in thermodynamically demanding reactions, offering a pathway toward efficient solar-driven reforming.

Acetic acid represents a pivotal target for CO2 reduction due to its dual function as a carbon-utilization product and industrial feedstock. However, photocatalytic CO2 reduction (PCCR) to acetic acid typically suffers from low acetic acid yields and selectivity, constrained by competing reactions from ethanol and inefficient C-C coupling. Herein, we report a chiral mesostructured ZnIn2S4 (CMZI) photocatalyst that achieves a remarkable acetic acid yield of 962 µmol g-1 h-1 with a high selectivity of 97.3%. This performance stems from synergistic chirality-induced spin polarization and sulfur site catalysis. Spin polarization stabilizes the triplet OCCO intermediate to enhance C-C coupling, while sulfur sites on ZnIn2S4 {102} facets thermodynamically and kinetically favor acetic acid formation. This work offers critical insights into catalytic strategies of the efficient synthesis of high-value multicarbon products and expanding the variety of synthetic products from CO2 reduction.

Ceria (CeO2) is a widely employed catalytic material in hydrogenation catalysis, and experimental studies have reported that reduced ceria (CeO2-x) can be oxidized by H2; however, the microscopic origin of this process remains unclear. Density functional theory calculations corrected by on-site Coulomb interaction in the current work show that surface oxygen vacancies at CeO2-x are essential for both the dissociation of H2 and the oxidation of the surface. Depending on the spatial arrangement of oxygen vacancies, H2 can either heterolytically dissociate to yield surface hydroxyls and hydrides while leaving Ce-4f electrons unperturbed or undergo homolytic dissociation to generate two hydrides coupled with the oxidation of two Ce3+ ions to Ce4+. The latter pathway becomes accessible only for cross-layer vacancy pairs, which stabilize the transition state in a Ce-H-H dihydrogen configuration. Electronic structure analysis further demonstrates an f-electron regulated channel for homolytic H2 dissociation, where the empty Ce-5d orbital serves as an Electronic Relay Orbital (ERO) that bridges the partially occupied Ce-4f states and the H2-σ* orbital. These findings identify the active sites for H2-induced oxidation of CeO2-x and highlight the central role of the f-d-σ* relay mechanism in H2 activation on f-electron oxides.

Metal-nitrogen-carbon (M-N-C) catalysts have attracted widespread attention due to their potential in promoting the electrochemical oxygen reduction reaction (ORR) for the selective production of hydrogen peroxide (H2O2). However, the effects of their diverse structures and complex compositions on the catalytic performance remain poorly understood. Herein, systematic theoretical calculations reveal that the Pd-N-C based single-atom catalyst featuring a 1 : 1 ratio of pyridinic and pyrrolic nitrogen adopts a centrosymmetric PdN4 structure (PdSAN2-2C), and the Pd dz2 orbital can strongly interact with the O 2p orbital of the adsorbed OOH intermediate, thereby strengthening its adsorption and facilitating subsequent conversion to H2O2. Guided by the theoretical insights, the PdSAN2-2C catalyst and a novel Pd@PdSAN2-2C core-shell catalyst with Pd nanoparticles encapsulated by an ultrathin PdSAN2-2C shell are synthesized, and the latter exhibits a remarkable H2O2 selectivity of 97% and a high yield of 35.88 mol g cat -1 h-1 at an industrially relevant current density of 200 mA cm-2, along with superior operational stability. This combined theoretical and experimental study provides useful guidance for the rational design of high-efficiency M-N-C catalysts for selective electrocatalysis.

The hydrogenation of dicyclopentadiene (DCPD) is an important catalytic reaction, as the resulting product, tetrahydrodicyclopentadiene (THDCPD), is a high-value propellant and specialty fuel. Cerium-based metal-organic frameworks (Ce-MOFs) have demonstrated notable promise as catalysts for this reaction. In this work, we first constructed a candidate structure dataset of 779 Ce-MOFs. To efficiently identify superior catalysts, we established a multi-scale high-throughput computational screening workflow that integrates machine learning stability prediction, pore topology analysis, and Monte Carlo simulation. The application of a set of criteria based on stability, pore-structure characteristics, and adsorption properties led to the identification of two optimal CeMOFs. As a final validation, we computed the adsorption energy of H2-an effective performance descriptor for this reaction-on the identified frameworks, thus confirming their potential as highly efficient catalysts for DCPD hydrogenation to THDCPD.

The development of robust machine learning models to assist the prediction and optimization of homogeneously catalyzed reactions has attracted wide interests. In this work, we propose a workflow to estimate the linear to branched ratio of the products in hydroformylation reactions using a stacking ensemble method that integrates Random Forest, eXtreme Gradient Boosting, and Light Gradient Boosting Machine algorithms, leveraging physicochemically significant features from small-batch experimental data. The stacking model achieves superior performance with R 2 and Root Mean Square Error values of 0.918 and 0.078, respectively. Moreover, the SHapley Additive exPlanations analysis and density functional theory calculations reveal the significant impact of the gap values between the highest occupied molecular orbital and lowest unoccupied molecular orbital of alkenes on the regioselectivity of hydroformylation reactions, indicating that larger gap values tend to result in a higher proportion of the linear products. This study illustrates that the combination of physicochemically significant features and interpretable ensemble models can serve as a useful strategy for predicting regioselectivity in homogeneously catalyzed reactions.

Mass spectrometry (MS) is a fundamental tool for chemical identification. The current in-silico prediction tools can handle broad instrument conditions, large molecular libraries or fragment structures only on a very limited level. In this work, we propose a dual-model machine learning strategy that can solve this problem by jointly a classification model for fragment identification and noise filtering, and a regression model for spectral prediction. With the help of attention mechanism, our method outperforms other algorithms in accuracy and efficiency, providing a deeper understanding of the molecular fragmentation behavior in mass spectra. Our method can facilitate the large-scale in-silico spectra calculations and the analysis of unknown molecular structures, which may promote wider applications for MS.

Electrochemical synthesis of hydrogen peroxide (H2O2) has been emerging as a green alternative technology of the traditional anthraquinone process, though the selectivity and yield of H(2)O(2 )are still hindered by the current catalysts with high cost or difficulties in precise and specific coordination environments. Herein, the boosted selectivity of electrochemical synthesis toward H2O2 with 82% Faradaic efficiency and high stability for above >20 h is manufactured by the atomic Pd sites being supported on the CeO2 nanorods (Pd-1/CeO2 ). The fabrication of atomically dispersed Pd sites and charge redistribution between Pd-1 and CeO2 support result in the enhancement of OOH* coverage, confirmed by in situ characterization techniques, thereby improving the H(2)O(2 )selectivity compared with Pd nanoparticles supported on CeO2 and pure CeO2 catalysts. Furthermore, with a promising H(2)O(2 )yield of 9.78 mol g(catalyst) (-1 )h(-1 ) and 80% Faraday efficiency at the current density of 100 mA cm(-2), Pd-1/CeO2 demonstrated efficient on-site degradation of rhodamine B and tetracycline.

Allyl acetate, an essential building block in petrochemical sector, can be produced through catalytic acetoxylation of propylene. However, an efficient catalyst may not be developed without a clear understanding of the property-performance relationship and reaction mechanism. In this work, we found antimony could be a quite effective promoter for propylene acetoxylation resulting in a selectivity nearly 100.0% (by propylene) and a space-time yield of 2.0 h-1 on the Pd catalyst by forming the Pd7Sb1 bimetallic active sites. With the systematical characterizations (HRTEM, XPS, in-situ DRIFTS, etc) and DFT calculations, we elucidated the geometric and electronic effects of Sb on the Pd catalysts. Electron transfer from Sb to Pd occurs in the bimetallic Pd-Sb alloy, which could efficiently promote the reduction of Pd species and maintain the stability of Pd0. The theoretical simulations also show that the addition of Sb can lower the d-band center of Pd and weaken the strong adsorption of propylene and acetic acid, which inhibits the over-oxidation. Furthermore, the coupling reaction between the dissociatively adsorbed C3H5* and OAc* species was determined to be the rate-determining step at low and high coverages of acetate, and it can be efficiently promoted at the Pd7Sb1 bimetallic sites.