Achieving intrinsic stability of reaction-formed catalytic sites, and understanding its origin, remains a central challenge in heterogeneous catalysis. Although CO-driven restructuring of atomically dispersed metals into subnanometer clusters has been observed in methane reforming and related reactions, the electronic basis of the resulting stability and the catalytic mechanism on these sites remain unknown. In this study, we show that atomically dispersed Rh on CeO2 nanorods spontaneously evolves into Rh3(CO)4 clusters during the water-gas shift (WGS) reaction, and that this restructuring resolves the inherent activity-stability trade-off. Metastable Rh3(CO)3 clusters with higher initial activity transform into thermodynamically stable Rh3(CO)4 that sustains performance over 5000 h at 300°C without apparent deactivation. Combining in situ spectroscopy, kinetic analysis, and density functional theory calculations, we reveal the dual origins of this intrinsic stability. Coordination of the fourth CO ligand lowers the cluster formation energy by 2.15 eV, driven by d z 2 ${{d}_{{{{\mathrm{z}}}^2}}}$ -π* hybridization through Rh-to-CO back-donation, rendering Rh3(CO)4 a thermodynamic sink resilient to reaction-induced perturbations. Meanwhile, surface hydride species generated at oxygen vacancies open a concerted COOH dehydrogenation pathway, markedly lowering the rate-determining barrier. This work demonstrates that reactive atmospheres can steer catalytic sites toward configurations where structural stability and catalytic function coexist.

The low-cost C3H8/C3H6/C3H4 separation for high-grade C3H6 is of paramount importance but extremely difficult in the chemical industry. Here we report an economic strategy of functionalizing Zr-based metal-organic frameworks (MOFs) with amino acids for one-step C3H6 purification from ternary C3 mixtures. The resulting UiO-67-AA exhibits exceptionally high C3H8 and C3H4 uptakes and benchmark selectivities for C3H8/C3H6 and C3H4/C3H6 separations, rivaling reported ternary C3 separating MOFs. Breakthrough experiments confirm its excellent performance in producing high-purity C3H6 in one step. Crucially, the estimated over 2250 times the cost reduction among reported C3H8/C3H4-selective MOFs makes UiO-67-AA an ideal candidate for industrial C3H6 purification. In situ infrared spectroscopy, in situ neutron powder diffraction, and theoretical calculations indicate that amino acids offer selective binding to dually strengthen both C3H8 and C3H4 affinity over that of C3H6, with the amino group dictating the supramolecular interactions. Systematic evaluation across UiO-67 with diverse nitrogen moieties establishes a monotonic relationship between the separation performance and the specific nitrogen electronegativity, providing an element‑specific and quantitative electronegativity-driven design rule for next-generation MOF adsorbents for industrial olefin purification.

The Hubbard U for a metal-oxo unit depends on how electrons are screened in its host material. This screening is governed by (i) local screening determined by coordination, oxidation state, and metal-ligand hybridization and (ii) the longer-range dielectric response of the surrounding lattice. Consequently, the common practice of directly transferring U from extended metal oxides to metal-organic frameworks (MOFs) with the same metal-oxo unit risks systematic errors. Here, we take UiO-66(Ce) as a prototypical MOF and determine the node-specific linear-response Hubbard parameter U (ULR) for four commonly employed GGA functionals used to describe the Ce 4f orbitals of the Ce6O8 node. We then benchmark GGA + ULR against experiment and HSE06 for both pristine and the node-reduced UiO-66(Ce). GGA + ULR reproduces the structural and electronic properties, whereas using the U value transferred from CeO2 leads to a deviated description of the redox activity. However, transferring node-specific ULR between MOFs that share the same node and comparable screening environments is physically justified and practically useful for GGA + U calculations of large-cell MOFs. This conditional transferability is validated by applying the ULR derived from UiO-66(Ce) to NU-1000(Ce), successfully reproducing hybrid-functional results across seven proton topologies. The larger ULR obtained for the Ce6O8 node compared to that for CeO2 reflects more ionic Ce-O bonding and distinct redox chemistry of the MOF node. Such deviations are not limited to the present case but are anticipated for metal-oxo units in MOFs more broadly, enabling node chemistries that are different from those of the extended phase.

Exciton effects play a vital role in photocatalytic reactions, yet their precise regulation remains highly challenging, as even subtle variations can lead to pronounced differences in exciton behavior. To date, the influence of intermolecular interactions on exciton dynamics remains largely unexplored. Herein, two isoreticular donor-acceptor hydrogen-bonded or ganic frameworks (D-A HOFs), PFC-19 and PFC-70, are synthesized. Notably, PFC-70's monomer lacks an intrinsic donor-acceptor structure. However, pronounced orbital perturbation and reorganization occur during its self-assembly, leading to an emergent D-A reconstruction. In contrast, PFC-19 retains orbital distribution similar to its monomer. These distinct behaviors originate from stronger intermolecular interactions in PFC-70, thereby inducing dramatic energy-level reorganization. Consequently, PFC-19 predominantly generates 1O2 via an energy-transfer pathway. On the contrary, PFC-70 shows a reduced exciton binding energy and enhanced charge-transfer efficiency, leading to the formation of O2•-/•OH via a charge-transfer-dominated process. Accordingly, photocatalytic aerobic organic transformations are achieved, exhibiting excellent efficiency in 1O2-mediated C-3 arylation of quinoxalin-2(1H)-ones with PFC-19 and predominant O2•--triggered oxidative coupling of benzylamines over PFC-70. This work not only provides a general strategy for regulating intermolecular interactions via molecular engineering but also gains deep insight into exciton regulation for controlling ROS species in noncovalently assembled systems.

Single-layer transition metal dichalcogenides (TMDs), such as WS2, offer promising catalytic performance and good electron mobility, making them attractive cocatalysts for photo- and electrocatalysis. However, their structural instability under reaction conditions often leads to formation of inactive bulk metal oxides and contamination of final products, limiting long-term performance and industrial applicability. Herein, we demonstrate that this instability can instead be harnessed as a constructive transformation pathway. Under mild aqueous conditions, exfoliated WS2 monolayers undergo spontaneous transformation at the interface with anatase TiO2, resulting in the formation of highly dispersed tungsten species anchored on the oxide surface and accompanied by the generation of abundant oxygen vacancies. Comprehensive structural, spectroscopic, and theoretical analyses reveal that strong interfacial interactions direct the oxidation pathway away from bulk oxide formation and toward stabilized, atomically dispersed active sites with modified local electronic structures. The resulting catalyst exhibits enhanced charge separation, improved conductivity, and markedly improved stability and performance under photocatalytic conditions. These serendipitous findings reframe TMD degradation as a beneficial process and establish a strategy for repurposing unstable metal sulfide monolayers into functional components of robust photocatalytic systems.

Developing earth-abundant electrocatalysts that rival the commercial platinum/carbon catalyst for the hydrogen evolution reaction (HER) remains a central challenge in renewable-energy conversion. Here, we reveal an electrochemically induced, in situ phase transformation in a Ru-MgO catalyst that leads to true active material during operation. Under acidic HER conditions, nominal 20 wt.% Ru nanoparticles supported on polar MgO(111) nanocrystals undergo a topotactic hydrolysis to Ru-Mg(OH)2(001), generating an ordered hydroxide layer that serves as a highly conductive proton-hopping network. After activation, the catalyst delivers performance comparable to commercial Pt/C under identical conditions, matching the current density of -1.1 V and surpassing it by approximately 10% at -2.3 V. Operando synchrotron X-ray diffraction combined with ex situ characterization techniques directly captures this transformation, while density-functional theory calculations reveal that water-assisted Grotthuss proton transfer across the hydroxide requires only a 0.10 eV energy barrier. These findings establish electrochemically driven oxide-to-hydroxide conversion as a new design principle for creating low-Pt or Pt-free HER electrocatalysts with intrinsically fast proton transport.

Integrating semiconductors into metal-organic frameworks (MOFs) typically compromises porosity due to pore blockage or coverage. Conversely, we report a CdS/UiO-66-NH2 composite, achieving a 1.5-fold increase in specific surface area. Through in-situ synthesis, CdS clusters are embedded into the tetrahedral pores of UiO-66-NH2. Structural analysis utilizing Rietveld-refined synchrotron X-ray diffraction (SXRD) and density functional theory (DFT) reveals the confined CdS clusters modulate the rotation of organic linkers, synchronously expanding the framework by a guest-induced gate-opening effect. In addition, CdS/UiO-66-NH2 heterostructure significantly facilitates efficient charge carrier separation. Consequently, the optimized CdS/UiO-66-NH2 exhibits a more than doubled photocatalytic water splitting rate compared to pristine UiO-66-NH2. This work offers molecular-level insights into leveraging structural flexibility for constructing high-efficiency photocatalysts.

The development of accurate and transferable force fields for metal-organic frameworks (MOFs) remains a significant challenge. Here, we introduce MODEX, a modular and extensible force field for MOFs. MODEX employs a building block approach in which the inorganometallic node and organic linker are parametrized separately and subsequently combined. Currently, MODEX is parametrized for ten representative Zr-based MOFs. Zr-based MOFs represent an important class of MOFs with a wide range of applications; however, limited transferable force fields have been developed exclusively for this family. The parametrization is driven by a custom multiobjective particle swarm optimization (PSO) algorithm implemented in our Force Field Factory program, enabling simultaneous fitting to multiple types of quantum chemistry reference data. The resulting force field accurately reproduces the structural, phonon, and mechanical properties of the ten target Zr-based MOFs. Furthermore, MODEX accurately captures the rotational dynamics of the linker in UiO-66, reproducing both the rotational barrier and the thermally accessible conformational space obtained from quantum chemistry calculations. MODEX is designed for continuous expansion; new building blocks can be readily parametrized using Force Field Factory. This work establishes MODEX as a robust force field for large-scale simulations of the ten Zr-based MOFs studied here and provides a platform for future extension to new frameworks.

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.

Developing efficient propane dehydrogenation (PDH) processes without uses of expensive Pt- and toxic CrOx-based catalysts are of broad interest and great importance. Co-feeding of hydrogen is a widely-adopted strategy to improve catalytic performance of various catalysts in the PDH reaction. Herein, we systematically study the promotion effect of co-fed H2 on different oxide catalysts in the PDH reaction. It comes mainly from the alleviated poisoning effect on ZnO and additionally from H2 reduction-enhanced coordination-unsaturated Zr3+ active sites on ZrO2, while mainly from the formation of dynamically-cycles metastable gallium hydride species on Ga2O3 capable of activating the C–H bond activation of propane at significantly reduced barriers ( C_3H_8 + 2Ga(III)_Ga_2O_3 - H^* = C_3H_6 + 2H_2 + 2Ga(III)_Ga_2O_3) . During the Ga2O3-catalyzed PDH reaction with co-fed H2, the Ga(III)_Ga_2O_3 - H^* species initially forms by H2 dissociation, then reacts with C3H8 to produce C3H6 and H2, and finally gets recovered by H2 dissociation, leading to the dynamically-cycled hydride active site on Ga2O3 with greatly enhanced catalytic performance. Such a hydride catalysis is highly sensitive to the structure of Ga2O3, being more efficiently on Ga2O3111 facets than on Ga2O3100 facets. A fine Ga2O3 nanocatalyst with a high ratio of exposed 111 facets and a large specific surface area is fabricated to give a C3H6 space-time yield (STY) as high as 4.9 kg_C_3H_6/( kg_catalyst h) with a C3H6 selectivity of 96.5

Green electricity-driven alkenol electrosynthesis via electrocatalytic alkynol semihydrogenation represents a sustainable route to conventional thermocatalysis. Both the electrocatalyst and electrolyte strongly impact the semihydrogenation performance. Despite significant progress in developing sophisticated electrocatalysts, a well-designed electrolyte in conjunction with industrial catalysts is an attractive strategy to advance the industrialization process of electrocatalytic alkynol semihydrogenation, but remains unexplored. Here, we develop a dimethyl sulfoxide (DMSO)-H2O cosolvent electrolyte for electrocatalytic alkynol semihydrogenation. At an alkynol conversion of about 100%, the DMSO-H2O electrolyte compared to the DMSO-free counterpart enables the alkenol selectivity on Cu catalysts to be promoted from 60-70% to over 90% at all measured current densities; meanwhile, the reaction rate is slightly decreased due to the inhibited water dissociation. Mechanistic studies reveal that the strong hydrogen-bond interactions between DMSO and H2O suppress the dissociation of interfacial H2O, leading to a decreased H* coverage at the electrode surface. The decreased H* coverage hinders the overhydrogenation of alkynols and favors the production of alkenols. Remarkably, the DMSO-induced enhancement of alkenol selectivity is applicable to a set of commercial catalysts and to the semihydrogenation of various alkynols. Eventually, a scaled-up 3 × 100 cm2 electrolyzer stack is established to achieve an alkynol conversion of ∼96% and an alkenol selectivity of ∼95% in the cosolvent electrolyte. This work not only presents an electrolyte strategy for boosting alkenol electrosynthesis, but also highlights the possibility of sustainable alkenol electro-production.

Enhancing intrinsic activity and increasing catalytic site density are two widely employed strategies to improve catalytic performance. Although typically considered independently, their interplay remains poorly understood. Here, two UiO-66 metal-organic frameworks (MOFs) with distinct catalytic site densities-linker-defective UiO-66L and cluster-defective UiO-66C-are synthesized and systematically compared. Despite a higher density of open Zr catalytic sites, UiO-66L exhibited lower catalytic activity than UiO-66C across four model reactions, performing similarly to defect-free UiO-66. Although defect engineering is expected to enlarge pore connectivity, diffusion-ordered spectroscopy (DOSY) and molecular dynamics (MD) simulations surprisingly reveal that UiO-66C exhibits similar diffusion rates to defect-free UiO-66, while UiO-66L shows significantly slower diffusion. This discrepancy is attributed to self-adsorption of reactants at the high-density catalytic sites, which induces local diffusion resistance even in the presence of expanded channels. These findings reveal a performance trade-off between catalytic site density and intrinsic activity, establishing a critical threshold beyond which further increases in site density can hinder rather than enhance catalysis.

Widespread industrial application of bisphenol A (BPA) has produced large amounts of contaminated wastewater, and its accumulation in the environment has threatened human health. In this study, MnOOH nanorods were deposited with the polydopamine layer containing incorporated Co precursor, which was derived to obtain carbon shell confined Co3O4 onto Mn2O3 nanorods. The controlled calcination temperature was optimized to improve the active state of metal species. Carbon shells mediate the electronic interactions between Co3O4 and Mn2O3, triggering more Co(II/III) redox cycles and an enhanced fraction of Mn(III) along with more oxygen vacancies in Mn2O3. In addition, more pyridinic N species were generated in the carbon shell of Mn@C/Co-600, affording better affinity to the polar contaminants and peroxymonosulfate (PMS). Therefore, these characters in Mn@C/Co-600 caused the accelerated reaction cycles in the PMS activation and BPA degradation. Compared with other catalysts, Mn@C/Co-600 showed the highest degradation efficiency of bisphenol A (BPA) with the rate constant of 0.827 min(-1), which was up to 30 times higher than that of Mn@C/Co-Cl-600 (0.027 min(-1)). The anions interference effect on BPA degradation follows the order of Cl- (0.925 min(-1)) O-2(-) in the degradation process. In addition, the optimal Mn@C/Co-600 catalysts were fixed on the melamine sponge as monolith catalysts by Ca2+-triggered alginate crosslinking strategy, affording pollutant removal in BPA (85.7 %, 60 min). The nanoreactor showed good adaptability for various pollutants and reusability in practical water treatment. This study provides an effective solution for the control of BPA and other cognate environmental pollutants and the utilization of water resources.

The co-production of hydrogen and value-added biochemicals from lignocellulose utilizing solar energy has been regarded as one of the technologies most potentially able to alleviate the current energy crisis. Here, we demonstrate a cost-effective photoreforming strategy for lignocellulose valorization using a carbon nitride-supported platinum single-atom photocatalyst. An advanced H2 evolution rate of 6.34 mmol molPt-1 h-1 is achieved over the optimal catalyst, which is around 4.6 and 30.5 times higher compared with the nanosized Pt counterpart and pristine carbon nitride, respectively. Meanwhile, the monosaccharides are oxidized to value-added lactic acid with >99% conversion and extraordinary selectivity up to 97%. The theoretical calculations show that with Pt incorporation, the photogenerated holes are predominantly localized on the metal sites while the photo-generated electrons are concentrated on C3N4, thus enhancing the effective separation of charge carriers. This work provides a promising avenue for the simultaneous production of green H2 and bio-based chemicals by biomass photorefinery. (c) 2025, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

The bridging hydride species (Zn-H-Zn) formed via H2 dissociation on ZnO surface play crucial roles in hydrogenation of unsaturated hydrocarbon to industrial production. Here, we find that the migration of surface hydroxyl in ZnO nanorods to nearby oxygen vacancy can also lead to the formation of this Zn-H-Zn species that are reactive to CO2 hydrogenation to methanol using solid-state NMR spectroscopy. Below 100 °C, bridging Zn-H-Zn species show no activity toward CO2 activation, while formate species are formed via the reaction of CO2 with surface hydroxyl groups. At 150-200 °C, Zn-H-Zn species hydrogenate formate to methoxy species. At 250 °C, methanol is produced and desorbs from the ZnO surface. These results confirm the methanol formation mechanism via formate and methoxy intermediates in the presence of active bridging Zn-H-Zn species. This work reveals a new source of active hydrogen species in ZnO nanorods without introducing H2, which is highly significant for heterogeneous hydrogenation reactions.

Upon interaction with H2, metal oxides can be reduced. Such a reduction may consequently alter their interactions as well as the evolution of hydrogen species on metal oxide surfaces. However, this has not been thoroughly and precisely studied on the atomic scale. Accordingly, systematic density functional theory (DFT) calculations were performed on a representative metal-oxide catalyst surface, namely β-Ga2O3(100). It was found that oxygen vacancy clusters can readily form upon reduction and that such vacancy clusters enable the infiltration of surface hydrogen species into the near-surface region. The calculated relative population of near-surface hydrogen species reaches approximately 5% under typical experimental conditions for hydrogenation and dehydrogenation reactions on Ga2O3 surfaces, and thus, these species cannot be ignored. To study the effect of near-surface hydrogen species on the surface chemistry of metal oxides, two important reactions were considered. The first is H2 dissociation, which is an important process in catalytic hydrogenation (and dehydrogenation) reactions. The second is CO2 hydrogenation, which is a representative hydrogenation reaction. It was found that the presence of near-surface hydrogen species results in modulation of the surface electronic and chemical properties of β-Ga2O3(100), leading to a change in the preferred pathway for these surface chemical reactions. These findings emphasize the crucial role of near-surface hydrogen species in tuning the selectivity of chemical reactions on metal oxide surfaces. This perspective has not been identified thus far, to the best of our knowledge, but is consistent with previously reported experimental results in many aspects.

The development of synthetic methods capable of converting elemental sulfur into conjugated porous sulfur-rich polymers remains a great challenge, although direct utilization of this readily available feedstock can significantly enrich its uses and circumvent environmental problems during sulfur storage. We report herein mechanochemical (MC) nucleophilic aromatic substitution (S N Ar) that enables sulfur conversion into thianthrene-bridged porous ladder polymer networks with dense donor-acceptor (D−A) molecular junctions. We demonstrate that the key lies in the generation of bent thianthrene units through a solid-state ball-milling condensation reaction between 1,2-dihaloarenes and elemental sulfur. We also show that the assembling of D−A structural motifs into porous networks affords efficient visible-light-driven photocatalytic reduction of carbon dioxide (CO 2 ) with water (H 2 O) vapor, in the absence of any additional photosensitizer, sacrificial agents or cocatalysts. Exceptional photoinduced charge separation along with boosted exciton dissociation results in a high-performance of carbon monoxide (CO) production rate of 306.1 μmol g −1  h −1 with near 100 % CO selectivity, which is accompanied by H 2 O oxidation to O 2 , as confirmed by both experimental and theoretical results. We anticipate this novel MC S N Ar approach will advance processing techniques for direct sulfur utilization and facilitate new possibilities for the synthesis of D−A ladder polymer networks with promising potential in photocatalysis.

Improving the efficiency of catalytic materials is vital to the chemical and energy industries. Constructing neighbouring active sites in metal-organic framework (MOF) materials for cooperative catalysis is a promising way to achieve the above goal. However, it is difficult to fine-tune active sites at the atomic level due to the challenge of visualising their local structures and their interaction with substrates. In this article, we report the direct visualisation of metal and defect active sites and binding of the phenol substrate in Ru-doped defective MOF-808. X-ray absorption spectroscopy, X-ray pair distribution function analysis, X-ray powder diffraction, and infrared spectroscopy reveal that the enhanced selective hydrogenation originates from the specific adsorption geometry of phenol over 7-centred Ru clusters and hydroxyl or water of defect sites. This mechanism also well explains the high catalytic activity in CO2 reduction. This work represents the first example of structural elucidation of metal-defect cooperative catalysis in MOFs and will lead to the rational design of new superactive MOF catalysts. Metal-defect cooperative catalysis in Ru-doped defective MOF-808 is directly visualised via combined XAS, XPDF, XRD, and IR analysis.

Maintaining high conversion under the premise of high oxygenates selectivity in syngas conversion is important but a formidable challenge in Rh catalysis. Monometallic Rh catalysts provide poor oxygenate conversion efficiency, and efforts have been focused on constructing adjacent polymetallic sites; however, the one-pass yields of C2+ oxygenates over the reported Rh-based catalysts were mostly <20 %. In this study, we constructed a monometallic Rh catalyst encapsulated in UiO-67 (Rh/UiO-67) with enhanced proximity to dual-site Rh1,2-Rhn ensembles. Unexpectedly, this catalyst exhibited high efficacy for oxygenate synthesis from syngas, giving a high oxygenate selectivity of 72.0 % with a remarkable CO conversion of 50.4 %, and the one-pass yield of C2+ oxygenates exceeded 25 %. The state-of-the-art characterizations further revealed the spontaneous formation of an ensemble of Rh single atoms/dimers (Rh1,2) in the proximity of ultrasmall Rh clusters (Rhn) confined within the nanocavity of UiO-67, providing adjacent Rh+-Rh0 dual sites dynamically during the reaction that promote the relay of the undissociated CHO species to the CHx species. Thus, our results open a new route for designing highly efficient Rh catalysts for the conversion of syngas to oxygenates by precisely tuning the ensemble and proximity of the dual active sites in a confined space.