Lead-free inorganic halide perovskites have triggered appealing interests in various energy-related applications including solar cells and photocatalysis. However, why perovskite-structured materials exhibit excellent photoelectric properties and how the unique crystalline structures affect the charge behaviors are still not well elucidated but essentially desired. Herein, taking inorganic halide perovskite Cs₃Bi₂Br₉ as a prototype, the significant derivation process of silver atoms incorporation to induce the structural transformation from Cs₃Bi₂Br₉ to Cs₂AgBiBr₆, which brings about dramatic differences in photoelectric properties is unraveled. It is demonstrated that the silver incorporation results in the co-operated orbitals hybridization, which makes the electronic distributions in conduction and valence bands of Cs₂AgBiBr₆ more dispersible, eliminating the strong localization of electron–hole pairs. As consequences of the electronic structures derivation, exhilarating changes in photoelectric properties like band structure, exciton binding energy, and charge carrier dynamics are verified experimentally and theoretically. Using photocatalytic hydrogen evolution activity under visible light as a typical evaluation, such crystalline structure transformation contributes to a more than 100-fold enhancement in photocatalytic performances compared with pristine Cs₃Bi₂Br₉, verifying the significant effect of structural derivations on the exhibited performances. The findings will provide evidences for understanding the origin of photoelectric properties for perovskites semiconductors in solar energy conversion.

In this study, we construct a 193 nm ultraviolet laser dissociation high-resolution mass spectrometry (HRMS) platform to produce Pt+ cations with high efficiency, which is in situ applied for monitoring the "Pt+ + alkanes" reactions (where alkanes include methane, ethane, and propane). The conversion intermediates and products could be accurately determined by an orbitrap detector with high resolution (up to 150 000). Importantly, methane conversion by Pt+ cations yields [Pt + ethane]+ and [Pt + ethylene]+ as the sole products formed via the cross-coupling reaction of the Pt-CH2 intermediate with gaseous methane. However, the Pt+ cations promote only the nonoxidative dehydrogenation of ethane and propane to give the corresponding [Pt + alkenes]+ and [Pt + alkynes]+. The details of the reaction mechanism are corroborated by density functional theory (DFT) calculations. These results highlight the power of HRMS with the laser dissociation of metal clusters in the generation and reaction characterization of metal ions.

Ag is a promising catalyst for the production of carbon monoxide (CO) via the electrochemical reduction of carbon dioxide (CO₂ER). Herein, we study the role of the formate (HCOO⁻) intermediate *OCHO, aiming to resolve the discrepancy between the theoretical understanding and experimental performance of Ag. We show that the first coupled proton-electron transfer (CPET) step in the CO pathway competes with the Volmer step for formation of *H, whereas this Volmer step is a prerequisite for the formation of *OCHO. We show that *OCHO should form readily on the Ag surface owing to solvation and favorable binding strength. In situ surface-enhanced Raman spectroscopy (SERS) experiments give preliminary evidence of the presence of O-bound bidentate species on polycrystalline Ag during CO₂ER which we attribute to *OCHO. Lateral adsorbate interactions in the presence of *OCHO have a significant influence on the surface coverage of *H, resulting in the inhibition of HCOO⁻ and H₂ production and a higher selectivity towards CO.

Mesoporous nitrogen-doped carbon nanoparticles with atomically dispersed iron sites (named mesoNC-Fe) are synthesized via high-temperature pyrolysis of an Fe containing ZIF-8 MOF. Hydrolysis of tetramethyl orthosilicate (TMOS) in the MOF framework prior to pyrolysis plays an essential role in maintaining a high surface area during the formation of the carbon structure, impeding the formation of iron (oxide) nanoparticles. To gain inside on the nature of the resulting atomically dispersed Fe moieties, HERFD-XANES, EXAFS and valence-to-core X-ray emission spectroscopies have been used. The experimental spectra (both XAS and XES) combined with theoretical calculations suggest that iron has a coordination sphere including a porphyrinic environment and OH/H₂O moieties responsible for the high activity in CO₂ electroreduction. DFT calculations demonstrate that CO formation is favored in these structures because the free energy barriers of *COOH formation are decreased and the adsorption of *H is impeded. The combination of such a unique coordination environment with a high surface area in the carbon structure of mesoNC-Fe makes more active sites accessible during catalysis and promotes CO₂ electroreduction.

Cu-exchanged zeolites are known to be active in the selective oxidation of methane to methanol at moderate temperatures. Among them, Cu-exchanged mordenite (MOR) is the system that has so far shown the highest methanol yield per Cu atom. This high efficiency is attributed to the ability of MOR to selectively stabilize an active tricopper cluster with a [Cu ₃ (μ-O) ₃ ] ²⁺ structure when activated in the presence of O ₂ at high temperatures. In this study, we investigate the elementary steps in the formation of [Cu ₃ (μ-O) ₃ ] ²⁺ by in situ X-ray absorption spectroscopy and ultraviolet-visible spectroscopy. We demonstrate that the Cu cations undergo a series of thermally driven steps during activation that precede the formation of the active oxidizing species. We hypothesize that the thermal formation of highly mobile Cu ⁺ species by autoreduction of Cu ²⁺ in an inert gas is essential to enable the reorganization of Cu ions in MOR, which is necessary for the formation of a reduced precursor of [Cu ₃ (μ-O) ₃ ] ²⁺ . Such a precursor can be oxidized in the presence of strong oxidants-such as O ₂ and N ₂ O-to form active [Cu ₃ (μ-O) ₃ ] ²⁺ at temperatures as low as 50 °C.

Mo/ZSM-5 is one of the most studied and efficient catalysts for the dehydroaromatization of methane (MDA), but the mechanism of its operation remains controversial. Here, we combine an ab initio thermodynamic analysis with a comprehensive mechanistic density functional theory study to address Mo-speciation in the zeolite and identify the active sites under the reaction conditions. We show that the exposure of Mo/ZSM-5 to the MDA conditions yields a range of reduced sites including mono- and binuclear Mo-oxo and Mo-carbide complexes. These sites can catalyze the MDA reaction via two alternative reaction channels, namely, the C-C coupling (ethylene) and the hydrocarbon-pool propagation mechanisms. Our calculations point toward the binuclear Mo-carbide species operating through the hydrocarbon-pool mechanism to be the most catalytically potent species. Although all other Mo sites in the activated catalyst can promote C-H activation in methane, they fail to provide a successful path to the desirable low-molecular-weight products.

Linear energy scaling laws connect the kinetic and thermodynamic parameters of key elementary steps for heterogeneously catalyzed reactions over defined active sites on open surfaces. Such scaling laws provide a framework for a rapid computational activity screening of families of catalysts, but they also effectively impose a fundamental limit on the theoretically attainable activity. Understanding the limits of applicability of the linear scaling laws is therefore crucial for the development of predictive models in catalysis. In this work, we computationally investigate the role of secondary effects of the active site environment on the reactivity of defined Fe complexes in ZSM-5 zeolite toward methane oxofunctionalization. The computed C-H activation barriers over Fe-sites at different locations inside the zeolite pores generally follow the associated reaction enthalpies and the hydrogen affinities of the active site, reflecting the O-H bond strength. Nevertheless, despite the close similarity of the geometries and intrinsic reactivities of the considered active complexes, substantial deviations from these linear scaling relations are apparent from the DFT calculations. We identify three major factors behind these deviations, namely, (1) confinement effects due to the zeolite micropores, (2) coordinative flexibility, and (3) multifunctionality of the active site. The latter two phenomena impact the mechanism of the catalytic reaction by providing a cooperative reaction channel for the substrate activation or by enabling the stabilization of the intrazeolite complex along the reaction path. These computational findings point to the need for the formulation of multidimensional property-Activity relationships accounting for both the intrinsic chemistry of the reactive ensembles and secondary effects due to their environmental and dynamic characteristics.

The active sites on the methane dehydroaromatization (MDA) catalyst Mo/HZSM-5 are very hard to characterize, because they are present in various geometries and sizes and only form under reaction conditions with methane at 700 °C. To address these issues an experimental strategy is presented that enables distinguishing different active sites for MDA present on Mo/HZSM-5 and helps determining the Mo charge, nuclearity and chemical composition. This approach combines a CO pretreatment to separate the active Mo site formation from coke formation, quasi-in situ spectroscopic observations using DNP, ¹³C NMR, CO IR and theory. This allows the discrimination between three different types of active sites. Distinct spectroscopic features were observed corresponding to two types of mono- or dimeric Mo (oxy-)carbide sites as well as a third site assigned to Mo₂C nanoparticles on the outer surface of the zeolite. Their formal Mo oxidation state was found to be between 4+ and 6+. Dynamic nuclear polarization (DNP) measurements of samples carburized in CO as well as in CH₄ confirm the assignment and also show that accumulated aromatic carbon covers the bigger Mo nanoparticles on the outer surface of the zeolite, causing deactivation. It was previously observed that after an initial period where no desired products are formed yet, benzene starts slowly forming until reaching its maximum productivity. Direct observation of the active site with ¹³C NMR confirmed that Mo-sites do not transform further once benzene starts forming, meaning that they are fully activated during the period where no desired products are observed yet. Therefore the slow increase of the benzene formation rate cannot be attributed to a further transformation of Mo sites.

Hydrogenation of CO₂ to methanol utilizing the hydrogen from renewable energy sources offers a promising way to reduce CO₂ emissions through the CO₂ utilization as a carbon source. However, it is a challenge to convert CO₂ to methanol with high activity and high methanol selectivity. Herein, we report a class of metal-oxide solid-solution catalysts: M_aZrO_x (M_a = Cd, Ga), which show a methanol selectivity up to 80% with the CO₂ single pass conversion reaching 4.3%-12.4% under the reaction conditions of H₂/CO₂ = 3/1, 24※000 h^-1, 5 MPa. Structural and electronic characterizations combined with denisty functional theory calculations suggest that the M_a and Zr components in M_aZrO_x (M_a = Cd, Ga) solid-solution catalysts show a strong synergetic effect, which enhances the H₂ heterolytic dissociation and results in high activity and high methanol selectivity. The solid-solution catalyst with dual metal oxide components offers an approach for the selective hydrogenation of CO₂ to chemicals.

Producing aromatics directly from the smallest hydrocarbon building block, methane, is attractive because it could help satisfy increasing demand for aromatics while filling the gap created by decreased production from naphtha crackers. The system that catalyzes the direct methane dehydroaromatization (MDA) best so far is Mo supported on zeolite. Mo has shown to outperform other transition metals (TMs). Here we attempt to explain the superiority of Mo by directly comparing Fe and Mo supported on HZSM-5 zeolite. To determine the most important parameters responsible for the superior performance of Mo, detailed characterization using X-ray absorption spectroscopy (XAS) techniques combined with catalytic testing and theoretical calculations are performed. The higher abundance of mono- A nd dimeric sites for the Mo system, their ease of carburization in methane, as well as intrinsically lower activation energy barriers of breaking the methane C-H bond over Mo explain the better catalytic performance. In addition, a pretreatment in CO is presented to more easily carburize Fe and thereby improve its catalytic performance.

Periodic density functional theory (DFT) calculations were carried out to investigate the mechanism of methane oxidation with H₂O₂ over the defined Fe sites in Fe/ZSM-5 zeolite. The initial Fe site is modeled as a [(H₂O)₂-Fe(III)-(μO)₂-Fe(III)-(H₂O)₂]²⁺ extraframework cluster deposited in the zeolite pore and charge-compensated by two anionic lattice sites. The activation of this cluster with H₂O₂ gives rise to the formation of a variety of Fe(III)-oxo and Fe(IV)-oxo complexes potentially reactive toward methane dissociation. These sites are all able to promote the first C-H bond cleavage in methane by following three possible reaction mechanisms: namely, (a) heterolytic and (b) homolytic methane dissociation as well as (c) Fenton-type reaction involving free OH radicals as the catalytic species. The C-H activation step is followed by formation of MeOH and MeOOH and regeneration of the active site. The Fenton-type path is found to proceed with the lowest activation barrier. Although the barriers for the alternative heterolytic and homolytic pathways are found to be somewhat higher, they are still quite favorable and are expected to be feasible under reaction conditions, resulting ultimately in MeOH and MeOOH products. H₂O₂ oxidant competes with CH₄ substrate for the same sites. Since the oxidation of H₂O₂ to O₂ and two [H⁺] is energetically more favorable than the C-H oxofunctionalization, the overall efficiency of the latter target process remains low.

Zeolites have a broad spectrum of applications as robust microporous catalysts for various chemical transformations. The reactivity of zeolite catalysts can be tailored by introducing heteroatoms either into the framework or at the extraframework positions that gives rise to the formation of versatile Brønsted acid, Lewis acid and redox-active catalytic sites. Understanding the nature and catalytic role of such sites is crucial for guiding the design of new and improved zeolite-based catalysts. This work presents an overview of recent computational studies devoted to unravelling the molecular level details of catalytic transformations inside the zeolite pores. The role of modern computational chemistry in addressing the structural problem in zeolite catalysis, understanding reaction mechanisms and establishing structure-activity relations is discussed. Special attention is devoted to such mechanistic phenomena as active site cooperativity, multifunctional catalysis as well as confinement-induced and multisite reactivity commonly encountered in zeolite catalysis.

Reaction paths underlying the catalytic oxidation of methane with H₂O₂ over an Fe containing MIL-53(Al) metal-organic framework were studied by periodic DFT calculations. Not only the activation of methane, but the full reaction network was considered, which includes the formation of the active site, the overoxidation of methane to CO₂ and the decomposition of H₂O₂ to H₂O and O₂. Calculations indicate that the activation barrier for the initial activation of the Fe sites upon reaction with H₂O₂ is comparable to that of the subsequent C-H activation and also of the reaction steps involved in the undesirable overoxidation processes. The pronounced selectivity of the oxidation reaction over MIL-53(Al,Fe) towards the target mono-oxygenated CH₃OH and CH₃OOH products is attributed to the limited coordination freedom of the Fe species encapsulated in the extended octahedral [AlO₆] structure-forming chains, which effectively prevents the direct overoxidation paths prior to product desorption from the active sites. Importantly, our computational analysis reveals that the active sites for the desired methane oxidation are able to much more efficiently promote the direct catalytic H₂O₂ decomposition reaction, rendering thus the current combination of the active site and the reactants undesirable for the prospective methane valorization process.

A new mechanism for glucose dehydration to HMF without the intermediate isomerization to fructose is discussed for surface models of anatase TiO₂ using periodic density functional theory calculations. Activation of the glucose at glucose's C3-OH position by titania starts the reaction resulting in adsorbed 3-deoxyglucosone. The mechanistic study reveals two possible pathways for the acyclic form of glucose. Comparison of different surface models shows that the presence of tetrahedral Ti⁴⁺ species on a defective TiO₂(101) anatase surface is essential for explaining the activity. Synergy between a strong Lewis acidic Ti site and a vicinal basic oxygen site of a TiOH group is essential to establish the direct conversion of glucose to HMF. IR spectroscopy of adsorbed chloroform in the presence of water confirms the presence of water tolerant Lewis acid sites in close proximity to basic sites. In conventional glucose dehydration, Lewis acid sites and proton donors act as catalytic sites for efficient sequential isomerization-dehydration to HMF, while direct dehydration to HMF requires the cooperation of Lewis acid-base pairs.

Although the local geometry of Mo in Mo/HZSM-5 has been characterized before, we present a systematic way to manipulate the configuration of Mo and link it to its catalytic properties. The location and geometry of cationic Mo-complexes, the precursor of the active metal site for methane dehydroaromatization, are altered by directing the way they anchor to the framework of the zeolite. The feature used to direct the anchoring of Mo is the location of Al in the zeolite framework. According to DFT calculations, the local geometry of Mo should change, while UV-vis and pyridine FTIR spectroscopy indicated differences in the dispersion of Mo. Both aspects, however, did not influence the catalytic behavior of Mo/HZSM-5, indicating that as long as enough isolated Mo species are present inside the pores of the zeolite, the catalytic behavior is unaffected. This paves the way to better understand how the Mo oxo precursor transforms into the active phase under the reaction conditions.

Hybrid materials bearing organic and inorganic motifs have been extensively discussed as playgrounds for the implementation of atomically resolved inorganic sites within a confined environment, with an exciting similarity to enzymes. Here, we present the successful design of a site-isolated mixed-metal metal organic framework (MOF) that mimics the reactivity of soluble methane monooxygenase enzyme and demonstrates the potential of this strategy to overcome current challenges in selective methane oxidation. We describe the synthesis and characterization of an Fe-containing MOF that comprises the desired antiferromagnetically coupled high-spin species in a coordination environment closely resembling that of the enzyme. An electrochemical synthesis method is used to build the microporous MOF matrix while integrating the atomically dispersed Fe active sites in the crystalline scaffold. The model mimics the catalytic C-H activation behavior of the enzyme to produce methanol and shows that the key to this reactivity is the formation of isolated oxo-bridged Fe units.

Although methanol synthesis via CO hydrogenation has been industrialized, CO₂ hydrogenation to methanol still confronts great obstacles of low methanol selectivity and poor stability, particularly for supported metal catalysts under industrial conditions. We report a binary metal oxide, ZnO-ZrO₂ solid solution catalyst, which can achieve methanol selectivity of up to 86 to 91% with CO₂ single-pass conversion of more than 10% under reaction conditions of 5.0 MPa, 24,000 ml/(g hour), H₂/CO₂ = 3:1 to 4:1, 320° to 315°C. Experimental and theoretical results indicate that the synergetic effect between Zn and Zr sites results in the excellent performance. The ZnO-ZrO₂ solid solution catalyst shows high stability for at least 500 hours on stream and is also resistant to sintering at higher temperatures. Moreover, no deactivation is observed in the presence of 50 ppm SO₂ or H₂S in the reaction stream.

Metal/metal oxide nanoparticles with controllable size and shape are of importance to tailor the catalytic performances of metal nanoparticles. However, a facile synthesis of supported monodisperse metal/oxide polyhedra in the absence of capping agents remains a significant challenge, especially at high metal loadings. In this work, a surfactant-free MOF (metal-organic framework) thermolysis strategy is developed for the synthesis of monodisperse ferrite octahedral nanocrystals with uniform composition for the first time. The achievement of our synthesis relies on the use of CO as directing agent that may control the growth rate of specific facets at the solid/gas interface and, subsequently, the shape of the resultant metal oxide nanostructures. As-prepared octahedral ferrite materials exhibited an interesting shape-dependent catalytic performance in 5-hydroxymethylfurfural (HMF) oxidation, achieving significantly improved activity and selectivity, compared to those synthesized under a pure inert atmosphere. Density functional theory (DFT) calculations suggest a relatively weak interaction between 2,5-diformylfuran (DFF) and the catalyst that is highly beneficial for product desorption, avoiding the overoxidation reactions that occur on the catalyst surface to some extent and partially contributing to the high DFF selectivity.