The development of a visible light-responsive photocatalyst for the synthesis of fine chemicals is a promising strategy for sustainable chemical transformations. In this work, a series of bismuth molybdate (BMO) materials were synthesized via hydrothermal or solvothermal methods using H2O or ethylene glycol as solvent with varying amounts of urea, and applied for the photocatalytic reduction of nitrobenzene to aniline in alcohol. The characterization results revealed that the amount of urea significantly influenced the phase composition and morphology of BMO materials synthesized in H2O. In contrast, the addition of urea to ethylene glycol up to a molar urea to Bi ratio of 10 to 1 did not alter the phase composition, which remained as pure Bi2MoO6. However, the presence of urea affected its morphology, increasing the amount of urea led to larger agglomerated spheres and eventually to broken spherical structures. The BMO materials synthesized in ethylene glycol show much higher photocatalytic activity for nitro group reduction than their counterparts prepared in water. Furthermore, the obtained results show that the type of alcohol used has a significant impact on the aniline formation as well as the transformation of the formed intermediates. When using methanol, complete nitrobenzene conversion was reached within 2 h of blue LED irradiation with 94% aniline selectivity. Finally, a mechanism for the reduction of nitrobenzene in alcohols over Bi2MoO6 under blue LED light irradiation was suggested.

Understanding the nature of active sites in heterogeneous catalysts and how to create them purposefully opens up the possibility of tailored catalyst design. Here we report mixed-valence subnanometre CoOx clusters, consisting of a few metallic Co0 atoms on top of Co2+, bound to a silicalite-1 support through lattice oxygen atoms as active species for non-oxidative propane dehydrogenation (PDH) to propene. Compared with commercial-like PtSn/Al2O3 and K-CrOx/Al2O3 catalysts also tested in the present study, as well as other state-of-the-art Pt- or Co-containing PDH catalysts, this system showed high on-stream stability, propene productivity and selectivity at close-to-equilibrium propane conversion. Moreover, it showed durability in a series of PDH/regeneration cycles between 500 and 550 degrees C. The performance of this catalyst system is industrially attractive in terms of propene production costs, as suggested by our initial techno-economic assessment.

Ammonia (NH3) oxidation to nitrous oxide (N2O) is a promising route to obtain this selective oxidant, but controlling product distribution is inherently challenging because N2O occupies an intermediate nitrogen oxidation state between N-2 and NO. Despite recent advances, leading CeO2-based catalytic systems have consistently encountered a selectivity limit in the range of 80-85%. Herein, CeO2-supported Mn single atoms are employed as a stable, selective benchmark to investigate the origins of the N2O selectivity losses. Thorough kinetic analysis revealed that direct oxidation of NH3 to N-2 is the main reason for incomplete N2O selectivity. This reaction dominates in a thin upstream catalyst bed layer, driven by its strong dependence on the NH3 partial pressure that ensures dense surface coverage by N-containing intermediates and promotes their irreversible coupling to N-2. However, due to the inhibiting effect of H2O, this reaction is increasingly hindered along the catalyst bed, with N2O becoming the dominant product. Based on these insights, N2O selectivity could be increased from 81% to 90% while N-2 selectivity decreased to 6% by water cofeeding and adjusting reactant partial pressures to tune surface coverage by N-containing intermediates. Evaluation of side reactions revealed a negligible impact of N2O decomposition or N2O reduction on product distribution. Conversely, employing isotopic tracing, reduction of in situ-formed NO by NH3 was established as a significant route to secondary N2O, and to a lesser extent, N-2. This was shown to be a general feature of CeO2-based catalysts, including Mn, Au, and Cr systems, providing a lever for selectivity control. This work demonstrates how kinetic analysis can disentangle complex reaction pathways and identify both catalyst- and process-level strategies to advance NH3 oxidation to N2O beyond current limits.

A fundamental understanding of the interactions between the support and the supported species in heterogeneous catalysis is crucial, as the support can significantly influence the structural and chemical properties of the active supported species, thereby affecting their catalytic performance. In this study, the intrinsic effects of VOx-support interactions on the structure of VOx species and catalytic behavior of VOx-Al2O3 catalysts were investigated using nonoxidative propane dehydrogenation (PDH) as a model reaction. Complementary characterization studies of the catalysts revealed the presence of distinct monomeric VOx species (m-VOx), which are bonded to coordinatively unsaturated (Al-cus) and saturated (Al-cs) aluminum sites, respectively. Compared to m-VOx anchored on the Al-cus sites, those bound to the Al-cs sites exhibit a weaker strength of the V-O-Al bonds and accordingly higher reducibility. Remarkably, selectively eliminating Al-cus sites but preserving Al-cs sites by treating the catalyst with an NH3H2O solution greatly enhanced the PDH activity, increasing the turnover frequency of VOx by more than 4-fold. Furthermore, kinetic analysis based on time-resolved in situ UV-vis spectroscopy demonstrated that the rate constant of the reduction of m-VOx species by H-2 correlates positively with the Al-cs content in the VOx-Al2O3 catalysts, establishing it as a reliable activity descriptor for the PDH reaction catalyzed by m-VOx. Thus, this work provides fundamental insights into how support identity matters, thereby contributing to the targeted development of active catalysts.

Non-oxidative propane dehydrogenation (PDH) to propene is the basis of several technologies developed for meeting the increasing demand for this olefin. Given the high cost of commercial Pt-based catalysts, a promising direction for improving the economics of propene production by PDH is to reduce Pt content without sacrificing high propene productivity and selectivity. We report that the 1Co-0.1Pt@silicalite-1(1Co-0.1Pt@S-1) catalyst, with only 0.1 wt% Pt and 1 wt% Co, outperforms an analog of commercial Pt-Sn/Al2O3 in terms of activity and on-stream stability despite the approximately 5-fold lower Pt loading. Its performance is also remarkable when compared to other state-of-the-art Pt-containing catalysts. The high activity of the 1Co-0.1Pt@S-1 catalyst is attributed to the presence of ultrasmall PtCo intermetallic compounds formed under reaction conditions. The developed catalyst also demonstrated high on-stream stability, with an apparent deactivation rate constant of just 4 & times; 10-4 h-1 determined over 110 h on stream at approximately 90% of the equilibrium propane conversion at 500 degrees C using a feed with 90 vol % propane.

ConspectusThe direct oxidation of methane, which is the main component of natural gas, shale gas, methane clathrates, and biogas, to value-added products is an economically attractive and environmentally friendly alternative to strongly endothermic methane steam reforming to synthesis gas (CO/H2). Among the different routes, the oxidative coupling of methane (OCM) to ethylene/ethane (C2-hydrocarbons) is the most promising one. A key limiting factor is insufficiently high selectivity to C2-hydrocarbons due to their overoxidation to carbon oxides (COx) at industrially relevant degrees of methane conversion. Although it is generally agreed that both selective and unselective reactions are initiated by oxygen species on the surface of catalysts, the kind, role, and origin of these species remain elusive, which hampers the tailored design of catalysts.In this Account, we summarize our recent progress in understanding how product selectivity in the OCM reaction can be tuned by controlling the type of oxygen species through catalyst composition or reaction conditions. The combination of in situ time- and temperature-resolved catalyst characterization with transient kinetic methods, i.e., temporal analysis of products (TAP) and steady-state isotopic transient kinetic analysis (SSITKA), has been proven to be effective for understanding the origin and role of oxygen species involved in selective and unselective pathways. We also present strategies for regulating the concentrations of selective and unselective oxygen species. For the Mn-M(M = Na, K, Rb, or Cs)2WO4 system, the electronegativity of the alkali metal was found to influence the ability of the catalysts to form selective oxygen species from gas-phase oxygen. The binding strength of atomic oxygen species is a key parameter for hindering the oxidation of methane to COx over Gd2O3-based catalysts. This property can be adjusted by using a metal oxide promoter. The nature and concentration of different oxygen species can also be controlled through the use of steam or an alternative oxidizing agent, N2O, and by performing the OCM reaction in a chemical looping mode, i.e., by alternating between CH4- and air-containing feeds. Using steam in the latter option enabled us to largely enhance the productivity of C2-hydrocarbons, thus making this technology more attractive for large-scale applications. The knowledge summarized in this Account is expected to present insights for further studies in the development of selective catalysts for various alkane oxidation reactions and in the optimization of reactor operation.

Non-oxidative dehydrogenation of ethane (EDH) is an attractive method for on-purpose ethene production, but achieving high activity and, especially, durability with catalysts based on earth-abundant metals remains challenging. Herein, we introduce the Co/SSZ-13 system with exclusively divalent cobalt (Co2+) ions that meets the above requirements. The use of complementary characterization techniques enabled us to reveal two Co2+ species: Co2+─Z2 located in the six-membered-ring windows and [Co(OH)]+─Z in the eight-membered-ring windows, with Z representing a charged zeolite framework site. A quantitative correlation between the rate of ethene formation and the site population establishes Co2+─Z2 as the active species. In situ X-ray absorption spectroscopy confirms their structural and electronic stability under high-temperature reaction conditions. The optimized 0.9Co/SSZ-13 (0.9Co) catalyst showed highly durable operation over 200 dehydrogenation/oxidative regeneration cycles at 600-650°C lasting for 150 h with industrially relevant productivity. In this regard, it outperforms almost all previously developed catalysts even those with platinum as an active component. The obtained results uncover the atomic-level origins of EDH activity/durability of the Co/SSZ-13 system and highlight the critical role of metal site location in designing highly active, selective, and durable catalysts for on-purpose ethene production.

The development of cost-effective and eco-compatible nonnoble metal oxide catalysts for large-scale propene production via nonoxidative propane dehydrogenation (PDH) is a key topic of current research in heterogeneous catalysis. Cobalt-based catalysts show remarkable catalytic performance and are promising alternatives to industrially established platinum- or chromium oxide-based catalyst systems. The formation of coke deposits under the reaction conditions has a significant influence on their performance. Time-resolved operando Raman spectroscopic experiments have been performed during the PDH reaction using a catalyst system containing 3-wt.% Co on silicalite-1 as a support (3Co/S-1) to elucidate the role of carbon-containing species. Three stages during the PDH process were identified. During the initial 5 min on propane stream, propane is preferentially oxidized to carbon oxides and water. This indicates the removal of lattice oxygen from Co3O4, whereby this species is reduced to metallic cobalt (Co0). With increasing time on propane stream, the formation of C1-C2 hydrocarbons was observed, pointing to the occurrence of cracking and deep dehydrogenation reactions of propane. Subsequently, intense G and D bands appeared in the Raman spectrum due to the formation of carbon deposits. Simultaneously, there was a substantial enhancement in propene formation, which indicates that carbon-containing species are necessary for the selective dehydrogenation of propane to propene. The catalyst showed high activity and durable operation in a series of seven dehydrogenation/reoxidation cycles under relevant conditions. The induction period observed for the fresh catalyst was shortened for the catalyst system in course of the PDH/reoxidation cycles.

Non-oxidative propane dehydrogenation (PDH) has emerged as a promising technology for on-purpose propene production, but the Pt-based catalysts currently used are expensive and prone to sintering of platinum, which negatively...

Non-oxidative dehydrogenation of propane (PDH) is a well-established large-scale route for on-purpose propene production. Cobalt-based catalysts have attracted increasing attention due to their attractive performance as environmentally friendly and cost-efficient alternatives to commercially used catalysts containing chromium or platinum. However, their further development to reach an industrially attractive level is hindered by insufficient knowledge of the structure-activity-selectivity relationships for tailored catalyst design and preparation. In this work, magnesium (Mg) is introduced as a promoter to regulate the local structure of CoO x species on the surface of silicalite-1. Owing to the formation of Co-O-Mg bond(s) in the presence of the promoter, the formed CoO x species become isolated, less reducible, and less acidic. These changes are key to catalyst activity and propene selectivity. The promoter effectively decreases the amount of strong acidic sites, thereby facilitating propene desorption and accordingly suppressing undesired cracking and deep dehydrogenation reactions involving adsorbed propene. The optimized catalyst outperforms an analogue of commercial K-CrO x /Al2O3 and demonstrates durability in a series of five PDH/regeneration cycles under industrially relevant conditions. The space-time yield of propene formation reached 1.2 kgC3H6 & centerdot;kgcat -1 & centerdot;h-1 at 550 degrees C and 68% of the equilibrium propane conversion, being higher in comparison to that of most previously reported cobalt-based catalysts under comparable conditions. In view of this result, the structural and mechanistic knowledge obtained on the promoter effect can be used to prepare highly efficient PDH catalysts with supported metal-oxide species, including those beyond CoO x .

Given the goals of reducing carbon emissions and overcoming the challenge of energy shortages, the efficient conversion of industrially abundant and cheap n-butane to high value-added light olefins and aromatics is of particular significance. In this study, Zn-ZSM-5 catalysts with highly dispersed Zn species were successfully prepared via a dual-bed method using commercial ZnSiO3 and ZSM-5. At 500 degrees C, the optimized catalyst with a Zn content of 0.41 wt% exhibits an outstanding n-butane conversion rate (0.39 mmol center dot g(-1)center dot min(-1)) which is approximately 4 and 30 times as high as that over a conventionally prepared Zn/ZSM-5 catalyst and pristine ZSM-5, respectively. The achieved performance is also remarkable in comparison with representative Pt-, or Gacontaining catalysts. In-situ DRIFTS analysis revealed that the high dispersion of Zn-containing species was achieved through the strong interplay between the Zn atoms formed during the preparation of Zn-ZSM-5 catalysts at 600 degrees C in H-2 and acidic hydroxyl groups in ZSM-5. Furthermore, the relationships between Zn species and butenes formation rates were identified, corroborating that the isolated [Zn(OH)](+) and binuclear ZnOx species synergistically interact resulting in high activity in n-butane dehydrogenation, and the former species contributes more. According to the selectivity-conversion relationship and kinetic analysis, the unique structure of Zn species in ZSM-5 matrix affects catalytic performance towards n-butane dehydrogenation, thus promoting the cleavage of C-H bonds, which is instrumental in the efficient utilization of n-butane. The obtained fundamentals provide hints for designing highly efficient Zn-containing catalysts for heterogeneous reactions beyond n-butane conversion.

Abstract Low-temperature CO2 hydrogenation to methane has the potential to form the basis of power-to-gas technologies, which could help close the carbon cycle and address environmental concerns. Catalysts with supported metals that can activate hydrogen are typically used for this reaction but do not yet meet the requirements of large-scale applications. Their tailored design remains challenging due to the ambiguity about the role of support and supported metal and how they interact with each other to ensure industrially relevant performance. To contribute to closing this knowledge gap, we prepared ZrO2- and YZrOx-supported catalysts possessing 1 nm Ru or Rh nanoparticles at a low metal loading of about 0.1 wt %, which was chosen for economic reasons. The best-performing Ru/ZrO2 catalyst outperformed various previously developed Ru- or/and Rh-containing catalysts in terms of metal-related activity despite operating at around 90% equilibrium conversion. To gain a detailed understanding of the kinetics and mechanism of CO2 methanation, we performed a comprehensive study combining steady-state isotopic transient kinetic analysis (SSITKA), temporal analysis of products (TAP), and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The SSITKA method enabled us to determine the concentration and the lifetime of the surface intermediates of gas-phase CH4. The concentration was found (i) to be significantly higher than that of surface atoms of Rh or Ru and (ii) to increase with increasing reaction temperature. Thus, support plays a pivotal active role in the reaction kinetics and mechanism. Moreover, a direct correlation was found between the lifetime and the strength of CO2 adsorption as determined by TAP experiments. This finding suggests that the adsorptive catalyst property is an important activity-governing factor. This property can be controlled by the degree of support reduction; the higher the reduction degree, the longer the lifetime. The reduction degree depends on the kind of supported metal and dopant for ZrO2. In situ DRIFTS studies confirmed that CO2 methanation proceeds on the support via the formate (HCOO–) and methoxy (OCH3) intermediates, ultimately yielding gas-phase CH4. The synergistic action of oxygen vacancies and weak OH– basic centers was suggested to facilitate CO2 adsorption and its rapid conversion into active HCOO– species, thereby enabling the fast formation of reaction intermediates. The coexistence of oxygen vacancies and weak OH– groups on the surface of ZrO2-based supports may provide a faster pathway for CH4 formation. Therefrom, the presented approach and the obtained knowledge may be used for the purposeful design of catalysts not only for CO2 methanation but also for CO2 hydrogenation to higher hydrocarbons to hinder the formation of CH4.

Non-oxidative dehydrogenation of propane (PDH) is an important route for large-scale on purpose propene production. Although cobalt-based catalysts are promising alternatives to currently used platinum-or chromium oxide-based catalysts, their further developments are hindered by the uncertainties related to the kind of the active sites involved in the desired and side reactions. To contribute to closing such a gap, we systematically investigate the role of oxidized CoOx and metallic Co0 species in the PDH reaction over catalysts based in Silicalite-1 with supported CoOx species differing in their redox properties. C3H8 pulse experiments with sub-millisecond and second resolution at pulse sizes of about 13 and 2200 nmol, respectively, combined with in-depth catalyst characterization and PDH tests at different propane conversions enabled us to understand how the reaction-induced reduction of CoOx affects product selectivity. Propane readily reacts with CoOxto yield propene, carbon oxides and water. The formed Co0 species show high activity to coking and cracking reactions. However, if the size of such species is below 2 nm, these undesired reactions are significantly hindered due to the coverage of the active sites by carbon-containing species. The remaining uncovered surface Co0 sites selectively dehydrogenate propane to propene. The best-performing catalyst showed higher activity than a commercial-like K-CrOx/Al2O3 and operated durable in a series of 10 dehydrogenation/regeneration cycles under industrial relevant conditions. The space time yield of propene formation of 0.97 kgh-1kgcat-1 was achieved at 550 degrees C, 52% equilibrium propane conversion and 95% propene selectivity. (c) 2025, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

The production of methanol (CH3OH) from CO2 is an attractive solution for closing the carbon cycle and thus addressing both environmental concerns and raw material changes in the chemical industry. CuZn-based catalysts are the most intensively investigated materials in this regard but suffer from CH3OH decomposition to CO with increasing CO2 conversion. Pd-containing materials also show promising performance, but they are less understood from a mechanistic point of view. To bridge this gap, a series of catalysts based on CeO2, ZrO2, Ce0.8Zr0.2O2, or CeO2-SiO2 supports with Pd or CuZnPd as active components were prepared. Comprehensive kinetic tests revealed that the catalysts containing only Pd species convert CO2 to CO exclusively, followed by the hydrogenation of CO to CH3OH. Using a feed consisting of CO and H-2, 100% CH3OH selectivity was achieved. The role of Pd is to convert CO2 to CO and to generate surface species from H-2, which are involved in the hydrogenation of CO to CH3OH probably on the surface of support. In situ Fourier transform infrared spectroscopy tests have identified HCOO- species formed from gas-phase CO as surface precursors of CH3OH. In contrast to the Pd/support catalysts, their CuZnPd/support counterparts convert CO2 directly into CH3OH in parallel with CO. These differences were explained by structural/electronic changes in Pd due to alloying with Cu as revealed by in situ X-ray photoelectron and X-ray absorption spectroscopy. Overall, this study enhances understanding of the mechanistic aspects of product formation in the course of CO2 hydrogenation to CH3OH and highlights the significance of steady-state catalytic tests at different space velocities to identify primary and secondary pathways, offering valuable insights for the tailored design of efficient catalysts for CH3OH production from CO2.

The hydrogenation of CO2 to higher hydrocarbons (C2+-hydrocarbons) over Fe-based catalysts represents a promising strategy for CO2 valorization. An in-depth understanding of the restructuring of Fe-containing phases under reaction conditions and their role in product formation is necessary to enable tailored catalyst design. To this end, we introduce a simple preparation method where Fe nanoparticles (NP) are simply mixed physically with Fe3O4 and/or a potassium-based promoter. To establish the direct influence of metallic Fe, Fe3O4 and/or a promoter on the catalyst restructuring and performance, the as-prepared physical mixtures are used in steady-state and time-resolved kinetic tests without any pretreatment. Combined with complementary in situ characterization methods, we demonstrate that Fe3O4 is not a necessary component in the initial catalyst or in the surface/bulk composition of the working catalyst to ensure efficient CO2 conversion to CO and subsequently C2+-hydrocarbons formation. Instead, metallic Fe reduces CO2 to gas-phase/surface CO species. Therefrom formed surface CO and/or C species should contribute to FeCx formation besides Fe carburization with the aid of gas-phase CO. This process is enhanced in the presence of a K-containing promoter. Its effectiveness depends on the ability of K species to migrate under reaction conditions, which is related to the type of K precursor. The catalysts based on physical mixtures of metallic Fe NP and K2CO3 developed in this study outperform the majority of previous catalysts in terms of higher hydrocarbon and C-2-C-4 olefin yield, yet suppressed CH4 formation. Thus, our strategy and results provide the basis for the development of efficient CO2 hydrogenation catalysts.

Oxidative coupling of methane (OCM) to C2H6 and C2H4 (C-2-hydrocarbons) is an industrially attractive method for methane valorization. However, its commercialization is hampered by the low selectivity to C-2-hydrocarbons, especially to C2H4. In this study, we demonstrate the use of a physical mixture of Li2CO3 or LiNO3 with differently supported catalysts based on the Mn-Na2WO4 system for the efficient continuous formation of the target products using O-2 as an oxidant. The selectivity to C-2-hydrocarbons and C2H4 of 90.5 and 35.7% or 87.6 and 43.3%, respectively, was obtained at 7.2 or 13.3% CH4 conversion over the Li2CO3-Mn-Na2WO4/Siral70 (AlSiOx with 70 wt % SiO2) catalyst, while its Li2CO3-free counterpart was unselective. Very similar performance is achieved by promoting the support with Li2CO3 followed by deposition of the active components. In situ temperature-resolved and ex situ X-ray diffraction characterization studies showed that the promoter reacted completely with the active components and the support to yield highly crystalline materials with a low specific surface area. Such restructuring resulted in a strong improvement in the selectivity to C-2-hydrocarbons due to inhibiting the direct heterogeneous oxidation of methane to carbon oxides. The selectivity changes were rationalized by steady-state isotopic transient kinetic analysis using OCM feeds with O-16(2) or O-18(2) and temporal analysis of products. Li2CO3-induced phase modifications affect both the concentration and lifetime of surface intermediates leading to CO2 and CO. The knowledge gained provides guidance for the development of OCM catalysts with improved C-2-selectivity. Moreover, the results obtained demonstrate the potential of our approach to elucidate the selectivity-governing factors relevant for tailored catalyst design and may stimulate future investigations of the development of selective catalysts in various alkane oxidation reactions.

The development of efficient catalysts for ethane dehydrogenation (EDH) to ethylene remains a challenge due to the lack of direct material property-performance relationships at the most elementary level. Here, we introduce the first application of ZrO2-based catalysts for EDH in a chemical looping mode. Their performance in the first 1 minute, primarily via the oxidative dehydrogenation, highlights their potential for large-scale ethylene production. LaZrOx achieves a space-time yield of 2.26 kg C 2 H 4 ⋅ kg cat - 1 ⋅ h - 1 at about 80% ethylene selectivity and 50% ethane conversion at 700 °C. Mechanistic studies have identified the reactivity and availability of lattice oxygen as crucial descriptors for mitigating coke formation and suppressing combustion reactions. These properties can be tuned by exposing less stable ZrO2 crystal planes or incorporating metal-oxide promoters. Strongly adsorbed oxygen species can also participate in ethane oxidation. Thus, this study establishes a catalyst system for chemical looping EDH and provides insights for designing more efficient EDH catalysts.

Knowledge about dynamic changes of the phase composition during catalytic reactions is indispensable for gaining a better understanding of catalyst structure‐reactivity relationships. For this purpose, in situ Raman spectroscopic experiments were conducted to monitor the structural changes of ferrous oxalate without and with an alkali metal promoter during CO 2 hydrogenation to C 2+ ‐hydrocarbons under realistic reaction conditions (340 °C, 15 bar). The kind of promoter had no significant influence on the thermal transition of iron oxalate into the magnetite (Fe 3 O 4 ) phase as the major phase under inert gas. In contrast, the promoters did have a substantial impact on the phase composition during CO 2 hydrogenation. The Raman spectroscopic results obtained, underpinned with X‐ray diffraction measurements, demonstrated a much stronger development of carbon‐containing species, notably iron carbides (FeC x ) and carbon deposits, when using the alkali metal‐promoted catalysts. The formation of carbon deposits may indirectly indicate the occurrence of carbidization, however, no quantitative correlation was discovered. It was also found that the presence of alkali metal promoters hampered the reoxidation of FeC x toward Fe 3 O 4 with water vapor.

La cus sites on defective La 2 O 3 catalyze propane dehydrogenation but deactivate due to strong propene adsorption. In situ decoration of La cus sites with H 2 forms new sites, weakens adsorption, and improves catalyst stability and selectivity.