Atomically Dispersed Fe-Cu Dual-Metal Sites Synergistically Boost Carbonylation of Methane.

The production of acetic acid, an important industrial chemical traditionally obtained through the carbonylation of methanol using noble metal-based homogeneous catalysts, encounters challenges arising from high equipment costs and sustainability concerns. The direct liquid-phase oxidative carbonylation of methane emerges as a promising alternative, capitalizing on abundant natural gas resources and featuring a potentially mild and straightforward process. However, most catalysts proposed for this process suffer from low acetic acid yields due to the scarcity of active sites and the swift generation of C1 oxygenates, posing difficulties for subsequent carbonylation and impeding their industrial feasibility. Herein, we report a highly efficient 0.1Cu/Fe-HZ5-TF catalyst featuring exclusively mononuclear Fe and Cu anchored in the ZSM-5 channels. Under optimized conditions, the catalyst achieved an unprecedented acetic acid yield of 40.5 mmol gcat-1 h-1 at 50 °C, surpassing the previous maximum (12.0 mmol gcat-1h-1) by more than threefold. Comprehensive characterization, isotope-labeled experiments and DFT calculations reveal that the homogeneous mononuclear Fe sites are responsible for the activation and oxidation of methane, while the neighboring Cu sites play a key role in retarding the oxidation process. This synergistic action promotes C-C coupling, resulting in the efficient synthesis of acetic acid.

Selectivity Descriptors of Methanol-to-Aromatics Process over 3-Dimensional Zeolites.

The zeolite-catalyzed methanol-to-aromatics (MTA) process is a promising avenue for industrial decarbonization. This process predominantly utilizes 3-dimensional 10-member ring (10-MR) zeolites like ZSM-5 and ZSM-11, chosen for their confinement effect essential for aromatization. Current research mainly focuses on enhancing selectivity and mitigating catalyst deactivation by modulating zeolites' physicochemical properties. Despite the potential, the MTA technology is at a low Technology Readiness Level, hindered by mechanistic complexities in achieving the desired selectivity towards liquid aromatics. To bridge this knowledge gap, this study proposes a roadmap for MTA catalysis by strategically combining controlled catalytic experiments with advanced characterization methods (including operando conditions and "mobility-dependent" solid-state NMR spectroscopy). It identifies the descriptor-role of Koch-carbonylated intermediates, longer-chain hydrocarbons, and the zeolites' intersectional cavities in yielding preferential liquid aromatics selectivity. Understanding these selectivity descriptors and architectural impacts is vital, potentially advancing other zeolite-catalyzed emerging technologies.

The synergistic interplay of hierarchy, crystal size, and Ga-promotion in the methanol-to-aromatics process over ZSM-5 zeolites.

In the context of advancing social modernization, the projected shortfall in the demand for renewable aromatic hydrocarbons is expected to widen, influenced by industries like high-end materials, pharmaceuticals, and consumer goods. Sustainable methods for aromatic production from alternative sources, particularly the methanol-to-aromatics (MTA) process using zeolite ZSM-5 and associated with the "methanol economy", have garnered widespread attention. To facilitate this transition, our project consolidates conventional strategies that impact aromatics selectivity-such as using hierarchical zeolites, metallic promoters, or altering zeolite physicochemical properties-into a unified study. Our findings demonstrate the beneficial impact of elongated crystal size and heightened zeolite hierarchy on preferential aromatics selectivity, albeit through distinct mechanisms involving the consumption of shorter olefins. While metallic promoters enhance MTA performance, crystal size, and hierarchy remain pivotal in achieving the maximized aromatics selectivity. This study contributes to a deeper understanding of achieving superior aromatics selectivity through physicochemical modifications in zeolite ZSM-5 during MTA catalysis, thereby advancing the field's comprehension of structure-reactivity relationships.

Isolated Ni Atoms Enable Near-Unity CH4 Selectivity for Photothermal CO2 Hydrogenation.

Photothermal hydrogenation of carbon dioxide (CO2) into value-added products is an ideal solution for addressing the energy crisis and mitigating CO2 emissions. However, achieving high product selectivity remains challenging due to the simultaneous occurrence of numerous competing intermediate reactions during CO2 hydrogenation. We present a novel approach featuring isolated single-atom nickel (Ni) anchored onto indium oxide (In2O3) nanocrystals, serving as an effective photothermal catalyst for CO2 hydrogenation into methane (CH4) with a remarkable near-unity (∼99%) selectivity. Experiments and theoretical simulations have confirmed that isolated Ni sites on the In2O3 surface can effectively stabilize the intermediate products of the CO2 hydrogenation reaction and reduce the transition state energy barrier, thereby changing the reaction path to achieve ultrahigh selective methanation. This study provides comprehensive insights into the design of single-atom catalysts for the highly selective photothermal catalytic hydrogenation of CO2 to methane.

Novel high-pressure/high-temperature reactor cell for in situ and operando x-ray absorption spectroscopy studies of heterogeneous catalysts at synchrotron facilities.

This paper presents the development of a novel high-pressure/high-temperature reactor cell dedicated to the characterization of catalysts using synchrotron x-ray absorption spectroscopy under operando conditions. The design of the vitreous carbon reactor allows its use as a plug-flow reactor, monitoring catalyst samples in a powder form with a continuous gas flow at high-temperature (up to 1000 °C) and under high pressure (up to 1000 bar) conditions, depending on the gas environment. The high-pressure/high-temperature reactor cell incorporates an automated gas distribution system and offers the capability to operate in both transmission and fluorescence detection modes. The operando x-ray absorption spectroscopy results obtained on a bimetallic InCo catalyst during CO2 hydrogenation reaction at 300 °C and 50 bar are presented, replicating the conditions of a conventional microreactor. The complete setup is available for users and permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental (CRG-FAME) sciences and French Absorption spectroscopy beamline in Material and Environmental sciences at ultra-high dilution (FAME-UHD) beamlines (BM30 and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

Advancing Membrane Technology: Ordered Macroporous ZIF-67 as a Filler in Mixed Matrix Membranes for Enhanced Propylene/Propane Separation.

Conventional separation technologies for valuable commodities require substantial energy, accounting for 10%-15% of global consumption. Mixed-matrix membranes (MMMs) offer a promising solution by combining processable polymers with selective inorganic fillers. Here, the potential of using ordered microporous structured materials is demonstrated as MMM fillers. The use of ordered macroporous ZIF-67 in combination with the well-known 6FDA-DAM polymer leads to superior performance in the important separation of propylene from propane. The enhanced performance can be rationalized with the help of advanced microscopy, which demonstrates that the polymer is able to penetrate the macroporous network around which the MOF (Metal-Organic Framework) is synthesized, resulting in a much better interphase between the two components and the homogeneous distribution of the filler, even at high loadings.

Tracking the Impact of Koch-Carbonylated Organics During the Zeolite ZSM-5 Catalyzed Methanol-to-Hydrocarbons Process.

A methanol-based economy offers an efficient solution to current energy transition challenges, where the zeolite-catalyzed methanol-to-hydrocarbons (MTH) process would be a key enabler in yielding synthetic fuels/chemicals from renewable sources. Despite its original discovery over half a century ago over the zeolite ZSM-5, the practical application of this process in a CO2 -neutral scenario has faced several obstacles. One prominent challenge has been the intricate mechanistic complexities inherent in the MTH process over the zeolite ZSM-5, impeding its widespread adoption. This work takes a significant step forward by providing critical insights that bridge the gap in our understanding of the MTH process. It accomplishes this by connecting the (Koch-carbonylation-led) direct and dual cycle mechanisms, which operate during the early and steady-state phases of MTH catalysis, respectively. To unravel these mechanistic intricacies, we have performed catalytic and operando (i.e., UV/Vis coupled with an online mass spectrometer) and solid-state NMR spectroscopic-based investigations on the MTH process, involving co-feeding methanol and acetone (cf. a key Koch-carbonylated species), including selective isotope-labeling studies. Our iterative research approach revealed that (Koch-)carbonyl group selectively promotes the side-chain mechanism within the arene cycle of the dual cycle mechanism, impacting the preferential formation of BTX fraction (i.e., benzene-toluene-xylene) primarily.

Uniformly Distributed Mixed Matrix Membranes via a Solution Processable Strategy for Propylene/Propane Separation.

Aggregation of filler particles during the formation of mixed matrix membranes is difficult to avoid when filler loadings exceed a 10-15 wt %. Such agglomeration usually leads to poor membrane performance. In this work, using a ZIF-67 metal-organic framework (MOF) as filler along with surface modification of Ag4 tz4 to improve processability and selective olefin adsorption, we demonstrate that highly loaded with a very low agglomeration degree membranes can be synthesized displaying unmatched separation selectivity (39) for C3 H6 /C3 H8 mixtures and high permeability rates (99 Barrer), far surpassing previous reports in the literature. Through molecular dynamics simulation, the enhanced compatibility between ZIF-67 and polymer matrix with adding Ag4 tz4 was proven and the tendency in gas permeability and C3 H6 selectivity in the mixed matrix membranes (MMMs) were well explained. More importantly, the membrane showed a wide range of pressure and temperature resistance, together with remarkable long-term stability (>900 h). The modification method might help solve interface issues in MMMs and can be extended to the fabrication of other fillers to achieve high performance MMMs for gas separation.

Ruthenium-Picolylamine-Incorporated Mixed-Linker MOFs: Highly Active Heterogeneous Catalysts for Olefin and Aldehyde Hydrogenation.

The selective hydrogenation of aldehydes and olefins plays a crucial role in the synthesis of various industrial products. Immobilizing noble metal catalysts on solid supports has been pursued to overcome the challenges associated with catalyst separation and recovery. In this study, we explore the use of metal-organic frameworks (MOFs) as supports for the immobilization of molecular ruthenium catalysts in the hydrogenation of olefins and aldehydes. We designed a mixed-linker MOF by incorporating the picolylamine moiety, which is a ligand known for its excellent catalytic activity. The ruthenium catalysts were prepared via a simple metal-ligand coordination process without the need for additional treatments. The resulting catalysts exhibit high catalytic activity and a uniform distribution of ruthenium sites on the MOF crystals. The choice of ruthenium precursor has a significant influence on the catalytic performance, with even lower metal content resulting in higher activity. The catalysts achieve high conversion rates and selectivities in the hydrogenation of various olefins. However, in the hydrogenation of aldehydes, due to the harsher conditions required, the formation of small nanoparticles is observed after the reaction. Overall, our findings highlight the potential of picolylamine-modified MOFs as effective supports for the development of highly active heterogeneous catalysts for selective hydrogenation reactions.

Highly Efficient and Stable Methane Dry Reforming Enabled by a Single-Site Cationic Ni Catalyst.

Zeolite-supported nickel (Ni) catalysts have been extensively studied for the dry reforming of methane (DRM). It is generally believed that prior to or during the reaction, Ni is reduced to a metallic state to act as the catalytic site. Here, we employed a ligand-protected synthesis method to achieve a high degree of Ni incorporation into the framework of the MFI zeolite. The incorporated Ni species retained their cationic nature during the DRM reaction carried out at 600 °C, exhibiting higher apparent catalytic activity and significantly greater catalytic stability in comparison to supported metallic Ni particles at the same loading. From theoretical and experimental evidence, we conclude that the incorporation of Ni into the zeolite framework leads to the formation of metal-oxygen (Niδ+-O(2-ξ)-) pairs, which serve as catalytic active sites, promoting the dissociation of C-H bonds in CH4 through a mechanism distinct from that of metallic Ni. The conversion of CH4 on cationic Ni single sites follows the CHx oxidation pathway, which is characterized by the rapid transformation of partial cracking intermediates CHx*, effectively inhibiting coke formation. The presence of the CHx oxidation pathway was experimentally validated by identifying the reaction intermediates. These new mechanistic insights elucidate the exceptional performance of the developed Ni-MFI catalyst and offer guidance for designing more efficient and stable Ni-based DRM catalysts.

Enabling the Methanol Economy: Opportunities and Challenges for Heterogeneous Catalysis in the Production of Liquid Fuels via Methanol.

ConspectusThirty years ago, George A. Olah proposed the concept of the methanol economy, where methanol replaces fossil fuels as a means of energy storage, ground transportation fuel, and raw material for the manufacture of other carbon-based products. Over the years, with rising global warming concerns, the concept has evolved. A special interest is devoted to the development of catalytic processes that allow the transformation of carbon dioxide, via methanol, into CO2 neutral liquid hydrocarbons. These products could replace the oil-based fuels currently used by combustion engines. The rapid depletion of such fuels would avoid a considerable amount of CO2 emissions during the current energy transition.Over the past decade, we have focused on different key processes that should allow for maximal atom efficiency and, therefore, minimal energy consumption in a field, CO2 valorization, that can easily become a zero-sum game. In this Account, we highlight the importance of catalyst design to overcome the process challenges in the production of liquid fuels from methanol. Additionally, progress in multifunctional catalysts able to directly convert, in one single reactor, CO2 to liquid fuels is also discussed in detail. This integrated option is of particular interest since it allows an important decrease in operational units while increasing throughput by converting, in situ, a thermodynamically limited intermediate.

Key Strategies for Enhancing H2 Production in Transition Metal Oxide Based Photocatalysts.

Transition metal oxides (TMOs) were one of the first photocatalysts used to produce hydrogen from water using solar energy. Despite the emergence of many other genres of photocatalysts over the years, TMO photocatalysts remain dominant due to their easy synthesis and unique physicochemical properties. Various strategies have been developed to enhance the photocatalytic activity of TMOs, but the solar-to-hydrogen (STH) conversion efficiency of TMO photocatalysts is still very low (<2 %), which is far below the targeted STH of 10 % for commercial viability. This article provides a comprehensive analysis of several widely used strategies, including oxygen defects control, doping, establishing interfacial junctions, and phase-facet-morphology engineering, that have been adopted to improve TMO photocatalysts. By critically evaluating these strategies and providing a roadmap for future research directions, this article serves as a valuable resource for researchers, students, and professionals seeking to develop efficient energy materials for green energy solutions.

Zeolite Synthesis in the Presence of Metallosiloxanes for the Quantitative Encapsulation of Metal Species for the Selective Catalytic Reduction (SCR) of NOx.

Metal encapsulation in zeolitic materials through one-pot hydrothermal synthesis (HTS) is an attractive technique to prepare zeolites with a high metal dispersion. Due to its simplicity and the excellent catalytic performance observed for several catalytic systems, this method has gained a great deal of attention over the last few years. While most studies apply synthetic methods involving different organic ligands to stabilize the metal under synthesis conditions, here we report the use of metallosiloxanes as an alternative metal precursor. Metallosiloxanes can be synthesized from simple and cost-affordable chemicals and, when used in combination with zeolite building blocks under standard synthesis conditions, lead to quantitative metal loading and high dispersion. Thanks to the structural analogy of siloxane with TEOS, the synthesis gel stabilizes by forming siloxane bridges that prevent metal precipitation and clustering. When focusing on Fe-encapsulation, we demonstrate that Fe-MFI zeolites obtained by this method exhibit high catalytic activity in the NH3 -mediated selective catalytic reduction (SCR) of NOx along with a good H2 O/SO2 tolerance. This synthetic approach opens a new synthetic route for the encapsulation of transition metals within zeolite structures.

Blue and green ammonia production: A techno-economic and life cycle assessment perspective.

Blue and green ammonia production have been proposed as low-carbon alternatives to emissions-intensive conventional ammonia production. Although much attention has been given to comparing these alternatives, it is still not clear which process has better environmental and economic performance. We present a techno-economic analysis and full life cycle assessment to compare the economics and environmental impacts of blue and green ammonia production. We address the importance of time horizon in climate change impact comparisons by employing the Technology Warming Potential, showing that methane leakage can exacerbate the climate change impacts of blue ammonia in short time horizons. We represent a constrained renewable electricity availability scenario by comparing the climate change impact mitigation efficiency per kWh of renewable electricity. Our work emphasizes the importance of maintaining low natural gas leakage for sustainability of blue ammonia, and the potential for technological advances to further reduce the environmental impacts of photovoltaics-based green ammonia.

Leaching in Specific Facets of ZIF-67 and ZIF-L Zeolitic Imidazolate Frameworks During the CO2 Cycloaddition with Epichlorohydrin.

Zeolitic imidazolate frameworks (ZIFs) have been profusely used as catalysts for inserting CO2 into organic epoxides (i.e., epichlorohydrin) through cycloaddition. Here, we demonstrate that these materials suffer from irreversible degradation by leaching. To prove this, we performed the reactions and analyzed the final reaction mixtures by elemental analysis and the resulting materials by different microscopies. We found that the difference in catalytic activity between three ZIF-67 and one ZIF-L catalysts was related to the rate at which the materials degraded. Particularly, the {100} facet leaches faster than the others, regardless of the material used. The catalytic activity strongly depended on the amount of leached elements in the liquid phase since these species are extremely active. Our work points to the instability of these materials under relevant reaction conditions and the necessity of additional treatments to improve their stability.

Interplay Between Particle Size and Hierarchy of Zeolite ZSM-5 During the CO2 -to-aromatics Process.

The CO2 -to-aromatics process is a chemical reaction that converts carbon dioxide (CO2 ) into valuable petrochemical, i. e., aromatics (especially, benzene, toluene, and xylene) over the metal/zeolite bifunctional catalytic systems. These aromatics are used in producing plastics, fibers, and other industrial products, which are currently exclusively sourced from fossil-derived feedstocks. The significance of this process lies in its potential to mitigate climate change by reducing greenhouse gas emissions and simultaneously producing valuable chemicals. Consequently, these CO2 -derived aromatics can reduce the reliance on fossil fuels as a source of feedstocks, which can help to promote a more sustainable and circular economy. Owing to the existence of a wider straight channel favoring the aromatization process, zeolite ZSM-5 is extensively used to yield aromatics during CO2 hydrogenation over bifunctional (metal/zeolite) catalytic systems. To provide a better understanding of this unique property of zeolite ZSM-5, this work investigates the impact of particle size and hierarchy of the zeolite and how these govern the reaction performance and the overall selectivity. As a result, an improved understanding of the zeolite-catalyzed hydrocarbon conversion process has been obtained.

Pore-Networked Gels: Permanently Porous Ionic Liquid Gels with Linked Metal-Organic Polyhedra Networks.

Porous liquids (PLs) are attractive materials because of their capability to combine the intrinsic porosity of microporous solids and the processability of liquids. Most of the studies focus on the synthesis of PLs with not only high porosity but also low viscosity by considering their transportation in industrial plants. However, a gap exists between PLs and solid adsorbents for some practical cases, where the liquid characteristics and mechanical stability without leakage are simultaneously required. Here, we fill in this gap by demonstrating a new concept of pore-networked gels, in which the solvent phase is trapped by molecular networks with accessible porosity. To achieve this, we fabricate a linked metal-organic polyhedra (MOPs) gel, followed by exchanging the solvent phase with a bulky liquid such as ionic liquids (ILs); the dimethylformamide solvent trapped inside the as-synthesized gel is replaced by the target IL, 1-butyl-3-methylimidazolium tetrafluoroborate, which in turn cannot enter MOP pores due to their larger molecular size. The remaining volatile solvents in the MOP cavities can then be removed by thermal activation, endowing the obtained IL gel (Gel_IL) with accessible microporosity. The CO2 capacities of the gels are greatly enhanced compared to the neat IL. The exchange with the IL also exerts a positive influence on the final gel performances such as mechanical properties and low volatility. Besides ILs, various functional liquids are shown to be amenable to this strategy to fabricate pore-networked gels with accessible porosity, demonstrating their potential use in the field of gas adsorption or separation.

Mapping the Methanol-to-Gasoline Process Over Zeolite Beta.

Decarbonizing the transportation sector is among the biggest challenges in the fight against climate change. CO2 -neutral fuels, such as those obtained from renewable methanol, have the potential to account for a large share of the solution, since these could be directly compatible with existing power trains. Although discovered in 1977, the zeolite-catalyzed methanol-to-gasoline (MTG) process has hardly reached industrial maturity, among other reasons, because maximizing the production of gasoline range hydrocarbons from methanol has proved complicated. In this work, we apply multimodal operando UV/Vis diffuse reflectance spectroscopy coupled with an online mass spectrometer and "mobility-dependent" solid-state NMR spectroscopy to better understand the reaction mechanism over zeolites H-Beta and Zn-Beta. Significantly, the influential co-catalytic role of oxymethylene species is linked to gasoline formation, which impacts the MTG process more than carbonylated species.

Mixed Matrix Membranes with Surface Functionalized Metal-Organic Framework Sieves for Efficient Propylene/Propane Separation.

Membrane technology, regarded as an environmentally friendly and sustainable approach, offers great potential to address the large energy penalty associated with the energy-intensive propylene/propane separation. Quest for molecular sieving membranes for this important separation is of tremendous interest. Here, a fluorinated metal-organic framework (MOF) material, known as KAUST-7 (KAUST: King Abdullah University of Science and Technology) with well-defined narrow 1D channels that can effectively discriminate propylene from propane based on a size-sieving mechanism, is successfully incorporated into a polyimide matrix to fabricate molecular sieving mixed matrix membranes (MMMs). Markedly, the surface functionalization of KAUST-7 nanoparticles with carbene moieties affords the requisite interfacial compatibility, with minimal nonselective defects at polymer-filler interfaces, for the fabrication of a molecular sieving MMM. The optimal membrane with a high MOF loading (up to 45 wt.%) displays a propylene permeability of ≈95 barrer and a mixed propylene/propane selectivity of ≈20, far exceeding the state-of-the-art upper bound limits. Moreover, the resultant membrane exhibits robust structural stability under practical conditions, including high pressures (up to 8 bar) and temperatures (up to 100 °C). The observed outstanding performance attests to the importance of surface engineering for the preparation and plausible deployment of high-performance MMMs for industrial applications.

Post-Synthetic Surface Modification of Metal-Organic Frameworks and Their Potential Applications.

Metal-organic frameworks (MOFs) are porous hybrid materials with countless potential applications. Most of these rely on their porous structure, tunable composition, and the possibility of incorporating and expanding their functions. Although functionalization of the inner surface of MOF crystals has received considerable attention in recent years, methods to functionalize selectively the outer crystal surface of MOFs are developed to a lesser extent, despite their importance. This article summarizes different types of post-synthetic modifications and possible applications of modified materials such as: catalysis, adsorption, drug delivery, mixed matrix membranes, and stabilization of porous liquids.