Electrochemically Formed Defect-Rich Bismuthene-Bismuth Oxycarbonate Nanosheets Promote Selective Reduction of CO to Formic Acid.

Formic acid has a high hydrogen storage capacity and is a valuable chemical for industrially important reactions. The industrial production of formic acid proceeds through the carbonylation of methanol to form methyl formate and its subsequent hydrolysis. This process requires high temperature and pressure, and it relies on the use of fossil fuels.

Selectivity Descriptors of Glycerol Valorization over 10-Member Ring Zeolites.

The shift to renewable feedstocks is essential for developing "smart drop-in" technologies to produce synthetic fuels and chemicals, playing a crucial role in industrial decarbonization. Herein, zeolite-catalyzed glycerol valorization offers a mature way to create higher-value chemicals. This study aims to identify the key factors influencing process efficiency by examining the reaction mechanisms of glycerol valorization using 10-membered ring zeolites: ZSM-5 (MFI, 3D), MCM-22 (MWW, 2D), and ZSM-22 (TON, 1D), each with unique topologies and channel structures.

Dynamic boron-doping switched chitin-based single-atom Pt catalyst for chemo-selective hydrogenation.

Biomass valorization is a way to promote the 'waste-to-wealth' concept, which is a pre-requisite condition for a future sustainable lifestyle. The direct utilization of natural polymer for value-added materials should be prioritized. With this object, we demonstrate a facile and economical method to prepare chitin-derived supramolecular nanowires-stabilized single-atom sites Pt catalysts (SS-Pt-CSNs).

Selectivity control by zeolites during methanol-mediated CO hydrogenation processes.

The thermocatalytic conversion of CO with green or blue hydrogen into valuable energy and commodity chemicals such as alcohols, olefins, and aromatics emerges as one of the most promising strategies for mitigating global warming concerns in the future. This process can follow either a CO-modified Fischer-Tropsch synthesis route or a methanol-mediated route, with the latter being favored for its high product selectivity beyond the Anderson-Schulz-Flory distribution. Despite the progress of the CO-led methanol-mediated route over bifunctional metal/zeolite catalysts, challenges persist in developing catalysts with both high activity and selectivity due to the complexity of CO hydrogenation reaction networks and the difficulty in controlling C-O bond activation and C-C bond coupling on multiple active sites within zeolites.

The Paradoxical Influence of Hydrothermally Treated Zeolites on the Hydrocarbon Pool Mechanism.

Understanding the mechanistic intricacies of hydrothermally treated zeolite is crucial for valorizing any oxygen-containing renewable feedstocks (e. g., methanol, carbon dioxide, biomass).

Selectivity descriptors of the catalytic -hexane cracking process over 10-membered ring zeolites.

Zeolite-mediated catalytic cracking of alkanes is pivotal in the petrochemical and refining industry, breaking down heavier hydrocarbon feedstocks into fuels and chemicals. Its relevance also extends to emerging technologies such as biomass and plastic valorization. Zeolite catalysts, with shape selectivity and selective adsorption capabilities, enhance efficiency and sustainability due to their well-defined network of pores, dimensionality, cages/cavities, and channels.

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.

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.

Toward Developing Superior Cu-Based Metal-Organic Framework-Derived Materials for Electrocatalytic Oxidation of Ethanol.

This project addresses the urgent need for efficient and cost-effective development of electrocatalysts for the ethanol oxidation reaction (EOR). This reaction offers promising renewable energy solutions but faces challenges due to the slow EOR kinetics, typically requiring costly noble metal catalysts. To overcome these limitations, this study focuses on developing CuZn-based EOR catalysts derived from metal-organic frameworks (MOFs), focusing on understanding the structure-performance relationship between pristine MOF-based electrocatalysts and their pyrolyzed counterparts.

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.

Controlling the C/C product selectivity of electrochemical CO reduction upon tuning bimetallic CuIn electrocatalyst composition and operating conditions.

Electrochemical carbon dioxide (CO) reduction (eCOR) over Cu-based bimetallic catalysts is a promising technique for converting CO into value-added multi-carbon products, such as fuels, chemicals, and materials. For improving the process efficiency, electrocatalyst development for the eCOR must be integrated with tuning of operating conditions. For example, CuIn-based materials typically lead to preferential C product selectivity, which delivers the desired C products upon varying the In/Cu ratio and operating conditions (, in 0.

Evaluating the efficacy of zeolites synthesized from natural clay for the methanol-to-hydrocarbon process.

Introducing sustainability into advanced catalytic material design is essential to address growing environmental concerns. Among them, synthesizing inorganic zeolite materials from non-traditional sources (like natural clay) offers several advantages, contributing to sustainability and environmental stewardship. With this objective, we used kaolin to synthesize zeolites with different topologies: SSZ-13 (8-MR with CHA topology), ZSM-5 (10-MR with MFI topology), and Beta (12-MR with BEA topology) (MR: member ring), where a simple and flexible synthetic protocol was adopted without any significant changes.

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

The CO -to-aromatics process is a chemical reaction that converts carbon dioxide (CO ) into valuable petrochemical, i. e., aromatics (especially, benzene, toluene, and xylene) over the metal/zeolite bifunctional catalytic systems.

Exploring Ligand-Controlled C Product Selectivity in Carbon Dioxide Reduction with Copper Metal-Organic Framework Nanosheets.

The suitable choice of an electrocatalyst is crucial in controlling the selectivity of electrocatalytic CO reduction products. Herein, we have explored the effect of different ligand environments in 2D metal-organic frameworks (MOFs), viz., copper naphthalenedicarboxylate (Cu-UNDC) and copper benzenedicarboxylate (Cu-UBDC).

Evaluating the efficacy of nanosized CuZnAl and CuZnZr mixed oxides for electrocatalytic CO reduction.

The increased awareness of carbon management has prompted the scientific community towards delivering sustainable catalytic technologies, preferably from CO. Copper-based multifunctional catalysts are the most frequently used for thermal hydrogenation and electrocatalytic reduction of CO (COR) processes. To improve the understanding and efficacy of these materials for the COR reaction, Cu-Zn oxides combined with AlO and ZrO were synthesized by the coprecipitation method and annealed at 500 °C, 600 °C, and 700 °C (, Cu/ZnO/AlO- and Cu/ZnO/ZrO systems-, where is the annealing temperature) to tune their multi-functionality.

First-Generation Organic Reaction Intermediates in Zeolite Chemistry and Catalysis.

Zeolite chemistry and catalysis are expected to play a decisive role in the next decade(s) to build a more decentralized renewable feedstock-dependent sustainable society owing to the increased scrutiny over carbon emissions. Therefore, the lack of fundamental and mechanistic understanding of these processes is a critical "technical bottleneck" that must be eliminated to maximize economic value and minimize waste. We have identified, considering this objective, that the chemistry related to the first-generation reaction intermediates (i.

Selectivity descriptors for the direct hydrogenation of CO to hydrocarbons during zeolite-mediated bifunctional catalysis.

Cascade processes are gaining momentum in heterogeneous catalysis. The combination of several catalytic solids within one reactor has shown great promise for the one-step valorization of C1-feedstocks. The combination of metal-based catalysts and zeolites in the gas phase hydrogenation of CO leads to a large degree of product selectivity control, defined mainly by zeolites.

Synthesis, Characterization, and Water Oxidation Activity of Isomeric Ru Complexes.

The synthesis and characterization of the isomeric ruthenium complexes with the general formula and [Ru(trpy)(qc)X] (trpy is 2,2':6',2″-terpyridine, qc is 8-quinolinecarboxylate, and , X = Cl, = 0; and , X=OH, = 1) with respect to the relative disposition of the carboxylate and X ligands are reported. For comparison purposes, another set of ruthenium complexes with general formula and [Ru(trpy)(pic)(OH)] (pic is 2-picolinate (-, -)) have been prepared. The complexes with a qc ligand show a more distorted geometry compared to the complexes with a pic ligand.

Electrochemical Oxidation Enables Regioselective and Scalable α-C(sp)-H Acyloxylation of Sulfides.

A highly selective, environmentally friendly, and scalable electrochemical protocol for the construction of α-acyloxy sulfides, through the synergistic effect of self-assembly-induced C(sp)-H/O-H cross-coupling, is reported. It features exceptionally broad substrate scope, high regioselectivity, gram-scale synthesis, construction of complex molecules, and applicability to a variety of nucleophiles. Moreover, the soft X-ray absorption technique and a series of control experiments have been utilized to demonstrate the pivotal role of the self-assembly of the substrates, which indeed is responsible for the excellent compatibility and precise control of high regioselectivity in our electrochemical protocol.

Manganese-Catalyzed Oxidative Azidation of C(sp)-H Bonds under Electrophotocatalytic Conditions.

The selective installation of azide groups into C(sp)-H bonds is a priority research topic in organic synthesis, particularly in pharmaceutical discovery and late-stage diversification. Herein, we demonstrate a generalized manganese-catalyzed oxidative azidation methodology of C(sp)-H bonds using nucleophilic NaN as an azide source under electrophotocatalytic conditions. This approach allows us to perform the reaction without the necessity of adding an excess of the substrate and successfully avoiding the use of stoichiometric chemical oxidants such as iodine(III) reagent or NFSI.