Showing papers on "Methanol published in 2020"

Hydrophobic zeolite modification for in situ peroxide formation in methane oxidation to methanol

Abstract: Selective partial oxidation of methane to methanol suffers from low efficiency. Here, we report a heterogeneous catalyst system for enhanced methanol productivity in methane oxidation by in situ generated hydrogen peroxide at mild temperature (70°C). The catalyst was synthesized by fixation of AuPd alloy nanoparticles within aluminosilicate zeolite crystals, followed by modification of the external surface of the zeolite with organosilanes. The silanes appear to allow diffusion of hydrogen, oxygen, and methane to the catalyst active sites, while confining the generated peroxide there to enhance its reaction probability. At 17.3% conversion of methane, methanol selectivity reached 92%, corresponding to methanol productivity up to 91.6 millimoles per gram of AuPd per hour.

Growth of E. coli on formate and methanol via the reductive glycine pathway.

Abstract: Engineering a biotechnological microorganism for growth on one-carbon intermediates, produced from the abiotic activation of CO2, is a key synthetic biology step towards the valorization of this greenhouse gas to commodity chemicals. Here we redesign the central carbon metabolism of the model bacterium Escherichia coli for growth on one-carbon compounds using the reductive glycine pathway. Sequential genomic introduction of the four metabolic modules of the synthetic pathway resulted in a strain capable of growth on formate and CO2 with a doubling time of ~70 h and growth yield of ~1.5 g cell dry weight (gCDW) per mol-formate. Short-term evolution decreased doubling time to less than 8 h and improved biomass yield to 2.3 gCDW per mol-formate. Growth on methanol and CO2 was achieved by further expression of a methanol dehydrogenase. Establishing synthetic formatotrophy and methylotrophy, as demonstrated here, paves the way for sustainable bioproduction rooted in CO2 and renewable energy. Redesigning the central carbon metabolism of Escherichia coli with the reductive glycine pathway enables growth on the one-carbon compounds formate and CO2, and the addition of methanol dehydrogenase further enables growth on methanol and CO2.

Unique hole-accepting carbon-dots promoting selective carbon dioxide reduction nearly 100% to methanol by pure water

Abstract: Solar-driven CO2 reduction by abundant water to alcohols can supply sustainable liquid fuels and alleviate global warming. However, the sluggish water oxidation reaction has been hardly reported to be efficient and selective in CO2 conversion due to fast charge recombination. Here, using transient absorption spectroscopy, we demonstrate that microwave-synthesised carbon-dots (mCD) possess unique hole-accepting nature, prolonging the electron lifetime (t50%) of carbon nitride (CN) by six folds, favouring a six-electron product. mCD-decorated CN stably produces stoichiometric oxygen and methanol from water and CO2 with nearly 100% selectivity to methanol and internal quantum efficiency of 2.1% in the visible region, further confirmed by isotopic labelling. Such mCD rapidly extracts holes from CN and prevents the surface adsorption of methanol, favourably oxidising water over methanol and enhancing the selective CO2 reduction to alcohols. This work provides a unique strategy for efficient and highly selective CO2 reduction by water to high-value chemicals.

Water-promoted interfacial pathways in methane oxidation to methanol on a CeO2-Cu2O catalyst

Abstract: Highly selective oxidation of methane to methanol has long been challenging in catalysis. Here, we reveal key steps for the pro-motion of this reaction by water when tuning the selectivity of a well-defined CeO2/Cu2O/Cu(111) catalyst from carbon monoxide and carbon dioxide to methanol under a reaction environment with methane, oxygen, and water. Ambient-pressure x-ray photoelectron spectroscopy showed that water added to methane and oxygen led to surface methoxy groups and accelerated methanol production. These results were consistent with density functional theory calculations and kinetic Monte Carlo simulations, which showed that water preferentially dissociates over the active cerium ions at the CeO2-Cu2O/Cu(111) interface. The adsorbed hydroxyl species blocked O-O bond cleavage that would dehydrogenate methoxy groups to carbon monoxide and carbon dioxide, and it directly converted this species to methanol, while oxygen reoxidized the reduced surface. Water adsorption also displaced the produced methanol into the gas phase.

Inverse ZrO2/Cu as a highly efficient methanol synthesis catalyst from CO2 hydrogenation

Abstract: Enhancing the intrinsic activity and space time yield of Cu based heterogeneous methanol synthesis catalysts through CO2 hydrogenation is one of the major topics in CO2 conversion into value-added liquid fuels and chemicals. Here we report inverse ZrO2/Cu catalysts with a tunable Zr/Cu ratio have been prepared via an oxalate co-precipitation method, showing excellent performance for CO2 hydrogenation to methanol. Under optimal condition, the catalyst composed by 10% of ZrO2 supported over 90% of Cu exhibits the highest mass-specific methanol formation rate of 524 gMeOHkgcat−1h−1 at 220 °C, 3.3 times higher than the activity of traditional Cu/ZrO2 catalysts (159 gMeOHkgcat−1h−1). In situ XRD-PDF, XAFS and AP-XPS structural studies reveal that the inverse ZrO2/Cu catalysts are composed of islands of partially reduced 1–2 nm amorphous ZrO2 supported over metallic Cu particles. The ZrO2 islands are highly active for the CO2 activation. Meanwhile, an intermediate of formate adsorbed on the Cu at 1350 cm−1 is discovered by the in situ DRIFTS. This formate intermediate exhibits fast hydrogenation conversion to methoxy. The activation of CO2 and hydrogenation of all the surface oxygenate intermediates are significantly accelerated over the inverse ZrO2/Cu configuration, accounting for the excellent methanol formation activity observed. Enhancing the intrinsic activity and space time yield of Cu based heterogeneous methanol synthesis catalysts is one of the major topics in CO2 hydrogenation. Here the authors develop a highly active inverse catalyst composed of fine ZrO2 islands dispersed on metallic Cu nanoparticles.

Highly Active ZnO-ZrO2 Aerogels Integrated with H-ZSM-5 for Aromatics Synthesis from Carbon Dioxide

Abstract: Bifunctional catalysis coupling CO2 to methanol and methanol to hydrocarbons is a promising strategy for the direct hydrogenation of CO2 into high-value chemicals. However, bifunctional catalysts s...

Single-pass transformation of syngas into ethanol with high selectivity by triple tandem catalysis

Abstract: Synthesis of ethanol from non-petroleum carbon resources via syngas (a mixture of H2 and CO) is an important but challenging research target. The current conversion of syngas to ethanol suffers from low selectivity or multiple processes with high energy consumption. Here, we report a high-selective conversion of syngas into ethanol by a triple tandem catalysis. An efficient trifunctional tandem system composed of potassium-modified ZnO–ZrO2, modified zeolite mordenite and Pt–Sn/SiC working compatibly in syngas stream in one reactor can afford ethanol with a selectivity of 90%. We demonstrate that the K+–ZnO–ZrO2 catalyses syngas conversion to methanol and the mordenite with eight-membered ring channels functions for methanol carbonylation to acetic acid, which is then hydrogenated to ethanol over the Pt–Sn/SiC catalyst. The present work offers an effective methodology leading to high selective conversion by decoupling a single-catalyst-based complicated and uncontrollable reaction into well-controlled multi-steps in tandem in one reactor. Direct synthesis of ethanol from non-petroleum carbon resources via syngas (CO/H2) is a highly attractive but challenging target. Here, the authors report a triple tandem catalytic system for single-pass conversion of syngas into ethanol with selectivity as high as 90%.

Novel Heterogeneous Catalysts for CO2 Hydrogenation to Liquid Fuels.

Abstract: Carbon dioxide (CO2) hydrogenation to liquid fuels including gasoline, jet fuel, diesel, methanol, ethanol, and other higher alcohols via heterogeneous catalysis, using renewable energy, not only effectively alleviates environmental problems caused by massive CO2 emissions, but also reduces our excessive dependence on fossil fuels. In this Outlook, we review the latest development in the design of novel and very promising heterogeneous catalysts for direct CO2 hydrogenation to methanol, liquid hydrocarbons, and higher alcohols. Compared with methanol production, the synthesis of products with two or more carbons (C2+) faces greater challenges. Highly efficient synthesis of C2+ products from CO2 hydrogenation can be achieved by a reaction coupling strategy that first converts CO2 to carbon monoxide or methanol and then conducts a C-C coupling reaction over a bifunctional/multifunctional catalyst. Apart from the catalytic performance, unique catalyst design ideas, and structure-performance relationship, we also discuss current challenges in catalyst development and perspectives for industrial applications.

Hydroxide Based Integrated CO2 Capture from Air and Conversion to Methanol

Abstract: The first example of an alkali hydroxide-based system for CO2 capture and conversion to methanol has been established. Bicarbonate and formate salts were hydrogenated to methanol with high yields in a solution of ethylene glycol. In an integrated one-pot system, CO2 was efficiently captured by an ethylene glycol solution of the base and subsequently hydrogenated to CH3OH at relatively mild temperatures (100-140 °C) using Ru-PNP catalysts. The produced methanol can be easily separated by distillation. Hydroxide base regeneration at low temperatures was observed for the first time. Finally, CO2 capture from ambient air and hydrogenation to CH3OH was demonstrated. We postulate that the high capture efficiency and stability of hydroxide bases make them superior to existing amine-based routes for direct air capture and conversion to methanol in a scalable process.

Activity and degradation study of an Fe-N-C catalyst for ORR in Direct Methanol Fuel Cell (DMFC)

Abstract: In this work a comprehensive study of the activity and stability of a non-precious metal catalyst of type Fe- N- C in acidic media is reported. The catalyst was prepared from polyaniline, dicyandiamide and iron acetate as precursors. Temperature-dependent rotating-disk electrode experiments were performed to determine the activation energy of the catalyst. Besides, load cycle durability tests with and without the addition of methanol show that there is no additional deactivation caused by methanol addition. In a Direct Methanol Fuel Cell (DMFCs) our catalyst performed similarly good in comparison to other Fe-N-C catalysts. Raman and Mossbauer spectroscopy provide valuable information on the structural composition and chemical changes induced by durability and stability testing of the catalyst. While the maximum power density during DMFC operation decreases by 85%, the qualitative distribution of iron sites might indicate the formation of iron and iron oxide clusters as decomposition product associated with the disintegration of FeN4 sites.

Methanol tolerance of atomically dispersed single metal site catalysts: mechanistic understanding and high-performance direct methanol fuel cells

Abstract: Proton-exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are promising power sources from portable electronic devices to vehicles. The high-cost issue of these low-temperature fuel cells can be primarily addressed by using platinum-group metal (PGM)-free oxygen reduction reaction (ORR) catalysts, in particular atomically dispersed metal–nitrogen–carbon (M–N–C, M = Fe, Co, Mn). Furthermore, a significant advantage of M–N–C catalysts is their superior methanol tolerance over Pt, which can mitigate the methanol cross-over effect and offer great potential of using a higher concentration of methanol in DMFCs. Here, we investigated the ORR catalytic properties of M–N–C catalysts in methanol-containing acidic electrolytes via experiments and density functional theory (DFT) calculations. FeN4 sites demonstrated the highest methanol tolerance ability when compared to metal-free pyridinic N, CoN4, and MnN4 active sites. The methanol adsorption on MN4 sites is even strengthened when electrode potentials are applied during the ORR. The negative influence of methanol adsorption becomes significant for methanol concentrations higher than 2.0 M. However, the methanol adsorption does not affect the 4e− ORR pathway or chemically destroy the FeN4 sites. The understanding of the methanol-induced ORR activity loss guides the design of promising M–N–C cathode catalyst in DMFCs. Accordingly, we developed a dual-metal site Fe/Co–N–C catalyst through a combined chemical-doping and adsorption strategy. Instead of generating a possible synergistic effect, the introduced Co atoms in the first doping step act as “scissors” for Zn removal in metal–organic frameworks (MOFs), which is crucial for modifying the porosity of the catalyst and providing more defects for stabilizing the active FeN4 sites generated in the second adsorption step. The Fe/Co–N–C catalyst significantly improved the ORR catalytic activity and delivered remarkably enhanced peak power densities (i.e., 502 and 135 mW cm−2) under H2–air and methanol–air conditions, respectively, representing the best performance for both types of fuel cells. Notably, the fundamental understanding of methanol tolerance, along with the encouraging DMFC performance, will open an avenue for the potential application of atomically dispersed M–N–C catalysts in other direct alcohol or ammonia fuel cells.

Hydrogenation of CO2 to Methanol on a Auδ+–In2O3-x Catalyst

Abstract: CO2 hydrogenation to methanol has attracted increasing attention with the development of renewable hydrogen. A big challenge is to identify catalysts able to achieve high conversion and selectivity...

Strong Electronic Oxide-Support Interaction over In2O3/ZrO2 for Highly Selective CO2 Hydrogenation to Methanol.

Abstract: Metal oxides are widely employed in heterogeneous catalysis, but it remains challenging to determine their exact structure and understand the reaction mechanisms at the molecular level due to their structural complexity, in particular for binary oxides. This paper describes the observation of the strong electronic interaction between In2O3 and monoclinic ZrO2 (m-ZrO2) by quasi-in-situ XPS experiments combined with theoretical studies, which leads to support-dependent methanol selectivity. In2O3/m-ZrO2 exhibits methanol selectivity up to 84.6% with a CO2 conversion of 12.1%. Moreover, at a wide range of temperatures, the methanol yield of In2O3/m-ZrO2 is much higher than that of In2O3/t-ZrO2 (t-: tetragonal), which is due to the high dispersion of the In-O-In structure over m-ZrO2 as determined by in situ Raman spectra. The electron transfer from m-ZrO2 to In2O3 is confirmed by XPS and DFT calculations and improves the electron density of In2O3, which promotes H2 dissociation and hydrogenation of formate intermediates to methanol. The concept of the electronic interaction between an oxide and a support provides guidelines to develop hydrogenation catalysts.

Mathematical Model of a Direct Methanol Fuel Cell.

Abstract: A one dimensional (1-D), isothermal model for a direct methanol fuel cell (DMFC) is presented. This model accounts for the kinetics of the multi-step methanol oxidation reaction at the anode. Diffusion and crossover of methanol are modeled and the mixed potential of the oxygen cathode due to methanol crossover is included. Kinetic and diffusional parameters are estimated by comparing the model to data from a 25 cm2 DMFC. This semi-analytical model can be solved rapidly so that it is suitable for inclusion in real-time system level DMFC simulations.

The unique interplay between copper and zinc during catalytic carbon dioxide hydrogenation to methanol

Abstract: In spite of numerous works in the field of chemical valorization of carbon dioxide into methanol, the nature of high activity of Cu/ZnO catalysts, including the reaction mechanism and the structure of the catalyst active site, remains the subject of intensive debate. By using high-pressure operando techniques: steady-state isotope transient kinetic analysis coupled with infrared spectroscopy, together with time-resolved X-ray absorption spectroscopy and X-ray powder diffraction, and supported by electron microscopy and theoretical modeling, we present direct evidence that zinc formate is the principal observable reactive intermediate, which in the presence of hydrogen converts into methanol. Our results indicate that the copper-zinc alloy undergoes oxidation under reaction conditions into zinc formate, zinc oxide and metallic copper. The intimate contact between zinc and copper phases facilitates zinc formate formation and its hydrogenation by hydrogen to methanol.

Materializing efficient methanol oxidation via electron delocalization in nickel hydroxide nanoribbon.

Abstract: Achieving a functional and durable non-platinum group metal-based methanol oxidation catalyst is critical for a cost-effective direct methanol fuel cell. While Ni(OH)2 has been widely studied as methanol oxidation catalyst, the initial process of oxidizing Ni(OH)2 to NiOOH requires a high potential of 1.35 V vs. RHE. Such potential would be impractical since the theoretical potential of the cathodic oxygen reduction reaction is at 1.23 V. Here we show that a four-coordinated nickel atom is able to form charge-transfer orbitals through delocalization of electrons near the Fermi energy level. As such, our previously reported periodically arranged four-six-coordinated nickel hydroxide nanoribbon structure (NR-Ni(OH)2) is able to show remarkable methanol oxidation activity with an onset potential of 0.55 V vs. RHE and suggests the operability in direct methanol fuel cell configuration. Thus, this strategy offers a gateway towards the development of high performance and durable non-platinum direct methanol fuel cell. Development of suitable methanol oxidation reaction catalysts for direct methanol fuel cells is challenging due to sluggish kinetics. Herein, authors show that four-coordinate nickel atoms form charge-transfer orbitals near the Fermi energy level, leading to remarkable methanol oxidation activity.

Selective Photo-oxidation of Methane to Methanol with Oxygen over Dual-Cocatalyst-Modified Titanium Dioxide

Abstract: Direct and selective oxidation of CH4 with dioxygen to methanol is a “dream reaction” in modern catalysis yet remains a great challenge. Here, we report that TiO2 loaded with dual cocatalysts, that...

Identifying the nature of the active sites in methanol synthesis over Cu/ZnO/Al2O3 catalysts.

Abstract: The heterogeneously catalysed reaction of hydrogen with carbon monoxide and carbon dioxide (syngas) to methanol is nearly 100 years old, and the standard methanol catalyst Cu/ZnO/Al2O3 has been applied for more than 50 years. Still, the nature of the Zn species on the metallic Cu0 particles (interface sites) is heavily debated. Here, we show that these Zn species are not metallic, but have a positively charged nature under industrial methanol synthesis conditions. Our kinetic results are based on a self-built high-pressure pulse unit, which allows us to inject selective reversible poisons into the syngas feed passing through a fixed-bed reactor containing an industrial Cu/ZnO/Al2O3 catalyst under high-pressure conditions. This method allows us to perform surface-sensitive operando investigations as a function of the reaction conditions, demonstrating that the rate of methanol formation is only decreased in CO2-containing syngas mixtures when pulsing NH3 or methylamines as basic probe molecules. Methanol synthesis has a high potential for global CO2 reduction. Here, the authors identify the oxidation state of the zinc sites on the metallic copper particles as partially positive for an industrial Cu/ZnO/Al2O3 catalyst under high-pressure reaction conditions.

Performance of an aliovalent-substituted CoCeOx catalyst from bimetallic MOF for VOC oxidation in air

Abstract: The aliovalent-substitution of cobalt into ceria lattice was demonstrated using a bimetallic CoCeBDC MOF to achieve a high degree of atomic level mixing in the CoCeOx catalyst. Spectroscopic analyses including X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed the successful insertion of cobalt atom with a concomitant increase in defects (i.e., Raman ID/IF2g = 0.25) and oxygen vacancies (i.e., XPS Oβ/(Oα+Oβ) = 0.33) that correlates well with catalytic activity for the oxidations of methanol, acetone, toluene, and o-xylene. The as-prepared CoCeOx performed a 50% conversion (T50) and 90% conversion (T90) in toluene oxidation at 212 °C and 227 °C that are significantly lower than the reference Co3O4/CeO2 nanocube catalyst that had T50 of 261 °C and T90 of 308 °C, indicating its better catalytic activity. Moreover, CoCeOx catalyst completely oxidizes organic compounds to carbon dioxide and water, while reaction over Co3O4/CeO2 nanocube catalyst produces significant carbon monoxide.