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Trends in Biotechnology Apr 2021Mitigating climate change is a key driver for the development of sustainable and CO-neutral production processes. In this regard, connecting carbon capture and... (Review)
Review
Mitigating climate change is a key driver for the development of sustainable and CO-neutral production processes. In this regard, connecting carbon capture and utilization processes to derive microbial C fermentation substrates from CO is highly promising. This strategy uses methylotrophic microbes to unlock next-generation processes, converting CO-derived methanol. Synthetic biology approaches in particular can empower synthetic methylotrophs to produce a variety of commodity chemicals. We believe that yeasts have outstanding potential for this purpose, because they are able to separate toxic intermediates and metabolic reactions in organelles. This compartmentalization can be harnessed to design superior synthetic methylotrophs, capable of utilizing methanol and other hitherto largely disregarded C compounds, thus supporting the establishment of a future circular economy.
Topics: Fermentation; Metabolic Engineering; Methanol; Synthetic Biology; Yeasts
PubMed: 33008643
DOI: 10.1016/j.tibtech.2020.08.008 -
Chemosphere Jul 2022This review explains the various methods of conversion of Carbon dioxide (CO) to methanol by using homogenous, heterogeneous catalysts through hydrogenation,... (Review)
Review
This review explains the various methods of conversion of Carbon dioxide (CO) to methanol by using homogenous, heterogeneous catalysts through hydrogenation, photochemical, electrochemical, and photo-electrochemical techniques. Since, CO is the major contributor to global warming, its utilization for the production of fuels and chemicals is one of the best ways to save our environment in a sustainable manner. However, as the CO is very stable and less reactive, a proper method and catalyst development is most important to break the CO bond to produce valuable chemicals like methanol. Litertaure says the catalyt types, ratio and it surface structure along with the temperature and pressure are the most controlling parameters to optimize the process for the production of methanol from CO. This article explains about the various controlling parameters of synthesis of Methanol from CO along with the advantages and drawbacks of each process. The mechanism of each synthesis process in presence of metal supported catalyst is described. Basically the activity of Cu supported catalyst and its stability based on the activity for the methanol synthesis from CO through various methods is critically described.
Topics: Carbon Dioxide; Catalysis; Electrochemical Techniques; Hydrogenation; Methanol
PubMed: 35304218
DOI: 10.1016/j.chemosphere.2022.134299 -
Journal of the American Chemical Society Sep 2022The relative stability of reactive intermediates and reactants on a surface, which dictates the rate and selectivity of catalytic reactions in both gas and liquid...
The relative stability of reactive intermediates and reactants on a surface, which dictates the rate and selectivity of catalytic reactions in both gas and liquid phases, is dependent on numerous factors. One well-established example is secondary interactions, such as van der Waals interactions between the catalyst surface and the pendant group of the intermediate, which can govern reaction selectivity for coupling reactions. Herein, we directly show that interactions between adsorbed reaction intermediates and reactant molecules increase the binding energy and affects the geometrical arrangement of coadsorbed reactant/solvent molecules. Evidence for this effect is demonstrated for the oxidative coupling reaction of methanol on a single crystal gold (Au(110)) surface. The rate-limiting reaction intermediate for methanol self-coupling, methoxy, stabilizes excess adsorbed methanol, which desorbs as a result of beta-hydride decomposition of the adsorbed methoxy. Direct molecular-scale imaging by scanning tunneling microscopy, supplemented by density functional theory, revealed interactive structures formed by methoxy and coadsorbed methanol. Interactions between the methoxy intermediate and coadsorbed methanol stabilizes a hydrogen-bonded network comprising methoxy and methanol by a minimum of 0.13 eV per methanol molecule. Inclusion of such interactions between reaction intermediates and coadsorbed reactants and solvents in kinetic models is important for microkinetic analysis of the rates and selectivities of catalytic reactions in both the gas and liquid phases whenever appreciable coverages of species from the ambient phase exist.
Topics: Catalysis; Ethanol; Gold; Hydrogen; Methanol; Solvents
PubMed: 36112426
DOI: 10.1021/jacs.2c02199 -
Angewandte Chemie (International Ed. in... Nov 2022Formaldehyde (HCHO) is a crucial C building block for daily-life commodities in a wide range of industrial processes. Industrial production of HCHO today is based on... (Review)
Review
Formaldehyde (HCHO) is a crucial C building block for daily-life commodities in a wide range of industrial processes. Industrial production of HCHO today is based on energy- and cost-intensive gas-phase catalytic oxidation of methanol, which calls for exploring other and more sustainable ways of carrying out this process. Utilization of carbon dioxide (CO ) as precursor presents a promising strategy to simultaneously mitigate the carbon footprint and alleviate environmental issues. This Minireview summarizes recent progress in CO -to-HCHO conversion using hydrogenation, hydroboration/hydrosilylation as well as photochemical, electrochemical, photoelectrochemical, and enzymatic approaches. The active species, reaction intermediates, and mechanistic pathways are discussed to deepen the understanding of HCHO selectivity issues. Finally, shortcomings and prospects of the various strategies for sustainable reduction of CO to HCHO are discussed.
Topics: Carbon Dioxide; Catalysis; Formaldehyde; Methanol; Oxidation-Reduction
PubMed: 36066469
DOI: 10.1002/anie.202204008 -
JAMA Jan 2021
Topics: Baths; History, 20th Century; Humans; Methanol; Quackery
PubMed: 33399837
DOI: 10.1001/jama.2020.17726 -
Chemical Society Reviews Jul 2022Ethanol, as one of the important bulk chemicals, is widely used in modern society. It can be produced by fermentation of sugar, petroleum refining, or conversion of... (Review)
Review
Ethanol, as one of the important bulk chemicals, is widely used in modern society. It can be produced by fermentation of sugar, petroleum refining, or conversion of syngas (CO/H). Among these approaches, conversion of syngas to ethanol (STE) is the most environmentally friendly and economical process. Although considerable progress has been made in STE conversion, control of CO activation and C-C growth remains a great challenge. This review highlights recent advances in the routes and catalysts employed in STE technology. The catalyst designs and pathway designs are summarized and analysed for the direct and indirect STE routes, respectively. In the direct STE routes (, one-step synthesis of ethanol from syngas), modified catalysts of methanol synthesis, modified catalysts of Fischer-Tropsch synthesis, Mo-based catalysts, noble metal catalysts and multifunctional catalysts are systematically reviewed based on their catalyst designs. Further, in the indirect STE routes (, multi-step processes for ethanol synthesis from syngas methanol/dimethyl ether as intermediates), carbonylation of methanol/dimethyl ether followed by hydrogenation, and coupling of methanol with CO to form dimethyl oxalate followed by hydrogenation, are outlined according to their pathway designs. The goal of this review is to provide a comprehensive perspective on STE technology and inspire the invention of new catalysts and pathway designs in the near future.
Topics: Catalysis; Ethanol; Hydrogenation; Metals; Methanol
PubMed: 35705080
DOI: 10.1039/d0cs01003k -
International Journal of Environmental... Jul 2018Alcohol-based hand rub (hand sanitizer) is heavily used in the community and the healthcare setting to maintain hand hygiene. Methanol must never be used in such a... (Review)
Review
Alcohol-based hand rub (hand sanitizer) is heavily used in the community and the healthcare setting to maintain hand hygiene. Methanol must never be used in such a product because oral, pulmonary and/or skin exposures can result in severe systemic toxicity and even deaths. However, sporadic cases of acute poisoning indicate that alcohol-based hand rub with undeclared methanol may be found in the market from time to time. The unexpected presence of methanol poses a serious threat to public health. Unintentional ingestion by young children and inadvertent consumption by older subjects as alcohol (ethanol) substitute can occur. Methanol is more lethal and poisoning often requires antidotal therapy, in addition to supporting therapy and critical care. However, specific therapy may be delayed because the exposure to methanol is initially not suspected. When repeatedly used as a hand rub, skin absorption resulting in chronic toxicity (e.g., visual disturbances) occurs, particularly if methanol induced desquamation and dermatitis are present. Nationwide surveillance systems, regional/international toxicovigilance networks and situational awareness among the healthcare professionals should facilitate the early detection, management and prevention of such poisoning incidents of public health significance.
Topics: Hand Sanitizers; Health Personnel; Humans; Methanol; Skin Absorption
PubMed: 29987197
DOI: 10.3390/ijerph15071440 -
The Journal of Physical Chemistry. B Mar 2022The Menshutkin reaction is a methyl transfer reaction relevant in fields ranging from biochemistry to chemical synthesis. In the present work, the energetics and solvent...
The Menshutkin reaction is a methyl transfer reaction relevant in fields ranging from biochemistry to chemical synthesis. In the present work, the energetics and solvent distributions for NH+MeCl and Pyr+MeBr reactions were investigated in explicit solvent (water, methanol, acetonitrile, benzene, cyclohexane) by means of reactive molecular dynamics simulations. For polar solvents (water, methanol, and acetonitrile) and benzene, strong to moderate catalytic effects for both reactions were found, whereas apolar and bulky cyclohexane interacts weakly with the solute and does not show pronounced barrier reduction. The calculated barrier heights for the Pyr+MeBr reaction in acetonitrile and cyclohexane are 23.2 and 28.1 kcal/mol compared with experimentally measured barriers of 22.5 and 27.6 kcal/mol, respectively. The solvent distributions change considerably between reactant and TS but comparatively little between TS and product conformations of the solute. As the system approaches the transition state, correlated solvent motions occur which destabilize the solvent-solvent interactions. This is required for the system to surmount the barrier. Finally, it is found that the average solvent-solvent interaction energies in the reactant, TS, and product state geometries are correlated with changes in the solvent structure around the solute.
Topics: Benzene; Methanol; Solutions; Solvents; Thermodynamics; Water
PubMed: 35196449
DOI: 10.1021/acs.jpcb.1c09710 -
Advances in Biochemical... 2022As an important building block in the chemical industry, methanol has become an attractive substrate in biorefinery owing to its abundance and low cost. With the...
As an important building block in the chemical industry, methanol has become an attractive substrate in biorefinery owing to its abundance and low cost. With the development of synthetic biology, metabolic engineering of non-methylotrophy to construct synthetic methylotrophy has drawn increased attention. As for the metabolic construction of methanol assimilation pathway in some industrial hosts, several artificial methanol assimilation pathways have recently been designed and constructed based on the computer-aided design. Particularly, these artificial methanol assimilation pathways possess advantages of shorter reaction steps, stronger driving forces, and independence on oxygen. Accordingly, this chapter reviewed strategies of constructing synthetic methylotrophs, including introducing methanol metabolic modules derived from natural methylotrophs and designing artificial methanol assimilation pathways. Future challenges and prospects were also discussed.
Topics: Metabolic Engineering; Methanol; Synthetic Biology
PubMed: 34545421
DOI: 10.1007/10_2021_176 -
Accounts of Chemical Research Nov 2022Reaction dynamics in the liquid-vapor interface is one of the crucial physical sciences but is still starving for in-depth exploration. It is challenging to selectively...
Reaction dynamics in the liquid-vapor interface is one of the crucial physical sciences but is still starving for in-depth exploration. It is challenging to selectively detect the interfacial species or the yields of chemical reaction therein, meanwhile shielding or reducing the interference from the vapor and liquid bulk. Mass spectrometry is a straightforward method but is also frustrated in such a selective detection. Using a liquid microjet in combination with a pulsed electron beam, a linear time-of-flight mass spectrometer, and a quadrupole mass filter, we recently innovated time-delayed mass spectrometry for investigations of the liquid-vapor interface. In this Account, we illustrate how this unique method succeeds in disentangling different sources, i.e., the vapor and liquid-vapor interface, of the ionic yields of the electron impacts with a liquid beam of alcohol in vacuum. These achievements are basically attributed to the application of an onion-peeling strategy in the ion detection. Concretely, the microsecond time scale of molecular volatilization can be resolved well by tuning the delay time between the nanosecond pulses of incident electron bunch and ion attractor. First, the specific orientation of the interfacial molecule, i.e., a well-known fact about the hydrophobic hydrocarbon groups pointing outside the liquid surface of alcohol, is validated again. More importantly, the dynamic features of time-delayed mass spectra, in particular, for the ionic yields from the liquid-vapor interface, are rationalized explicitly. Moreover, we demonstrate evidence of molecular dimers in the liquid-vapor interface of 1-propanol. As the first example of electron-induced reaction in the liquid-vapor interface, dimethyl ether can be synthesized in the liquid methanol interface due to local interfacial acidification by high-energy electron impacts. On the contrary, the low energy electron can lead to local basicity through dissociative electron attachment (DEA). Besides the primary low-energy electrons, the low-energy secondary and inelastically scattered electrons in the higher-energy impacts of the primary electrons can also participate in the DEA process. In contrast to the gas- or solid-phase DEAs, that in the liquid-vapor interface shows distinct differences in both the types and efficiencies of anionic products. With these and efforts in the future, we develop a molecular-level understanding of how the chemical reactions happen in the liquid-vapor interface.
Topics: Electrons; Ions; Methanol; Anions; Gases
PubMed: 36251270
DOI: 10.1021/acs.accounts.2c00428