Harnessing dimethyl ether and methyl formate fuels for direct electrochemical energy conversion

In this work,the oxidation of a mixture of dimethyl ether(DME) and methyl formate(MF) was studied in both an aqueous electrochemical cell and a vapor-fed polymer electrolyte membrane fuel cell(PEMFC)utilizing a multi-metallic alloy catalyst,Pt_(3)Pd_(3)Sn_(2)/C,discovered earlier by us.The current obtained during the bulk oxidation of a DME-saturated 1 M MF was higher than the summation of the currents provided by the two fuels separately,suggesting the cooperative effect of mixing these fuels.A significant increase in the anodic charge was realized during oxidative stripping of a pre-adsorbed DME+MF mixture as compared to DME or MF individually.This is ascribed to greater utilization of specific catalytic sites on account of the relatively lower adsorption energy of the dual-molecules than of the sum of the individual molecules as confirmed by the density fu nctional theory(DFT) calculations.Fuel cell polarization was also conducted using a Pt_(3)Pd_(3)Sn_(2)/C(anode) and Pt/C(cathode) catalysts-coated membrane(CCM).The enhanced surface coverage and active site utilization resulted in providing a higher peak power density by the DME+MF mixture-fed fuel cell(123 mW cm^(-2)at 0.45 V) than with DME(84mW cm^(-2)at 0.35 V) or MF(28 mW cm^(-2)at 0.2 V) at the same total anode hydrocarbon flow rate,temperature,and ambient pressure.

Promoting effect of chloride ions on selective oxidation of methanol to methyl formate over zirconia-supported ruthenium oxide catalysts

The effect of chloride ions on a monoclinic ZrO2-supported RuOx （RuOx/m-ZrO2） catalyst with a Ru surface density of 0.3 Ru/nm2 was studied in the selective oxidation of methanol to methyl formate （MF） at a low temperature of 373 K. The m-ZrO2 support was Cl-free, and Cl- ions were introduced into the RuOx/m-ZrO2 catalyst by impregnation with zirconium oxychloride or ammonium chloride and subsequent thermal treatment in air at 673 K. The structures of these catalysts were characterized by X-ray diffraction, Raman and X-ray photoelectron spectroscopies. Their reducibility was probed by temperature-programmed reduction in H2. The RuOx domains were present as highly dispersed Rut42- structure on m-ZrO2 with similar reducibility for the RuOx/m-ZrO2 samples irrespective of modification with or without Cl ions. Introduction of appropriate amounts of zirconium oxychloride into RuOx/m-ZrO2 led to a remarkable increase in the methanol oxidation rate and MF selectivity, whereas introduction of ammonium chloride or zirconyl nitrate significantly inhibited the catalytic performance of RuOx/m-ZrO2. The promoting effect of Cl- ions derived from zirconium oxychloride can be tentatively attributed to their roles in facilitating the adsorption of methanol and desorption of MF product or its intermediates. This finding provides novel insights into the promoting effect of Cl- ions on oxides-based catalysts for selective oxidation reactions.

Pd nanoparticles immobilized on MIL-53(Al)as highly e ective bifunctional catalysts for oxidation of liquid methanol to methyl formate

A series of Pd/MIL-53(Al) heterogeneous bifunctional catalysts with di erent Pd contents were prepared by an impregnation method. The prepared metal–organic frameworks MIL-53(Al) and catalysts were characterized by XRD, SEM, HRTEM,FT-IR and N2 adsorption/desorption techniques. The results showed that MIL-53(Al) was synthesized successfully, and the structure was unchanged during and after the preparation of the catalysts. The Pd nanoparticles(NPs) with an average particle size of 4.6 nm were uniformly dispersed on the MIL-53(Al). The catalyst exhibited good catalytic activity in the selective oxidation of liquid methanol to methyl formate. Under the conditions of 150 °C, 2 MPa O2 and solvent-free for5 h, the conversion of methanol could reach 60.3%, and the selectivity of methyl formate was up to 62.2%. In addition, the Pd/MIL-53(Al) bifunctional catalyst exhibited excellent stability and maintained high catalytic activity after five cycles.

Photopromoted methoxycarbonylation of olefin with methyl formate by Co(OAc)2

The photopromoted methoxycarbonylation of olefin with methyl formate catalyzed by Co（OAc）2 at ambient conditions has been carried out. The results indicated that the reaction activity increased with the increasing temperature. Methyl formate decomposed into CO and CH3OH firstly under irradiation, and then the methoxycarbonylation of olefin proceeded under catalysis of Co（OAc）2. The mechanism of methyl formate participating in the methoxycarbonylation is verified by the IR analysis and the labeling experiments of CDHOD and CH3^18OH.

Condensation reaction of formaldehyde and methyl formate catalyzed by a composite catalyst system

The condensation reaction of formaldehyde and methyl formate to form methyl glycolate and methyl methoxy acetate catalyzed by p-toluenesulfonic acid and different Lewis acid compounds has been investigated. The composite catalytic system consisting of p-toluenesulfonic acid and NiX2 （X = Cl, Br, I）, especially NiI2, exhibited a high catalytic performance for the condensation reaction, the total yield of MG and MMAc was up to 72.37%.

Catalytic Systems Containing p-Toluenesulfonic Acid for the Coupling Reaction of Formaldehyde and Methyl Formate

The coupling reaction of formaldehyde （FA） and methyl formate （MF） to form methyl glycolate （MG） and methyl methoxy acetate （MMAc）, catalyzed by p-toluenesulfonic acid （p-TsOH） as well as assisted by different kinds of solvents or Ni-containing compounds, had been investigated. The results showed that when the reaction was carried out at 140 ℃, with a molar ratio of FA to MF of 0.65 ： 1, molar fraction of p-TsOH to total feedstock of 11.0%, and reaction time of 3 h, the yield of MG and MMAc was 31.1% and 17.1%, respectively, p-TsOH catalyzed the coupling reaction by means of the synergistic catalysis of protonic acidity and soft basicity. Adding extra solvents to the reaction system was unfavorable for the reaction. The composite catalytic system consisting of p-TsOH and NiX2 （X=Cl, Br, I） exhibited a high catalytic performance for the coupling reaction, and NiX2 acted as a promoter in the reaction, whose promotion for the catalysis increased in the following order： NiCl2〈NiBr2〈NiI2. The present system is less corrosive when compared with the previous system, in which strong inorganic liquid acids were used as catalysts.

New methyl formate synthesis method:Coal to methyl formate

Methyl formate is one of the most important intermediates in C1 chemistry, which has been employed in a wide range of industrial applications. Current synthesis methods for methyl formate mainly include esterification of methanol and formic acid, liquid-phase methanol carbonylation, oxidative dehydrogenation of methanol, one-step syngas synthesis, and carbon dioxide hydrogenation and condensation with methanol, Liquid-phase methanol carbonylation is currently a main commercially viable process devel- oped by BASF Corp, for the industrial production of methyl formate. Recently, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences has developed a new synthesis method to con- vert coal to methyl formate （denoted as CTMF）, Different from the liquid-phase methanol carbonylation using homogeneous catalysts, CTMF method features with vapor-phase methanol carbonylation using het- erogeneous nanocatalysts, which can effectively utilize the coal-based syngas and produce value-added fine chemicals （i.e., methyl formate）. The newly developed method not only provides a new methyl for- mate synthesis technology but also contributes to the development of strategies for synthesizing valuable chemicals from coal. In this review, we firstly provide introduction on the development of existing methyl formate synthesis methods and then highlight the research progress of CTMF method. Finally, a perspec- tive on the future of CTMF is given,

Preparation of MIL-88B(Fe_(x),Co_(1‒x))catalysts and their application in one-step liquid-phase methanol oxidation to methyl formate using H_(2)O_(2)

The selective oxidation of methanol to methyl formate is one of the most attractive processes to obtain value-added methanol-downstream products.The development of highly efficient and stable catalysts is critical for this transformation.In this study,a series of MIL-88B(Fe_(x),Co_(1‒x))bimetallic catalysts with different Fe/Co molar ratios were prepared through a one-pot hydrothermal method.X-ray diffraction,scanning electron microscopy,high-resolution transmission electron microscopy,energy dispersive spectroscopy,Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy,N2 adsorption-desorption,and inductively coupled plasma-mass spectrometry characterization were performed to elucidate the structure of the catalysts.The activity of the catalysts were assessed in the one-step oxidation of methanol to methyl formate with H_(2)O_(2)in a liquid-phase batch reactor.The results show that the MIL-88B(Fe_(x),Co_(1‒x))catalysts exhibit uniform needle-like morphologies with an average length and width of 400-600 nm and 100-150 nm,respectively.Co^(2+)is incorporated into the framework by partially replacing Fe^(3+)in MIL-88B.Moreover,the catalyst efficiently promoted the conversion of methanol to methyl formate.When MIL-88B(Fe_(0.7),Co_(0.3))catalyst was used with a molar ratio of H_(2)O_(2)to methanol of 0.5 at 80℃for 60 min,34.8%methanol conversion was achieved,and the selectivity toward methyl formate was 67.6%.The catalysts also showed great stability with a steady conversion and selectivity even after four cycles.The preliminary oxidation mechanism was also studied.It was determined that H_(2)O_(2)is first adsorbed on the Fe^(3+)sites and subsequently activates these sites.Methanol is adsorbed by the O atoms of the framework through hydrogen bonding and is gradually oxidized to formic acid.Subsequently,formic acid reacts with the residual methanol at the Fe^(3+)and Co^(2+)Lewis acid sites to form methyl formate.

Catalytic Preparation of Methyl Formate from Methanol over Silver

A catalytic reaction over a silver catalyst performed in an unregarded temperature region（473-873 K） with a long catalytic lifetime for the production of methyl formate from methanol was provided as a potential preparing route. The optimal yield of methyl formate（ca. 14. 8% ） with a selectivity 〉90% was obtained at about 573 K. Because α- oxygen species and bulk oxygen species coexist in the unregarded temperature region, a synergistic process concerning α-oxygen species and bulk oxygen species was proved over Oα -rich and Oγ-rich samples.

Kinetics of Methanol Carbonylation to Methyl Formate Catalyzed by Sodium Methoxide

Kinetics of synthesis of methyl formate from carbon monoxide and methanol, using sodium methoxide as the catalyst and pyridine as the promoter in a batch reactor, was studied. Kinetic parameters such as the apparent reaction orders, the rate constant and the apparent activation energies were obtained. The experimental results showed that both the reaction orders with respect to CO and methanol equal to 1, the general reaction kinetic equation is (-r)=-dp(CO)/dt=k, p(CO).[MeOH], and the rate constant is k=8.82×10~6exp [-61.19×10~3/(R·T)] in the presence of pyridine. The apparent activation energies had decreased 6.44 kJ/mol and the rate constant had increased more than 1.5 times when pyridine was used as the promoter in the catalyst system.

Study of Catalysts on the Synthesis of Methyl Acrylate by Hydroesterification of Methyl Formate with Acetylene

The catalytic hydroesterification of methyl formate (MF) with acetylene to methyl acrylate (MA) over nickel-based catalysts prepared by impregnation has been comprehensively studied in a fixed bed reactor at 160 similar to 240 degrees C and under 4 similar to 6MPa GHSV: 630h(-1), CO:N-2:C2H2 = 65:28:7. In present work, we have found a catalyst of 11wt%NiO/Al2O3 (80 similar to 100 mesh) prepared by wet impregnation with NiCl2 aqueous solution, then calcined in air at 500 degrees C for 5 h. The selectivity to methyl acrylate and the conversion of methyl formate over 11wt%NiO/Al2O3 catalyst are higher than other catalysts studied in this paper. The optimum reaction temperature for the hydroesterification of methyl formate with acetylene to methyl acrylate is around 220 degrees C.

Simultaneous production and utilization of methanol for methyl formate synthesis in a looped heat exchanger reactor configuration

In this investigation, a novel thermally coupled reactor （TCR） containing methyl formate （MF） production in the endothermic side and methanol synthesis in the exothermic side has been investigated. The interesting feature of this TCR is that productive methanol in the exothermic side could be recycled and used as feed of endothermic side for MF synthesis. Other important advantages of the proposed system are high production rates of hydrogen and MF. The configuration consists of two thermally coupled concentric tubular reactors. In these coupled reactors, autothermal system is obtained within the reactor. A steady-state heterogeneous model is used for simulation of the coupled reactor. The proposed model has been utilized to compare the performance of TCR with the conventional methanol reactor （CMR）. Noticeable enhancement can be obtained in the performance of the reactors. The influence of operational parameters is studied on reactor performance. The results show that coupling of these reactions could be feasible and beneficial. Experimental proof-of-concept is required to validate the operation of the novel reactor.

Ordered mesoporous Cu-Ca-Zr:A superior catalyst for direct synthesis of methyl formate from syngas

It is still a big challenge to obtain both highly active and stable Cu-based catalysts for direct synthesis of methyl formate(MF)from syngas.To address the issue,we have designed and synthesized a series of ternary Cu-Ca-Zr catalysts,namely,the ordered mesoporous Cu-Ca-Zr catalyst prepared by one-pot evaporation-induced self-assembly(EISA)method,and the supported CuO/CaO-ZrO_(2)catalysts by impregnating with copper precursor or by immobilizing copper nanoparticles.In the latter two catalysts,the ordered mesoporous CaO-ZrO_(2)support was also prepared by the EISA method.The catalysts were characterized by techniques such as ICP,XRD,TEM,N2 isotherm adsorption-desorption,XPS and H2-TPR,and used for direct synthesis of MF.The results indicated that the catalyst prepared by onepot EISA method,in which the CuO species are highly dispersed in frame of CaO-ZrO_(2),exhibits much better activity and stability as compared with the other two catalysts with most of CuO located on the outer surface of the CaO-ZrO_(2)support,because the former has a higher specific surface area,enhanced synergistic effect and stronger interaction between the CaO-ZrO_(2)support and CuO active constituent.

Catalytic Oxidation of Dimethyl Ether to Hydrocarbons over SnO_2/MgO and SnO_2/CaO Catalysts

A novel reverse microemulsion method was used to prepare SnO2/MgO and SnO2/CaO catalysts. It was found that both the catalysts were active for the reaction of catalytic oxidation of dimethyl ether （DME） in the temperature range of 275 to 300 ℃. SnO2/CaO catalyst exhibits much higher activity than SnO2/MgO. On SnO2/CaO catalyst, DME conversion of 21.8% was obtained at 300℃, while selectivities to methyl formate （MF） and dimethoxyethane （DMET） of 19.1% and 59.0% respectively were obtained at 275 ℃.

Tiny pollutant emissions of a dimethyl ether fuelled engine

Emissions of dimethyl ether(DME) fuelled engines were investigated by orthogonal experiments on a ZS195 diesel engine.The study mainly focused on the tiny pollutant emissions of formaldehyde(CH2O),methyl formate(CH3OCHO) and formic acid(HCOOH).The presence of CH2O,CH3OCHO and HCOOH are proved in the exhaust by gas chromatograph and Fourier transform infrared spectroscopy.The analysis of variance results indicate that the fuel delivery advance angle is the most important factor for CH2O emission.The fuel delivery advance angle and the interaction of injection pressure and nozzle diameter are considerable factors for unburned hydrocarbon(UHC) emission.The mechanism forming tiny pollutants,primarily through CH2O formation,is suggested to be similar to the mechanism forming UHC by DME partial oxidation existing in crevices and boundary zones,and is verified via DME combustion simulation of a multizone chemical kinetic model.

Syntheses and Evaluations of CdS with Various Morphologies for Photocatalytically Reducing CO_2

A series of CdS with various shapes of microsphere, flower-like and leaf-like were templatefreely synthesized by a hydrothermal method. Powder X-ray diffraction（XRD）, Brunauer-Emmett-Teller（BET）, scanning electron microscopy（SEM） and UV-vis absorption spectroscopy（UV-vis） were applied to characterize the morphology, optical and other physical properties of the as-prepared CdS. An optical spectrum analyzer was used to measure the wavelength of the illuminant on the slurry in the activity evaluations of photocatalytic reduction of CO2 over CdS. Both sources of cadmium and sulfur had great impact on the CdS morphology as can be seen in the SEM images. By means of a series of activity evaluations, the microspheric CdS made from cadmium nitrate and thioacetamide showed better photocatalytic activity for the reduction of CO2 to methyl formate（MF） in methanol than the flower-like and leaf-like CdS catalysts.

Experimental and mechanistic understanding of photo-oxidation of methanol catalyzed by CuO/TiO2-spindle nanocomposite:Oxygen vacancy engineering

We report experimental and mechanistic understanding of methanol oxidation to produce methyl formate using CuO/Ti02-spindle composite as a promising photocatalyst under mild conditions with over 97%conversion and 83%selectivity.The catalysts are obtained via precise depositing of CuO nanoclusters(size:~3.5 nm)at the{101}facet of the TiO2 to optimally tune exciton recombination through oxygen vacancies generation,evidenced by photoluminescence and Raman spectroscopy measurements.The turnover frequency(TOF)and the apparent quantum efficiency(AQE)of the 7%CuO/TiO2-spindle composites reach up to 23.8 molmethanol·gcat^-1·h^-1 and 55.2%at 25℃,respectively,which are substantially higher than these previously reported photocatalysts.Further,the in-situ attenuated total reflection infrared spectroscopy analysis reveals that the methanol oxidation most likely takes place through the conversion of adsorbed methoxy(CH30^*)to formaldehyde(CHO^*)intermediate,a subject of major debate for a long time.The adsorbed formaldehyde(CHO^*)thus produced reacts with another CH30^*species in its close proximity to form the final product of methyl formate.Results of this study provide insights into the reaction mechanism,and offer guidelines to systematically develop and apply photocatalysts for methanol conversion and related reactions via surface engineering.