NH3-TPD Studies Research Articles

Non-thermal plasma-catalytic ammonia synthesis over alumina-supported iron catalyst: Insights into the effect of alumina calcination temperature

Non-thermal plasma-catalytic ammonia synthesis (NTPCAS) has been regarded as a promising route to store hydrogen by utilizing renewable electricity. Alumina is a suitable support of the catalysts in NTPCAS and its properties can influence the performance of catalysts remarkably. In this study, the influence of the alumina calcination temperatures (Tc) on the catalytic performance of Fe-Al-x (x represents the value of Tc) was analyzed in a dielectric barrier discharge (DBD) reactor for NTPCAS. The results suggested that an increase in Tc transforms the alumina crystalline from γ phase to α phase. The best performance with a synthesized ammonia concentration of 11833 ppm was achieved over Fe-Al-900 with coexisting γ and θ phases of alumina under N2: H2 = 1:1 and SEI = 37.05 kJ/L conditions, which was 37 % higher than that of Fe-Al-800 with only γ phase. In addition, the larger Tc (i.e. 1100 and 1200 °C) decreased the specific surface area, increased the mean catalyst particle size, and led to the non-uniform dispersion of Fe species. The NH3-TPD and XPS studies suggested that an increase in Tc could influence the surface acidity and oxygen vacancy concentration of Fe catalysts, which were crucial to adjusting the catalytic activity for NTPCAS. This study clarifies the value of a suitable design of support of catalysts for improving NTPCAS.

In situ synthesis NiO@TiO2/MXene as a promoter for ammonium perchlorate based solid propellants

The carrier can widely affect or even dominate the catalytic activity and selectivity of nanoparticles for ammonium perchlorate (AP). In this work, a novel catalyst NiO@TiO2/MXene (TN) nanocomposite was prepared by a simple hydrothermal method using two-dimensional MXene as the catalyst carrier. System characterization reveals that the utilization of MXene supports facilitates effective dispersion of NiO nanoparticles. TiO2/MXene itself exhibits commendable catalytic activity and possesses a substantial specific surface area, thereby enabling regulation of the catalytic performance of NiO. TN surpasses both NiO and TiO2/MXene in promoting the high temperature decomposition (HTD) of AP. By increasing the concentration of Ni2+ in the precursor, the loading capacity of NiO on the carrier is enhanced, consequently improving its catalytic capability towards AP. As the load of NiO increases, there is a decrease in high decomposition temperature (THTD) from 437.3 ℃ to 313.3 ℃, a reduction in activation energy (Ea) from 216.1kJ/mol to 114.6 kJ/mol, and an increase in heat release by 118 %. NH3-TPD and O2-TPD studies have shown that catalysts with strong surface adsorption capacity for NH3 and O2 exhibit excellent catalytic performance, leading to differences in their catalytic behavior. TG/FT-IR analysis further confirms that TN nanocomposites accelerate N2O conversion to NO, which contributes to rapid AP decomposition.

Conversion of fly-ash into pristine ZSM-5 and its application for methane dehydroaromatization reaction

Increasing Fly-Ash (FA) residues as a by-product in pulp/paper industries requires efficient routes for green and economical ash management. Converting FA into zeolite shows great potential for its efficient utilization. In this work, FA received from Indian paper mills was converted into pristine ZSM-5, support in methane dehydroaromatization (MDA). Following acid leaching, Fe and Al content were reduced to make ash residue, a precursor for ZSM-5 synthesis. Synthesized FA-derived ZSM-5 consisted of a highly crystalline structure (91 %) and high BET surface area (468 m2/g) comparable to commercial ZSM-5. Synthesized ZSM-5 (FA) possessed micropores/mesopores, with comparatively smaller particle size as confirmed by pore size distribution analysis/N2-sorption isotherms and SEM analysis. NH3-TPD study confirmed the acidity content (1.16 mmol/gcat) over ZSM-5 (FA) and was found to be compatible with that of commercial ZSM-5 (1.58 mmol/gcat). Further, the activity of ZSM-5 (FA) with 5 wt% Mo loading was evaluated towards MDA reaction and compared its activity with conventional Mo/HZSM-5. Higher activity was achieved with 5Mo/HZSM-5 (FA-derived) exhibiting a higher benzene production rate than the 5Mo/HZSM-5 due to effective textural properties and suitable acidity, which provides sites for dispersion of MoOx species in case of Mo/ZSM-5 (FA) thereby conferring improved activity.

Importance of the Nature of Acidic Sites of Different Aluminosilicates on Fixation of Carbon Dioxide with Styrene Oxide.

The nature of acidic sites in commercially available aluminosilicates, zeolite Na-Y, zeolite NH4 + -ZSM-5, and as-synthesized Al-MCM-41 have been investigated by employing them as catalysts for capturing CO2 by styrene oxide. The catalysts, in tandem with tetrabutylammonium bromide (TBAB), produce styrene carbonate, and the yield of the product is observed to be governed by the acidity of the catalysts and hence, the Si/Al ratio. All these aluminosilicate frameworks have been characterized by IR, BET, TGA, and XRD. XPS, NH3 -TPD, and 29 Si solid-state NMR studies have been carried out to analyze the Si/Al ratio and the acidity of these catalysts. According to TPD studies, the number of weak acidic sites of these materials follow an order as NH4 + -ZSM-5 < Al-MCM-41 < zeolite Na-Y, which is just in accordance with their Si/Al ratios and the yield of the cyclic carbonates obtained, i. e., 55.3 %, 68 %, and 75.4 % respectively. The TPD data and the yield of the product carried out with calcined zeolite Na-Y indicate that not only the weak acidic sites but also the role of strong acidic sites might appear crucial in the cycloaddition reaction.

Vapour Phase Synthesis of 2-Methylpyridine and 4-Methylpyridine Over Potassium Salts of 12-Tungstophosphoric Acid

Vapor phase dehydrocyclization reaction of acetaldehyde and ammonia was investigated over K salts of 12-tungstophosphoric acid as catalysts in a continuous flow fixed bed reactor at 350–450℃. The yield of 2-methylpyridine and 4-methylpyridine were found to be in the range of 38.0–64.5%. The 2-methylpyridine and 4-methylpyridine are used for the preparation of insecticides, poultry drugs, cattle drugs and anti-tuberculosis drugs, veterinary analgesics etc. respectively. The reaction conditions such as temperature, contact time, and molar ratio for achieving optimal yield with respect to 2-methylpyridine and 4-methylpyridine were discussed. Catalysts were characterized through BET surface area, FT-IR, XRD and TGA. NH3-TPD studies exhibit the moderate acidity. The morphology of the catalysts was also studied by FESEM.

Efficient Bifunctional Catalysts for Enhanced Carbon Conversions and Alky-Aromatics Production in Crude Bio-glycerol Methanol Processes

The present study reports the development of an alkali earth metal (Ba)-modified Zn/ZSM-5 catalyst for efficient carbon conversion of bio-derived crude glycerol toward aromatics production in a methanol (GMTA) co-process. The metal functionality caused considerable alteration in acidity to improve the dehydrogenation properties of the catalyst to produce more aromatics and to simultaneously control the undesired cracking reactions responsible for the gas product formation. The methanol concentration in the feed mixture was also observed to influence the carbon conversions toward liquid and gas products, especially aromatics. At optimized reaction conditions, the 0.1Ba-1Zn/ZSM-5 catalyst produced 69C% high-value gasoline blending stock possessing ∼57C% aromatics and ∼116 research octane number suitable for fuel applications. The aromatics formation was accompanied by 28 mol % of H2 as a valuable byproduct. XRD, FT-IR, and 27Al-NMR studies confirmed the structural integrity of ZSM-5 even after metal loading treatments. XPS and UV–Vis DRS spectra confirmed the presence of Zn in the form of (ZnOH)+ species. NH3-TPD and pyridine-IR studies revealed a decrease in the strong acidity of ZSM-5 along with a simultaneous increase in Lewis acidity. Thus, the enhanced carbon conversion and aromatics yield in the GMTA process observed on 0.1Ba-1Zn/ZSM-5 might be understood by two main factors, namely, (i) decreased strong Bronsted acid sites to suppress undesirable cracking reactions and (ii) increased Lewis acid sites to promote dehydrogenation reactions.

β-Si4Al2O2N6 supported Ni catalyst for enhanced ethanol steam reforming: Tuning metal-support interaction by high-temperature solution of Si3N4 with Al2O3

Developing a high-performance Ni-based catalyst for ethanol steam reforming (ESR) reaction is desirable for sustainable hydrogen production. In this work, β-Si4Al2O2N6, the high-temperature solid solution of Si3N4 and Al2O3, was utilized as support to fabricate Ni catalyst (Ni/Si4Al2O2N6) for ESR reaction to enhance hydrogen-production efficiency. The catalytic experiments demonstrated that Ni/Si4Al2O2N6 catalyst exhibited higher C–C bond cleavage capacity, hydrogen-production efficiency, catalytic durability and better anti-coke performance as compared with Ni/Si3N4 and Ni/Al2O3 catalysts. H2-TPR, XPS and NH3-TPD studies revealed that the stronger metal-support interaction (MSI) in Ni/Si4Al2O2N6 catalysts induced more distinct charge transfer from Ni species to Si4Al2O2N6 support, fabricating Ni active sites with higher oxidation state and achieving higher catalytic activity and durability for ESR reaction.

Highly efficient removal of tetracycline hydrochloride under neutral conditions by visible photo-Fenton process using novel MnFe2O4/diatomite composite

A simple solvothermal method was used to prepare poly-porous MnFe2O4/diatomite (MFD) with excellent catalytic performance. The characteristics of the prepared catalysts were examined by XRD, SEM, BET, XPS, UV-DRS, PL and NH3-TPD. BET analysis indicated that introduction of diatomite could increase the specific surface and porosity of the MFD. NH3-TPD studies clearly revealed that loading onto diatomite increased the availability of acid sites and surface hydroxyl groups in the composite materials. Under the combination of visible light and H2O2, the degradation effect of 80 mg/L 100 mL tetracycline hydrochloride (TC-HCl) reached 96.7% within 60 min at 0.1 g/L MFD and initial pH value, according to the experimental results. The proposed heterogeneous photo-Fenton system with MnFe2O4/diatomite showed an extremely wide pH range of 3–11 for TC-HCl degradation. At pH = 7, 91.8% of the TC-HCl (80 mg/L 100 mL) could be degraded within 60 min. In addition, the removal rate remained close to 90% after 60 min of irradiation at pH = 9 and 11. Free radical capture experiment showed that superoxide radicals (•O2−) and holes (h+) play a crucial role in the removal of TC-HCl. Moreover, the synergistic activation of H2O2 by Fe and Mn was confirmed to promote the degradation, leading to higher TC-HCl removal efficiency.

Performance of geopolymer as adsorbent on desulphurization of heavy gas oil

AbstractGeopolymer is a porous aluminosilicate material and chemically similar to zeolites. As a low‐cost construction material, its suitability for adsorptive desulphurization (ADS) was studied using a petroleum feedstock. Geopolymer was produced by alkali activation of metakaolin and characterized by BET, NH3–TPD, SEM, FTIR, XRD, and XPS. The XRD and SEM studies evidenced the amorphous nature of geopolymer and the existence of macro‐ and mesopores. The XPS and NH3–TPD studies revealed the presence of surface Na and Al, and strong acid sites, respectively, in the prepared geopolymer. These sites interact with sulphur compounds of heavy gas oil through π‐π and acid–base interactions. The geopolymer showed a high sulphur adsorption capacity of 38.4 mg/g. The effects of adsorption parameters such as operating temperature, amount of adsorbent, and time for absorption on the adsorption capacity were examined using the Box–Behnken design statistical model. All three operating parameters significantly influenced the sulphur adsorption capacity of geopolymer. The adsorption of sulphur compounds on the geopolymer followed pseudo‐first‐order kinetics and did not affect its structural stability. Finally, the thermodynamic study revealed that adsorption of sulphur compounds on the geopolymer was spontaneous and exothermic.

Acetalization of glycerol and benzaldehyde to synthesize biofuel additives using SO42-/CeO2–ZrO2 catalyst

Synthesis of 1,3- dioxane and 1,3-dioxolane, using sulfated CeO2–ZrO2 catalyst for acetalization of glycerol with benzaldehyde, is the focus of present work. SO42-/CeO2–ZrO2 catalyst was synthesized using combustion method. Experiments were carried out to analyze the effect of various solvents (n-hexane, toluene, tert-butyl alcohol, pentanol), molar ratios (1:3, 1:5, 1:7), catalyst loadings (3 wt%, 5 wt%, 9 wt %) and temperatures (80 °C, 90 °C, 100 °C) on glycerol conversion and selectivity of the products. Selectivity of 87.20% dioxolane and 12.80% dioxane was obtained at molar ratio of 1:3, 9 wt% catalyst loading and temperature of 100 °C.Strong NH3 desorption peak from NH3-TPD study indicated the high acidic strength of sulphated catalyst. Strong surface acidity and surface porosity (observed from TEM and SEM analysis) contributed to an enhanced activity of the catalyst for glycerol acetalization reaction. The kinetics of the reaction was studied using an elementary kinetic law. A correlation coefficient of 0.98 from the selected kinetic model proved that the rate of acetalization reaction was dependent on glycerol concentration and acetal formation was instantaneous. The study demonstrated the application of an environmentally benign, inexpensive, thermally stable, active SO42-/CeO2–ZrO2 catalyst for glycerol acetalization reaction to synthesize 1,3-dioxolane as the desired product.

Selective hydrodeoxygenation of 5-hydroxymethylfurfural to 2, 5-dimethylfuran over mesoporous silica supported copper catalysts

Selective catalytic hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) to prepare 2, 5-dimethylfuran (DMF) was studied as this product is a good biofuel. A sequence of copper dispersed on SBA-15 catalysts are designed and tested their activity for HMF hydrodeoxygenation reaction. The physico-chemical characteristics of the catalysts are gained from powder XRD, TEM, N2-adsorption desorption, NH3-TPD, H2-TPR and N2O-chemisorptions studies. Characterization results indicate the fine dispersion of Cu metal on SBA-15 with high surface area and appropriate acidic sites. The catalyst with 15%Cu on SBA-15 showed high activity towards DMF with 90% yield. The optimized reaction conditions were 180 °C of reaction temperature, 20 bar H2 pressure, and a reaction time of 8 h to achieve maximum yield. The catalyst is recyclable and exhibits consistent activity.

Creating Brønsted acidity at the SiO2-Nb2O5 interface

Catalytically active acid sites associated with the silica-niobia interface were probed with a series of overcoated SiO2 on Nb2O5 (SiO2/Nb2O5) mixed oxide materials prepared by deposition of tetraethyl orthosilicate onto niobic acid (Nb2O5·nH2O) or calcined niobia (Nb2O5). NH3 TPD and pyridine DRIFTS studies indicated that the speciation of acid sites in the materials evolved as a function of SiO2 loading, impacting the quantity and stability of Brønsted sites. Catalyst activity was highly dependent on SiO2 loading in the liquid phase hydroalkoxylation of dihydropyran with n-octanol. At SiO2 surface densities corresponding to approximately 1 Si per 2 surface Nb, the activity of these catalysts passed through a maximum approximately 20 times higher than the activity of calcined Nb2O5. Apparent reaction barriers measured over the most active SiO2/Nb2O5 catalysts were 10 kJ/mol lower than those measured over niobic acid, suggesting that the OH features unique to the SiO2-Nb2O5 interface were slightly more reactive than those on niobic acid.

Synthesis of less acidic VO-salen complex grafted onto graphene oxide via functionalization of surface carboxyl groups for the selective oxidation of norbornene

Oxidation of norbornene was carried out over oxovanadium Schiff base complex grafted on –OH and –COOH modified graphene oxide (GO) as heterogeneous catalysts using 30% H2O2 as an oxidant and ethylene glycol as a solvent. Amongst them, the carboxylic acid group modified GO was found to be better for this transformation. The lower conversion with –OH modified catalyst was ascribed to the higher acidic nature of the catalyst. NH3-TPD study confirmed the less acidic sites on the –COOH modified catalyst and this less acidic nature and controlled addition of 30% H2O2 became the centre of action for this catalytic transformation. Absolute conversion of norbornene (100%) with 98.8% 2,3-epoxy norbornane was achieved at 60 °C in 1 h. This catalyst was recycled four times without significant loss of activity. This durability of the catalyst was believed to be due to strong π–π stacking interaction of GO sheet and an unsaturated ring of ligand and cyclic structure of ligand which protect the metal to leach out.

Synthesis of 2,2,4-trimethyl-1,2-dihydroquinolines over metal-modified 12-tungstophosphoric acid-supported γ-Al2O3 catalyst

In spite of having significant pharmacological importance, scalable synthesis of 2,2,4-trimethyl-1,2-H-dihydroquinoline (TMQ) is always being cumbersome due to harmful solvents, drastic reaction conditions, and high recovery cost of homogeneous catalysts. Heterogeneous catalytic condensation of aniline with acetone was employed here to synthesize TMQ. As efficient materials, Zn2+-, Sn2+-, and Cu2+-exchanged tungstophosphoric acid (TPA) supported on γ-Al2O3 was synthesized by microwave-assisted hydrothermal method. The synthesized catalysts were thoroughly characterized by XRD, Raman, FE-SEM, etc. and were screened for condensation reaction. Among the metal-exchanged catalysts, Zn0.5TPA/Al2O3 showed highest aniline conversion with the highest yield of TMQ up to three consecutive cycles. The acidic sites over the catalysts were probed by pyridine-adsorbed FT-IR spectra and NH3-TPD studies. The reaction conditions were optimized, and plausible reaction mechanistic pathway was derived from FT-IR and GC–MS data.

Bifunctional rice husk-derived SiO2-Cu-Al-Mg nanohybrid catalyst for one-pot conversion of biomass-derived furfural to furfuryl acetate

Developing one-pot reaction methodologies, which typically require multifunctional catalyst systems, is crucial for sustainable production of bio-derived fuels and chemicals. This work reports one-pot hydrogenation-esterification of furfural to furfuryl acetate using a bifunctional metal-based nanohybrid catalyst, composed of rice husk (RH) derived SiO2, Cu, Al, and Mg species (RHSiO2-Cu-Al-Mg). For comparison, the catalytic efficiency of RHSiO2-Cu and RHSiO2-Cu-Al were tested under similar reaction conditions. Various analytical techniques were used to elucidate the physicochemical, textural, and acid-redox properties of the catalysts. It was found that the RHSiO2-Cu-Al-Mg catalyst contains an optimum amount of acid and redox sites, as illustrated by NH3-TPD and H2-TPR studies, respectively. Especially, Mg addition played a vital role in tailoring acidity of the RHSiO2-Cu-Al catalyst to promote in-situ esterification of furfuryl alcohol with acetic acid to yield furfuryl acetate. As a result, the RHSiO2-Cu-Al-Mg catalyst exhibited the best performance in one-pot conversion of furfural to furfuryl acetate, outperforming various noble metal/silica based catalysts. This study offers potential opportunities for the rational design of novel, bifunctional heterogeneous catalysts for efficient production of bio-derived fuels and value added chemicals.

Fischer-Tropsch synthesis: Synergistic effect of hybrid Pt-Cd additives on a 15%Co/Al2O3 catalyst

The study investigated a synergistic effect of the hybrid Pt-Cd additives on a cobalt catalyst. Adding 1%Cd to 0.5%Pt-15%Co/Al2O3 led to 90% activity loss and significantly increased CH4 and CO2 selectivities. HR-TEM/STEM micrographs revealed that a fraction of Cd nanoparticles deposited on large Co particles, resulting in the severe deactivation. More interestingly, the hybrid Cd-Pt additives were found to have a synergistic effect on the secondary reactions of 1-olefins; each modifier counteracted the other individual additive's role for the formation of olefins. For example, Cd suppressed the 1-olefin hydrogenation ability of Pt and Pt suppressed the 1-olefin isomerization ability of Cd. The XPS, TEM and NH3-TPD studies revealed that the Pt-Cd dual additives provided unique electronic effect (e.g., Pt and Cd enhanced electronic backdonation and Pt blocked electron transfer), which improved 1-olefin selectivity and suppressed 2-olefin selectivity of the cobalt catalyst.

Cobalt-doped magnesium fluoride as a support for platinum catalysts: The correlation of surface acidity with hydrogenation activity

The binary Mg-Co fluorides have been employed for the first time as platinum catalyst supports and tested for o-chloronitrobenzene hydrogenation in batch, flow and aqueous-phase reforming conditions. Isomorphous substitution of Co2+ cations for Mg2+ ones in the tetragonal structure of MgF2 was verified by XRD analysis. The DFT calculations showed a decrease in the strength of surface Lewis acid centers with increasing cobalt content in the binary fluorides and were confirmed by NH3-TPD and Py-FTIR studies. The activity of Pt/MgCoF catalysts for o-chloronitrobenzene hydrogenation correlates with Lewis acidity and the amount of chemisorbed nitrobenzene. The latter forms on the catalyst surface adsorbed species not described in the literature yet. The mode of chloronitrobenzene adsorption on platinum-support boundary centers via electron-deficient Mg2+ and electron-rich platinum centers has been proposed. It has been found that the application of in-situ generated hydrogen from APR of methanol makes it possible to obtain o-chloroaniline with 100% selectivity.

Catalytic Transfer of Fructose to 5-Hydroxymethylfurfural over Bimetal Oxide Catalysts

Direct conversion of fructose into 5-hydroxymethylfurfural (HMF) is achieved by using modified aluminum-molybdenum mixed oxide (S-AlMo) as solid acid catalysts. The synthesized catalyst was characterized by powder XRD, nitrogen adsorption-desorption isotherm, NH3-TPD, and SEM. As a result, the presence of strong acidity, mesostructures, and high surface area in the S-AlMo catalyst was confirmed by nitrogen adsorption-desorption isotherm and NH3-TPD studies. A study by optimizing the reaction conditions such as catalyst dosage, reaction temperature, and time has been performed. Under the optimal reaction conditions, HMF was obtained in a high yield of 49.8% by the dehydration of fructose. Moreover, the generality of the catalyst is also demonstrated by glucose and sucrose with moderate yields to HMF (24.9% from glucose; 27.6% from sucrose) again under mild conditions. After the reaction, the S-AlMo catalyst can be easily recovered and reused four times without significant loss of its catalytic activity.

Partial Oxidation of Propylene over as Prepared and Acid Enriched Bi2Mo1-xWxO6 System

The compounds Bi2Mo1-xWxO6 (x = 0.0, 0.2, and 0.4) were obtained through a Citrate sol-gel process. Thermogravimetric differential thermal analysis (TG-DTA), X-ray diffraction (XRD), Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) techniques were used for characterization. Reitveld refinement of the XRD data confirmed the crystal structure of all the compositions to be orthorhombic, having Pca21 space group. XPS studies indicated the presence of +6 as well as +4 oxidation state for Mo. Surface acid enrichment of all the catalysts was done and monitored by NH3-TPD studies. Partial oxidation of propylene was studied over all the compounds. The W doping was found to increase the catalytic activity. Moreover, as-prepared catalysts and acid enriched catalysts were compared for their catalytic activity wherein, acid-enriched catalysts showed the improved conversion of propylene without hampering the product selectivity profile.

Eliminating reverse water gas shift reaction in CO2 hydrogenation to primary oxygenates over MFI-type zeolite supported Cu/ZnO nanocatalysts

This study reports the synthesis of Cu/ZnO supported on Al2O3, SiO2, ZrO2 and solid acid catalyst ZSM-5 for the hydrogenation of CO2 to methanol (MeOH). The activity of all the supported catalysts except Cu/ZnO supported on ZSM-5 (CZZSM) tested at 250°C and 2.25MPa for 13h time-on-stream (TOS) showed carbon monoxide as byproduct due to the nefarious reverse water gas shift reaction (RWGS) that typically compete with MeOH production during CO2 hydrogenation. Methyl formate and dimethyl ether which are value added specialty chemicals were the byproducts when CZZSM was tested and their production mechanism was ascribed to the acidity of the ZSM-5 support. According to the NH3-TPD and CO2-TPD studies, CZZSM has considerable acidity of 15.02μmol/m2 which is about 20 folds higher than the 0.74μmol/m2 measured for the basic sites. Furthermore, the extreme high resolution scanning electron microscopy (XHR-SEM) and BET results showed that the ZSM-5 framework, structural and textural properties were retained after the synthesis of CZZSM which showed that the synthesis protocol was expedient. Thus, the effect of the solid acid catalyst was easily evaluated. In addition, the XHR-SEM, TEM and XRD results showed that the Co-oxide particles were highly dispersed nano-particle with average size of 2.4nm. The CZZSM achieved and impressive CO2 conversion of 20.25% with average space-time yield of 60 and 16gproductgcat−1min−1, and selectivity of 77.70% and 10.0% for MeOH and MeF, respectively which are promising for industrial application.