Bifunctional Heterogeneous Catalyst Research Articles

Avoiding Sabatier’s conflict in bifunctional heterogeneous catalysts for the WGS reaction

Summary A new strategy for designing efficient bifunctional heterogeneous catalysts for the water-gas-shift (WGS) reaction (CO + H2O → CO2 + H2) is presented. We avoid conflicting tasks that require ∗OH or ∗O from dissociated water to adsorb on and then desorb from the substrate of a catalyst. Instead, the CO on metal directly obtains OH from water that is connected by weak hydrogen bonds to the substrate. The task of the substrate is to efficiently channel ∗H on its surface and release them as H2 gas. Experimental and theoretical results show that bifunctional catalysts with weakly reactive substrates have significantly higher CO conversion rates compared with highly reactive substrates that follow either the LH-associative or LH-redox process.

Phosphotungstic acid-modified zeolite imidazolate framework (ZIF-67) as an acid-base bifunctional heterogeneous catalyst for biodiesel production from microalgal lipids

To provide more acid-base active sites for catalyzing esterification and transesterification, a novel bifunctional heterogeneous catalyst was synthesized by modifying ZIF-67 with phosphotungstic acid (HPW) for biodiesel production. The proportion of coordinated Co-N bonds in ZIF-67 decreased from 32.4% to 21.7%, because they were destroyed by HPW to form coordinatively unsaturated Co cations and N− extremities of imidazolate ligands. Then terminal W = O groups in HPW interacted with N− extremities in ZIF-67 via covalent W-O-N bonds, which strengthened catalysts recyclability. The released coordinatively unsaturated Co cations and N− extremities enhanced Lewis acid-base properties of catalysts, facilitating conversion of microalgal lipids to fatty acid methyl ester. The ratio of Lewis acid sites to Brønsted acid sites increased from 0.1 to 0.66 and Lewis base sites increased from 0.45 to 4.53 mmol/g. The conversion efficiency of 98.5% over optimum HPW-modified ZIF-67 (weight ratio = 0.25) was higher than that of 72.7% over pure ZIF67 catalyst.

Highly efficient and selective one-pot tandem imine synthesis via amine-alcohol cross-coupling reaction catalysed by chromium-based MIL-101 supported Au nanoparticles

One-pot tandem synthesis of imines from alcohols and amines is regarded as an effective, economic and green approach under mild conditions. In this work, Au nanoparticles (NPs) dispersed on MIL-101 (Au/MIL-101) were demonstrated as highly active and selective bifunctional heterogeneous catalyst for production of various imine derivatives with excellent yields, via amine-alcohol cross-coupling reaction at 343 K in an open flask under an Ar atmosphere. Various physicochemical techniques, including inductively coupled plasma optical emission spectroscopy (ICP-OES), powder X-ray diffraction (P-XRD), X-ray photoelectron spectroscopy (XPS) transmission electron microscopy (TEM) and N2 adsorption-desorption, were used to characterize of the Au/MIL-101 catalyst. The obtained bifunctional catalyst is highly active and selective towards one-pot imine formation and exhibited the highest TOF (30.15-51.47 h−1) among all the ever-reported MOF-supported Au catalysts. The reaction mechanism of the imine formation from alcohol and amine over Au/MIL-101 catalyst was proposed. Mechanism experiment results demonstrate that Au NPs highly effective in activating oxidation of benzyl alcohol to benzaldehyde while the Lewis acid sites on MIL-101 catalyzed the second condensation step without interfering with the oxidation step. As a result, the excellent catalytic performance of Au/MIL-101 can be ascribed to the synergistic effect between Au NPs with Lewis acid sites in MIL-101.

One-pot Synthesis of Acetals by Tandem Hydroformylation-acetalization of Olefins Using Heterogeneous Supported Catalysts

A green route for one−pot synthesis of acetals by tandem hydroformylation−acetalization of olefins using supported Rh−based catalysts was developed. Experimental results demonstrated that suitable Rh loading (1 wt%) with appropriate reaction temperature (120 °C) and reaction time (8 h) were favorable for the formation of acetals, and a high acetals selectivity of 94.6% was achieved. More importantly, the selectivity to valuable linear products was enhanced in this tandem catalysis. Based on the catalytic mechanism study, highly dispersed RhOx nanoparticles and abundant acid sites on the supports were responsible for the hydroformylation and acetalization, respectively. One-pot synthesis of acetals directly from olefins with high selectivity was achieved over heterogeneous bifunctional catalysts via tandem hydroformylation-acetalization.

Homogeneous and heterogeneous catalysts for hydrogenation of CO2 to methanol under mild conditions.

In the context of a carbon neutral economy, catalytic CO2 hydrogenation to methanol is one crucial technology for CO2 mitigation providing solutions for manufacturing future fuels, chemicals, and materials. However, most of the presently known catalyst systems are used at temperatures over 220 °C, which limits the theoretical yield of methanol production due to the exothermic nature of this transformation. In this review, we summarize state-of-the-art catalysts, focusing on the rationales behind, for CO2 hydrogenation to methanol at temperatures lower than 170 °C. Both hydrogenation with homogeneous and heterogeneous catalysts is covered. Typically, additives (alcohols, amines or aminoalcohols) are used to transform CO2 into intermediates, which can further be reduced into methanol. In the first part, molecular catalysts are discussed, organized into: (1) monofunctional, (2) M/NH bifunctional, and (3) aromatization-dearomatization bifunctional molecular catalysts. In the second part, heterogeneous catalysts are elaborated, organized into: (1) metal/metal or metal/support, (2) active-site/N or active-site/OH bifunctional heterogeneous catalysts, and (3) cooperation of catalysts and additives in a tandem process via crucial intermediates. Although many insights have been gained in this transformation, in particular for molecular catalysts, the mechanisms in the presence of heterogeneous catalysts remain descriptive and insights unclear.

Bifunctional Catalysts Containing Zn(II) and Imidazolium Salt Ionic Liquids for Chemical Fixation of Carbon Dioxide.

Zn(II) can efficiently promote the catalytic performance of imidazolium salt ionic liquids (imi-ILs) for the chemical fixation of CO2 into epoxides. To obtain sustainability, immobilized bifunctional catalysts containing both imi-ILs and Zn(II) were prepared using bimodal mesoporous silica (BMMs) as carrier, through grafting of Zn(OAc)2 and 1-(trimethoxysilyl)propyl-3-methylimidazolium chloride (Si-imi) separately in the nanopores. The catalysts, named as BMMs-Zn&ILs, were identified as efficient catalysts for cycloaddition reaction of CO2 into epoxides under solvent-free conditions. BMMs-Zn&ILs showed good catalytic activity, which increased with the increase of the molar ratio of Zn(II) to Si-imi. As a comparison, different catalytic systems including homogeneous imi-IL, BMMs-ILs and BMMs-Zn were studied to demonstrate different cooperation behaviors. Furthermore, the kinetics studies of homogeneous and heterogeneous bifunctional catalysts were employed to confirm the differences, as well as to support the proposed cooperative catalysis mechanism in the nanopores.

Liquid-phase synthesis of methyl isobutyl ketone over bifunctional heterogeneous catalysts comprising cross-linked perfluorinated sulfonic acid Aquivion polymers and supported Pd nanoparticles

The solvent-free hydrogenation reaction of acetone over bifunctional heterogeneous catalysts, comprising cross-linked perfluorosulfonic acid (PFSA) resins and supported Pd nanoparticles, was investigated in the liquid phase under batch conditions. A systematic study was performed by analyzing separately the effect of the main reaction parameters on the reaction outputs. Acetone conversion, selectivity and productivity to methyl isobutyl ketone (MIBK) were measured as a function of the reaction temperature, the amount of catalyst, the Pd loading, the H2 pressure, the reaction time and the cross-linkage of the polymeric support. Reproducible trends were observed that could be explained in terms of properties of the catalyst, conversion path and kinetics. Best compromise results between selectivity (92 %) and productivity (37.0 mmolMIBK gcat−1 h-1) at 19.7 % acetone conversion were obtained for the 0.26Pd@X-link-08-PW79 catalyst, based on 0.8 % cross-linked PFSA support and 0.26 % wt Pd content.

Polyoxometalate-Based Metal-Organic Frameworks with Unique High-Nuclearity Water Clusters.

The maximum exposure of polyoxometalates (POMs) is of great significance to enhance the catalytic performance of HKUST-1 with incorporated Keggin-type POMs. Herein, two phosphovanadomolybdates were encapsulated into the HKUST-1 via a hydrothermal method to obtain two polyoxometalate-based metal-organic frameworks, formulated as [Cu12(BTC)8(H2O)12][H4PMo11VO40]@(H2O)30 (1) and [Cu12(BTC)8(H2O)12][H5PMo10V2O40]@(H2O)49 (2). Single-crystal X-ray diffraction analysis indicates that two compounds contain unique high-nuclearity water clusters without organic counter cations. The octahedral-shaped water cluster (H2O)30 was constructed from square-pyramid-shaped (H2O)5 for compound 1, while the huge cage-shaped water cluster (H2O)49 of compound 2 consisted of crown-like (H2O)8 and one water molecule, which substitute the organic counter cations involved in the structural construction. More importantly, after removing the water clusters via simple heat treatment, the active sites of the two compounds were fully exposed, leading to good catalytic activities for both benzene hydroxylation reaction and oxidative desulfurization. Furthermore, the catalytic test confirmed that compound 2 may be a bifunctional heterogeneous catalyst with great promise for both benzene hydroxylation and oxidative desulfurization.

Synthesis of biaryl compounds via Suzuki homocoupling reactions catalyzed by metal organic frameworks encapsulated with palladium nanoparticles

Heterogeneous homocoupling reactions of phenylboronic acids were greatly accelerated via Suzuki homocoupling reactions. In this work, a tandem route was designed which firstly one part of phenylboronic acids reacted with iodine to form iodobenzenes, then another part of phenylboronic acids coupled with iodobenzenes to produce biaryl compounds. The tandem reaction were catalyzed by a bifunctional heterogeneous catalyst of metal organic frameworks encapsulated with palladium nanoparticles (Pd@MOFs). This strategy for forming symmetric C-C bond between benzene rings has obvious advantages such as high efficiency, easy separation, good recyclability and no addition of toxic halogenated benzene.

Highly Robust 3s-3d {CaZn}-Organic Framework for Excellent Catalytic Performance on Chemical Fixation of CO2 and Knoevenagel Condensation Reaction.

In terms of ligand-directed synthetic strategy, multifunctional metal-organic frameworks (MOFs) could be assembled by employing organic ligands with nitrogen-containing heterocycles, which could serve as Lewis base sites in crystallized porous frameworks. Here, the acidic one-pot hydrothermal reaction of CaCl2, Zn(NO3)2, and 2,4,6-tri(2,4-dicarboxyphenyl)pyridine (H6TDP) generates one robust honeycomb-shaped double-walled material of {[(CH3)2NH2]2[CaZn(TDP)(H2O)]·3DMF·3H2O}n (NUC-21), which has the excellent physicochemical characteristics of nanoscopic channels, high porosity (58.3%), large specific surface area, and high heat/water-resisting property. To the best of our knowledge, this is the first 3s-3d dinuclear [CaZn(CO2)6(OH2)]-based nanoporous host framework, whose activated state possesses the coexistence of Lewis acid-base sites including four-coordinated Zn2+ ions, four-coordinated Ca2+ ions, uncoordinated carboxyl oxygen atoms, and Npyridine atoms. As expected, because of the coexistence of Lewis acid-base nature, desolvated NUC-21 displays satisfactory catalytic activity on the chemical cycloaddition of various epoxides with CO2 into the corresponding alkyl carbonates under comparatively mild conditions. Furthermore, the efficient conversion of benzaldehydes and malononitrile confirms that NUC-21 is simultaneously a bifunctional heterogeneous catalyst for Knoevenagel condensation reactions. Hence, the achievements broaden the way for assembling nanoporous multifunctional MOFs by employing ligand-directed synthetic strategy, which can accelerate the transformation from simple structural research to socially demanding applications.

Dimethyl ether as circular hydrogen carrier: Catalytic aspects of hydrogenation/dehydrogenation steps

DME may be considered a promising circular hydrogen carrier, as it can be produced also from CO 2 . Catalytic aspects of both hydrogenation/dehydrogenation steps are deeply discussed for pushing advances in this field. The intermittent nature of renewable resources requires for most applications the development of efficient and cost-effective technologies for steady supply of electrical energy. The storage of energy in the form of hydrogen chemically bound within organic molecules (rather than physically as compressed gas or cooled liquid) represents an alternative approach that is attracting great research interest. Compared to other liquid organic hydrogen carriers (LOHCs), dimethyl ether (DME) appears to have the largest potential impact on society, especially if inserted in technological chains of CO 2 sequestration and utilization, so to determine an effective mitigation of environmental issues, without any net effect on the carbon footprint. Specifically, the steps of H 2 storage and H 2 release can take place in two coupled chemical processes, constituted by the exothermic synthesis of DME via CO 2 hydrogenation and the endothermic steam reforming of DME, respectively. Herein, the latest advances in the development of heterogeneous bifunctional and hybrid catalysts for the direct hydrogenation of CO 2 to DME are thoroughly reviewed, with special emphasis on thermodynamics, catalyst design and process feasibility. Despite many aspects behind the mechanism of DME synthesis from H 2 -CO 2 streams are still to be uncovered, the recent progress in the research on H 2 release by DME steam reforming is increasing the interest for effectively closing this binary H 2 loop, in view of future green deals and sustainable research developments.

In situ growth of NiSe@Co0.85Se heterointerface structure with electronic modulation on nickel foam for overall water splitting

Constructing heterointerface engineering has becoming an effective and general strategy for developing highly efficient and durable nonnoble electrocatalysts for catalyzing both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this work, we synthesized a self-supporting heterogeneous NiSe@Co0.85Se/NF electrocatalyst using a facile in situ selenization of transition metal precursors that coated on the nickel foam (NF) in polyol solution. The NF was used as both conductive substrate and nickel source, ensuring superior electronic conductivity for catalyzing. The NiSe@Co0.85Se/NF exhibited remarkable bifunctional electrocatalytic activities with HER overpotential of 168 mV and OER overpotential of 258 mV to achieve 10 mA·cm−2. The water splitting system using NiSe@Co0.85Se/NF as both anode and cathode electrodes achieved a current density of 10 mA·cm−2 at 1.61 V with nearly 100% faradaic efficiency and impressively long-term stability. The efficient bifunctional catalytic performance of NiSe@Co0.85Se/NF should be attributed to the electronic modulation and synergistic effect between NiSe and Co0.85Se, the intrinsic metallic conductivity and the enlarged active sites exposure. This work provides a facile method for developing heterogeneous bifunctional catalysts for advanced electrochemical energy conversion technologies.

Metal and Co‐Catalyst Free CO2 Conversion with a Bifunctional Covalent Organic Framework (COF)

AbstractThe excessive growth of CO2 brings about the global warming and subsequent climate change, which is an increased public concern issue. Currently, the chemical fixation of CO2 is identified as one of the most effective approaches to reduce and utilize CO2. Thus, it is a great challenge to rationally design and construct high‐efficient catalysts for CO2 conversion and utilization. Here, a unique metal‐free bifunctional COF heterogeneous catalyst was successfully achieved via the post‐modified strategy, which simultaneously bears −COOH as Brønsted acidic center and Br− ion as nucleophilic active site. By virtue of abundant porosity, excellent stability, favorable CO2 adsorption, and dual catalytic sites, this material can efficiently facilitate the coupling reaction of CO2 with epoxide to form cyclic carbonate without co‐catalyst under mild conditions. Moreover, it has excellent reusability, without significant reduction of the catalytic activity after at least five cycles.

Effect of Substituents on the Crystal Structures, Optical Properties, and Catalytic Activity of Homoleptic Zn(II) and Cd(II) β-oxodithioester Complexes.

Five novel zinc(II) and cadmium(II) β-oxodithioester complexes, [Zn(L1)2] (1), [Zn(L2)2]n (2), [Zn(L3)2]n (3) [Cd(L1)2]n (4), [Cd(L2)2]n (5), with β-oxodithioester ligands, where L1 = 3-(methylthio)-1-(thiophen-2-yl)-3-thioxoprop-1-en-1-olate, L2 = 3-(methylthio)-1-(pyridin-3-yl)-3-thioxoprop-1-en-1-olate, and L3 = 3-(methylthio)-1-(pyridin-4-yl)-3-thioxoprop-1-en-1-olate, were synthesized and characterized by elemental analysis, IR, UV-vis, and NMR spectroscopy (1H and 13C{1H}). The solid-state structures of all complexes were ascertained by single-crystal X-ray crystallography. The β-oxodithioester ligands are bonded to Zn(II)/Cd(II) metal ions in an O∧S and N chelating/chelating-bridging fashion leading to the formation of 1D (in 2-4) and 2D (in 5) coordination polymeric structures, but complex 1 was obtained as a discrete tetrahedral molecule. Complex 4 crystallizes in the C2 chiral space group and has been studied using circular dichroism (CD) spectroscopy. The multidimensional assemblies in these complexes are stabilized by many important noncovalent C-H···π (ZnOSC3, chelate), π···π, C-H···π, and H···H interactions. The catalytic activities of 1-5 in reactions involving C-C and C-O bond formation have been studied, and the results indicated that complex 3 can be efficiently utilized as a heterogeneous bifunctional catalyst for the Knoevenagel condensation and multicomponent reactions to develop biologically important organic molecules. The luminescent properties of complexes were also studied. Interestingly, zinc complexes 1-3 showed strong lumniscent emission in the solid state, whereas cadmium complexes 4 and 5 exhibited bright luminescent emission in the solution phase. The semiconducting behavior of the complexes was studied by solid-state diffuse reflectance spectra (DRS), which showed optical band gaps in the range of 2.49-2.62 eV.

A Primary Amide-Functionalized Heterogeneous Catalyst for the Synthesis of Coumarin-3-carboxylic Acids via a Tandem Reaction.

A crystalline primary amide-based bifunctional heterogeneous catalyst, {[Cd2(2-BPXG)(Fum)2(H2O)2]·2H2O}n (1) (where, 2-BPXG = 2,2'-((1,4-phenylenebis(methylene))bis((pyridin-2-ylmethyl)azanediyl)) diacetamide and Fum = fumarate), has been developed for the one-pot synthesis of a series of potentially biologically active coumarin-3-carboxylic acids at room temperature via a Knoevenagel-intramolecular cyclization tandem reaction. Catalyst 1 is prepared at room temperature from a one-pot self-assembly process in 81% yield and high purity within a few hours and has a ladder-like polymeric architecture based on single-crystal X-ray diffraction. Additional characterization of 1 includes elemental analysis, infrared spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. Based on the optimized conditions, it is determined that 1 is highly efficient (conditions: 2 mol % catalyst, 3 h, and 26-28 °C in methanol) for this reaction. Its recyclability up to five cycles without significant loss of activity and structural integrity is also demonstrated. Using both electron-donating and electron-withdrawing substituents on the salicylaldehyde substrate, seven different derivatives of coumarin-3-carboxylic acid were made. Additionally, the monoamine oxidase (MAO) inhibitor, coumarin-3-phenylcarboxamide, has also been synthesized from coumarin-3-carboxylic acid obtained in the catalysis process. A detailed mechanism of action is also provided.

Confinement Self-Assembly of Metal-Organic Cages within Mesoporous Carbon for One-Pot Sequential Reactions

Summary Well-defined discrete metal-organic cages have been widely explored in the field of supramolecular catalysis. However, these metal-organic cages have been rarely explored as heterogeneous catalysts for one-pot reactions. Herein, we present the first successful confinement self-assembly of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)-containing metal-organic cages within amino-functionalized mesoporous carbon to realize a new family of bifunctional heterogeneous catalyst (Cage@FDU-ED) for one-pot reactions. The orthogonal features of the isolated catalytically active sites within the obtained bifunctional catalyst lead to enhanced catalytic activities, selectivity, and recyclability with the overall transformation yielding up to 96% conversion. These results demonstrate that continuous chemical transformation with high efficiency is possible through careful design of catalytic sites in both metal-organic cages and mesoporous matrix isolatedly. This study paves a new way toward metal-organic cages as a promising platform for heterogeneous sequential reactions.

Unprecedented High Temperature CO2 Selectivity and Effective Chemical Fixation by a Copper-Based Undulated Metal-Organic Framework.

Post- and precombustion CO2 capture and separation are the vital challenges from industrial viewpoint, as the accessible technologies are not cost-effective and cumbersome. Thus, the development of functional metal-organic frameworks (MOFs) that are found to be promising materials for selective CO2 capture, separation, and conversion is gaining an importance in the scientific world. Based on the strategic design, a new functionalized triazine-based undulated paddle-wheel Cu-MOF (1), {[Cu(MTABA)(H2O)]·4H2O·2EtOH·DMF}n (where, H2MTABA = 4,4'-((6-methoxy-1,3,5-triazine-2,4-diyl)bis(azanediyl))dibenzoic acid), has been synthesized under solvothermal conditions and fully characterized. MOF 1 contains a one-dimensional channel along the a-axis with pore walls decorated with open metal sites, and multifunctional groups (amine, triazine, and methoxy). Unlike other porous materials, activated 1 (1') possesses exceptional increment in CO2/N2 and CO2/CH4 selectivity with increased temperature calculated by the ideal adsorbed solution theory. With an increase in temperature from 298 to 313 K, the selectivity of CO2 rises from 350.3 to 909.5 at zero coverage, which is unprecedented till date. Moreover, 1' behaves as a bifunctional heterogeneous catalyst through Lewis acid (open metal) and Brönsted acid sites to facilitate the chemical fixation of CO2 to cyclic carbonates under ambient conditions. The high selectivity for CO2 by 1' even at higher temperature was further corroborated with configurational bias Monte Carlo molecular simulation that ascertains the multiple CO2-philic sites and epoxide binding sites in 1' to further decipher the mechanistic pathway.

Beyond the Sabatier Optimum in Bi-Functional Heterogeneous Catalysts

A new strategy for designing efficient bi-functional heterogeneous catalysts is presented. We avoid assigning conflicting tasks to a single catalyst component. Each component is allowed to maximize the efficiency of the task/tasks assigned to it. With conflicts avoided, the Sabatier volcano plot is avoided. The water-gas-shift (WGS) reaction (CO + H2O -> CO2 + H2) is used as an example to illustrate this idea. Experimental and theoretical results show that bi-functional catalysts designed under this new framework have significantly lower rate-limiting reaction barriers.

Pyridinium-Functionalized Ionic Metal-Organic Frameworks Designed as Bifunctional Catalysts for CO2 Fixation into Cyclic Carbonates.

Ionic metal-organic frameworks (MOFs) offer a new platform to design and construct complete heterogeneous bifunctional catalytic systems for the chemical fixation of CO2 with epoxides. Herein, we developed a series of bifunctional pyridinium ionic MOF heterogeneous catalysts (66Pym-RXs and 67BPym-MeI) by the postsynthetic N-alkylation of noncoordinated pyridine sites in porous MOFs. The synergetic catalytic effect of acidic sites with nucleophilic anions in the ionic MOF significantly enhanced the catalytic activity toward the cycloaddition of CO2 with epoxides to produce cyclic carbonates under cocatalyst-free and solvent-free mild conditions. The catalytic activity of ionic MOFs is easily tuned by the introduction of different alkyl groups into pyridinium cations and halide ions. The 66Pym-iPrI catalyst displayed the highest catalytic performance in terms of the turnover number value for the synthesis of cyclic carbonates. The proposed alternative method provides the means of developing functional N-heterocyclic groups for the new design of bifunctional ionic MOFs as potential heterogeneous catalysts for CO2 fixation applications.

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.