Furfural Research Articles

Sustainability in Biofuel Production Technology

It is highly desirable but quite challenging to replace precious metals with cheaper elements in the catalytic selective hydrogenation of unsaturated aldehydes. Herein, we report the preparation of a series of CuxNi3−xAlOy mixed-metal oxides (x = 0.5, 1, 2) derived from CuxNi3−xAl hydrotalcite to be used as catalysts for the promotion of the selective hydrogenation of furfural (FAL) to furfuryl alcohol (FOL). It was found that the catalyst with the Cu2Ni1AlOy stoichiometry exhibited the best performance, with 98% FAL conversion and 99% selectivity toward FOL after 1.5 h at 120 °C and under a H2 pressure of 1.6 MPa, and also good reusability. On the basis of the combined results from catalyst characterization studies using XRD, H2-TPR, TEM, XPS, and in-situ FT-IR, it was concluded that the CuOx species on the surface of the CuxNi3−xAlOy catalysts can be reduced in situ to metallic copper during reaction, and that this Cu0 species is likely the responsible for the adsorption and conversion of FAL. The addition of Ni to these mixed-metal oxides helps disperse the Cu phase and hence make it easier to reduce and activate. It may also be that NiO can promote H2 dissociation to aid with the hydrogenation catalysis. Our work advances a new strategy for the design of simple, cheap, and efficient catalysts for the hydrogenation of FAL to FOL.

Catalytic aldol condensation of bio-derived furanic aldehydes and acetone: Challenges and opportunities

Bio-derived furfural and 5-hydroxymethylfurfural can be combined with acetone to yield aldol condensation products that may serve as biofuel and polymer precursors. We have explored different catalytic systems to obtain and purify each product in the most efficient way. The results of the catalytic tests of the cross-condensations and of the self-condensation of acetone allowed the comparison of the different reactivity of the two aldehydes. Online and in situ/operando ATR-IR was used to monitor the reaction over time and to study the interaction of the reaction species with the solid catalyst, especially the formation of deactivating organic matter that covers the surface, which is a major issue in heterogeneous condensation processes. In situ NMR was used to study the ongoing reaction, assessing its stereoselectivity, and to study the behavior of deuterated species in the catalytic system. Finally, the preparation of C14, a hetero-double-condensation product, was also explored.

Synthesis 2-((Furan-2-yl) Methylene)-1-Phenilhydrazone from Furfural Results of Corn Isolation and Its Utilization as Corrosion Inhibitor in Zinc (Zn) Metal

Synthesis of 2-((furan-2-yl) methylene)-1-phenylhydrazone has been carried out by reaction of condensation of furfural aldehyde groups obtained from the isolation of corn cobs with phenylhydrazine. Furfural condensation with phenylhydrazine was carried out by refluxing in ethanol solvent for 1 hour. Of the 9.6 g (0.1 mol) furfural which was condensed with 5.4 g (0.05 mol) phenylhydrazine obtained yield of 10.54 g (67.02%) phenylhydrazone which was then analyzed by FT-IR spectroscopy showing the presence of vibration C = N in the area around 1597 cm-1. Fenilhidrazone was tested for inhibitor with 78.47% and compared with furfural as much as 58.18%, and phenylhydrazine as much as 50.04%. The results obtained by phenylhydrazone were more efficient at inhibiting the results of 78.47% while furfural and phenylhydrazine were only 58.18% and 50.04%.

Dimethyl carbonate solvent assisted efficient conversion of lignocellulosic biomass to 5- hydroxymethylfurfural and furfural

An efficient, economic, and one-pot process has been developed for the direct conversion of untreated biomass feedstock such as corn-cob, sugarcane bagasse, rice-straw, and corn-straw into 5-HMF and furfural (FF) synthesis in dimethyl carbonate (DMC) solvent conditions under a pressurized hydrothermal steel vial system. The use of DMC as a green solvent under acidic medium was explored first time for the transformation of complex lignocellulosic biomass into furanic compounds. Moreover, the DMC solvent under acidic environment partially produced CO2 that facilitates the depolymerization of recalcitrant biomass substrate and subsequently participates in conversion under the set conditions. Notably, the influence of various parameters such as temperature, time, solvents, and the synergistic functions of AlCl3 and HCl was examined to optimize the reaction conditions. After optimization, the maximum yield of 5-HMF and furfural from various biomass feedstock was recorded as 35–60% and 61–98% respectively within 6 h at 180 °C. Furthermore, we have described the relative compositions of biopolymers (cellulose, hemicellulose, and lignin), moisture/and ash content in each biomass substrate. The SEM analysis provided information about particle size and shape via calculating aspect ratio of mechanical grinded lignocellulosic biomass. Subsequently, the quantification of products was scrutinized through UPLC and further reconfirmed via NMR and ESI-MS analysis techniques.

A novel and highly efficient Zr-containing catalyst supported by biomass-derived sodium carboxymethyl cellulose for hydrogenation of furfural.

Functional use of biomass based on its structural properties is an efficient approach for the valuable utilization of biomass resources. In this work, carboxymethyl cellulose zirconium-based catalyst (Zr-CMC) was constructed by the coordination between the carboxylic groups in sodium carboxymethyl cellulose (CMC-Na) with transition metal Zr4+. The prepared catalyst was applied into the synthesis of furfuryl alcohol (FAL) by catalytic transfer hydrogenation of biomass-derived furfural (FF) using isopropanol as hydrogen donor. Both the preparation conditions and the reaction conditions of Zr-CMC catalyst were investigated and optimized. The results showed that Zr-CMC was efficient for the reaction with the FF conversion, FAL yield and selectivity reaching to 92.5%, 91.5 %, and 99.0%, respectively, under the mild conditions (90°C). Meanwhile, the Zr-CMC catalyst could be reused at least for five times without obvious decrease in efficiency, indicating the catalyst had excellent stability. With the advantages of sustainable raw materials, high efficiency, and excellent stability, the prepared catalyst is potential for application in the field of biomass conversion.

Selective Oxidation of Furfural at Room Temperature on a TiO2-Supported Ag Catalyst

The catalytic performance of the Ag/TiO2 catalyst was evaluated in the oxidation of furfural (FF) to furoic acid (FA) in an alkaline aqueous solution under 15 bar of air in a batch reactor. The catalytic activity, yield, and stability of the catalyst were compared as a function of different reaction parameters including temperature (25–110 °C), nature of the atmosphere, base equivalent (nbase/nFF = 0.25–3), and nature of the inorganic bases used (NaOH, NaHCO3, and Na2CO3). Under optimum conditions, the yield of FA (96%) was achieved at room temperature, with an excellent carbon balance (>98%). The recyclability of the catalyst was also studied and the catalytic activity of the Ag/TiO2 catalyst slightly declined due to an increase in particle size as confirmed by TEM studies.

Removal of lignin and silica from rice straw for enhanced accessibility of holocellulose for the production of high-value chemicals

The intricate nature and rigidity of rice straw, particularly the presence of lignin and silica, hinders the catalytic valorization, consequently decreasing the yield of target products. This study reports the concurrent removal of lignin and silica from rice straw to obtain enriched holocellulose, then transforming it to furfural (FUR) and levulinic acid (LA). Interestingly, rice straw in the form of powder displays an improved removal of lignin (51.0%) and silica (92.0%) during ammonia treatment. Encouragingly, adding organic solvents, such as THF, to the aqueous system during the pretreatment of rice straw improves the lignin removal to 60.0%. Upon improving lignin removal to 60%, the obtained holocellulose enriched solid residue yields 71.0% FUR along with 52.0% LA, which is 8 and 4-fold higher than what is obtained with parent rice straw, signifying the importance and the prerequisite of lignin and silica removal from rice straw.

Recent advances in heterogeneous catalytic hydrodeoxygenation of biomass-derived oxygenated furanics mediated by formic acid

The hydrodeoxygenation is a prominent valorization approach to upgrade biomass-derived platform compounds, i.e. furfural (FF) and 5-hydroxymethylfurfural (HMF), into the value-added fuels and chemicals. As a promising alternative to molecular H2, formic acid (HCOOH) has been extensively investigated as a liquid organic hydrogen donor for the transfer hydrogenation of biomass derivatives. In this study, the recent advances in the heterogeneous catalytic HCOOH-mediated hydrodeoxygenation processes of FF and HMF (especially, the hydrogenation of C=O bond and hydrogenolysis of C–O bond) are systematically reviewed by summarizing the heterogeneous catalysts developed and reaction conditions reported in literature. Furthermore, the reaction mechanisms including the individual and combined activations of hydrogen donor (HCOOH) and substrates (FF and HMF) on the catalyst surface are also discussed in order to provide fundamental insights into the associated reaction mechanisms for the future catalyst design. It is believed that this review may serve as a concise guideline on the development of heterogeneous catalysts for the upgradation of biomass-derived oxygenated furanics using HCOOH as the hydrogen donor.

Insights Provided By Modeling of Electrochemical Hydrogenation and Hydrogenolysis of Furfural on Cu and Side Reactions in Acidic Media

Fine chemicals and fuels can be generated by electrochemical methods as an alternative to the currently in place thermocatalytic methods. The thermocatalytic methods require harsher reaction conditions, such as elevated pressures and temperatures, but also requires hydrogen gas as a reactant for reduction reactions which largely is produced by non-sustainable methods which emit high amounts of CO2. Electrochemical methods, in comparison, use in-situ generated protons in lieu of hydrogen gas which reduces the overall CO2 generation. Electrifying the chemical industry will allow for the reduction in anthropogenic CO2 generation by coupling a neutral or negative carbon emitting process with renewable electricity. Furfural (FF) is a biomass derived platform molecule produced at a scale above 300,000 metric tons annually and can used to produce furfuryl alcohol (FA) and 2-methylfuran (MF) through electrochemical hydrogenation and hydrogenolysis (ECH) respectively. FA is a fine chemical that is highly desirable for use in furanic molds, while MF has been identified as a fuel or fuel precursor. In this work, the kinetics of the FF ECH electrochemical system is decoupled and modeled to understand the conversion of FF.In this work, the electrochemical kinetics and non-electrochemical side reactions investigated in our previous works [1,2,3] are modeled to gain further insights into the mass balance and the longer-term phenomena associated with the FF ECH system. The FF ECH system is modeled as three contributing pieces: the ECH reactions, the non-electrochemical side reactions, and the evaporation of MF to the solvent trap for collection. The desired electrochemical reactions were investigated using a 2 compartment H-cell with a Cu flag electrode in the cathode compartment, and connected to a solvent trap held at -15°C. Experimentation was done in 0.1 and 0.5 M H2SO4 with concentrations of FF between 10 and 120 mM FF. The catholyte had a cosolvent of 80:20 vol% water: acetonitrile and was purged with 60mL/min of nitrogen gas. To study the non-electrochemical reactions, vials of electrolyte with FF, FA, and MF in concentrations matching those found in electrochemical experiments were prepared and sample over time without the presence of any electrochemistry. The vial samples over time showed that mass loss occurred for the three furanics, however much more significantly for FA and MF, the two desired products. Lastly, the evaporation of MF from the catholyte to the solvent trap was studied by preparing the H-cell with a known concentration of MF and sampling over time. By modeling the FF ECH system this way, we were able to show the prominence of the competing side reactions and evaporation of MF to the solvent trap which provides insights into the mass balance and performance of the FF ECH system. We find that while the side reactions are more prevalent in the 0.5M H2SO4 than the 0.1M H2SO4, that a higher MF yield is reached due to the evaporation and collection of MF in the solvent trap. A higher FA yield is found in the 0.1M H2SO4 compared to the 0.5M H2SO4.[1] May, Andrew S., Steven M. Watt, and Elizabeth J. Biddinger. "Kinetics of furfural electrochemical hydrogenation and hydrogenolysis in acidic media on copper." Reaction Chemistry & Engineering 6, no. 11 (2021): 2075-2086[2] Jung, Sungyup, and Elizabeth J. Biddinger. "Electrocatalytic hydrogenation and hydrogenolysis of furfural and the impact of homogeneous side reactions of furanic compounds in acidic electrolytes." ACS Sustainable Chemistry & Engineering 4, no. 12 (2016): 6500-6508[3] Jung, Sungyup, and Elizabeth J. Biddinger. "Controlling competitive side reactions in the electrochemical upgrading of furfural to biofuel." Energy Technology 6, no. 7 (2018): 1370-1379

Understanding of the Furfural Electrochemical Hydrogenation and Hydrogenolysis System in a Semi-Batch Reactor

Furfural (FF) is a platform molecule that can undergo electrochemical hydrogenation and hydrogenolysis (ECH) over copper catalysts to form furfuryl alcohol (FA) and 2-methylfuran (FA) respectively. FA is a fine chemical used in creating furanic molds, and MF has been identified as a fuel candidate. An acidic electrolyte is necessary to obtain the MF product, however the acidic conditions are also the cause of homogeneous side reactions [1,2]. In our group we studied the kinetics of the FF ECH reactions in a 2-compartment H-cell connected to a solvent trap with inert gas sparging into the catholyte to promote the evaporation of MF to the solvent trap for capture. We showed the kinetics of the FF ECH reactions in 0.1 and 0.5M H2SO4 with concentrations of FF between 10 and 120 mM at -560mV vs RHE followed a non-competitive Langmuir-Hinshelwood model [3], in timeframes where side reactions did not influence the results significantly.In this work, we build on our previous kinetic study by modeling the system of competing reactions and MF transfer to the solvent trap. We show the importance of sparging inert gas into the catholyte to promote evaporation of MF for collection in the solvent trap to avoid side reactions of MF in the acidic catholyte.[1] Jung, Sungyup, and Elizabeth J. Biddinger. "Electrocatalytic hydrogenation and hydrogenolysis of furfural and the impact of homogeneous side reactions of furanic compounds in acidic electrolytes." ACS Sustainable Chemistry & Engineering 4, no. 12 (2016): 6500-6508[2] Jung, Sungyup, and Elizabeth J. Biddinger. "Controlling competitive side reactions in the electrochemical upgrading of furfural to biofuel." Energy Technology 6, no. 7 (2018): 1370-1379[3] May, Andrew S., Steven M. Watt, and Elizabeth J. Biddinger. "Kinetics of furfural electrochemical hydrogenation and hydrogenolysis in acidic media on copper." Reaction Chemistry & Engineering 6, no. 11 (2021): 2075-2086

In situ construction of hierarchical Ag-decorated Cu nanowire arrays as an efficient and durable electrocatalyst for hydrogenation of 5-hydroxymethylfurfural and furfural

Electrochemical hydrogenation of biomass-furan derivatives to produce high-value-added fine chemicals has been regarded as a green and sustainable route since it uses water as the hydrogen source instead of extra H2 and can proceed in ambient conditions. The key to improve electrocatalytic efficiency is developing capable and stable electrocatalysts based on advanced design. In this work, a novel hierarchical structure of Ag-decorated Cu nanowire arrays was in-situ synthesized on Cu foam (Ag@Cu NWAs/CF) for electrochemical hydrogenation of biomass-derived 5-hydroxymethylfurfural (HMF) and furfural (FUR) to 2,5-bis(hydroxymethyl)furan (BHMF) and furfuryl alcohol (FAL), respectively. By owning a large electrochemically active surface area, efficient electronic transmission network, open and sturdy structure, and synergic combination of Cu and Ag active sites, the electrode shows outstanding electrochemical hydrogenation performance for HMF and FUR by achieving above 95% selectivity and faradaic efficiency (FE) of BHMF and FAL, and maintaining above 92% FE towards BHMF and FAL after six electrolysis cycles. Based on the optimization of reaction conditions and investigation of relationship between catalyst structure and performance, reaction mechanism of this system was further elucidated for efficient and sustainable conversion of biomass-derived furan compounds to value-added fine chemicals.

Synergistic effects of inhibitors and osmotic stress during high gravity bioethanol production from steam-exploded lignocellulosic feedstocks

High gravity second-generation bioethanol production (solid loading ≥30% w w−1) suffers from prolonged fermentation times and low ethanol productivities due to high concentrations of toxic by-products (inhibitors) and high monosaccharide concentrations. To better understand inhibition during high gravity bioethanol production, this study focused on ethanol production from a variety of different steam-exploded feedstocks with different inhibitor concentrations. The effects of inhibitors on enzymatic hydrolysis and fermentation were investigated by selective removal of inhibitors by means of biological detoxification. The degree of lignocellulose depolymerization and inhibitor formation during steam explosion varied significantly between different feedstock types. Subsequent enzymatic hydrolysis and fermentation indicated that lignocellulosic inhibitors had no significant effect on cellulolytic enzymes, but showed strong inhibition on fermentation performance. Biological detoxification of furan aldehydes and organic acids had no impact on monosaccharide yield during enzymatic hydrolysis, but reduced the fermentative lag phase by up to 48 h. While the detoxification significantly improved fermentation performance, the maximal ethanol yield of 52.6 g L−1 with wheat straw or miscanthus could not be increased. A key finding of this study was that the effect of lignocellulosic inhibitors is greatly increased in environments with high osmotic stress. This synergistic effect is hypothesized to be caused by an inhibitor-induced redox imbalance, impeding the cells’ ability to counteract osmotic stress.

NiyCo2-yP alloy catalysts with assistance of Y for boosting Low-pressure hydrogenation transformation of Biomass-derived levulinic acid or furfural in water

Acquiring practical catalysts was crucial for promoting the application of advanced chemical transformations. Here, a series of Co-Ni-P catalysts with addition of Y were designed for hydrogenation transformation of biomass-derived levulinic acid (LA) or furfural (FAL) in water. The molar-composition-manipulated catalysts were characterized in Co-Ni phosphide alloy nanostructure with YPO4 enriched on surface and denoted as (YPO4)x/CoyNi2-yP. By comprehensive catalytic measurements, both Co:Ni ratio in phosphide alloy and amount of YPO4 were testified to be key factors to modulate intrinsic catalytic properties (hydrogen activation and acid catalysis) along Y-Co-Ni-P interface, the attractive and reproducible yield for desired product γ-valerolactone (up to 98 %) or cyclopentanone (up to 93%) could achieve under low H2 pressure of 0.1–0.5 MPa over the well modulated catalyst (YPO4)0.2/Co1.0Ni1.0P in comparison with high H2 pressure (beyond 1.0 MPa) required in most of literature systems, indicating that the efficiency and feasibility of these important biomass transformations could be greatly enhanced on the low-cost and robust (YPO4)x/CoyNi2-yP catalysts. These findings suggested that the phosphide-alloy engineering technique provided in this work could serve as a novel and practical method for innovating competitive catalysts to boost advanced heterogeneous catalysis applications as well as current aqueous hydrogenation transformations of biomass derivatives.

Co decorated low Pt loading nanoparticles over TiO2 catalyst for selective hydrogenation of furfural

Selective hydrogenation of carbonyl groups in biobased chemicals to alcohols is crucial to the economics of broadly sustainable product portfolios. Furfuryl alcohol (FOL), the most prominent chemical of hemicellulose, has been produced by furfural (FAL) hydrogenation over heterogeneous catalysts. In this work, we show the outstanding activity, selectivity, and stability of supported bimetallic PtCo nanoparticle (np) synthesized from a pre-made stock solution of zero valent atomic Pt precursor and Co2(CO)8. With only 0.5 wt% Pt on TiO2, the np-PtCo/TiO2 catalyst exhibits TOF of 14,023 h−1 at 30 °C with > 99.9% FOL selectivity. The stability of the np-PtCo/TiO2 catalyst is verified by the steady performance in reuses at both moderate and full conversions. The oxyphilic Coδ+ in the PtCo nanoparticles induces nucleophilic chemisorption of -CO, resulting in deeply polarized CO bond. DFT calculated FAL adsorption energies on np-Pt and np-PtCo are − 0.22 eV and − 0.74 eV, respectively.

Comparison of the Effects of 5-Hydroxymethylfurfural in Milk Powder Matrix and Standard Water on Oxidative Stress System of Zebrafish.

5-Hydroxymethylfurfural (5-HMF) and furfural (FF) are products of the maillard reaction (MR) in milk powder and their safety is controversial. The concentration changes of 5-HMF and FF after a period of cold storage were determined by high-performance liquid chromatography (HPLC). Then, we compared the toxicity effects of 5-HMF (2, 20, or 200 μM) in milk powder matrix and standard water on the oxidative stress system of zebrafish embryos. The results showed that the concentration of 5-HMF was stable, and the concentration of FF degraded over time. 5-HMF-exposed zebrafish embryos had a LC50 value of 961 μM for 120 h. High-concentration of 5-HMF exposure resulted in developmental toxicity and induced oxidative stress. 5-HMF exposure resulted in low expression of gstr gene at 200 μM in both matrices. Moreover, sod, cat, gstr, and gpxla genes were differentially highly expressed in other groups or showed no significant difference. Residual levels in all groups were well below the exposed dose, with a maximum value of only 0.4‰. These results provided a theoretical basis for understanding the effects of 5-HMF exposure in milk powder matrix on the oxidative stress system and suggested that the presence of 5-HMF in our daily consumption of milk powder does not produce significant toxic effects and need not be overstressed.

Synthesis of Dual-Active-Sites Ni-Ni2In catalysts for selective hydrogenation of furfural to furfuryl alcohol

The rational design of efficient heterogeneous catalysts for selective hydrogenation of unsaturated aldehyde to unsaturated alcohol is a long-term scientific challenge and pursuit. Herein, we prepared an effective NiIn0.2/MgO-Al2O3 catalyst with dual active sites for hydrogenation of furfural (FAL) to furfuryl alcohol (FOL), delivering a high activity and a maximum 98.9% FOL yield. Moreover, the NiIn0.2/MgO-Al2O3 exhibited excellent catalytic performances for the other unsaturated aldehydes and good durability in a 100 h stability test. Characterization and theoretical calculations reveal that H2 and FAL are adsorbed and activated on the active sites of metallic Ni and Ni2In intermetallic compound, respectively. Hydrogenation of FAL to FOL occurs on the surface of Ni2In via hydrogen spillover from metallic Ni. Sequentially, FOL easily desorbs from the surface of Ni2In owing to the active-site isolation and electron transfer effect in Ni2In. The metal-IMCs dual-active-sites mechanism provides a novel strategy for synthesizing efficient hydrogenation catalysts.

Promoted Hydrogenolysis of Furan Aldehydes to 2,5‐Dimethylfuran by Defect Engineering on Pd/NiCo2O4

Promoted Hydrogenolysis of Furan Aldehydes to 2,5‐Dimethylfuran by Defect Engineering on Pd/NiCo₂O₄

Design and synthesis of hollow Ce/Zr-UiO-66 nanoreactors for synergistic and efficient catalysis

Hollow MOFs nanoreactors with controlled shape, size, pore volume, and shell thickness have been considered as emerging materials for a variety of applications. Selecting environmentally friendly and cheap colloidal carbon (CNs) as the template, bimetallic hollow Ce/Zr-UiO-66 nanoreactors were synthesized. The PXRD, TEM, EDS and other characterization analysis proved that hollow structure was formed, accompanied with incorporating of Ce(III) in UiO-66 and the crystal morphology was good. Furthermore, bimetallic hollow Ce/Zr-UiO-66 was studied as a catalyst to catalyze the conversion of furfural (FF) to furfuryl alcohol (FAL) without exogenous hydrogen. The results showed that the hollow structure and bimetallic UiO-66 was beneficial to the catalytic reaction by modulating the ratio of Ce(III) and Zr(IV). Among then, the 1:4 ratio of Ce(III) and Zr(IV) displayed good catalytic activity, the conversion rate of FF was 95% and selectivity of FAL was 94%. This study opens a new avenue for further rational design and construction of well-performing MOFs nanoreactors.

Magnetic Nanoparticles Supported on g‐C3N4 : An Efficient Heterogeneous Catalyst for Selective Transfer Hydrogenation of Furfural to Furfuryl alcohol

AbstractA series of economic and environmental benign g‐C3N4 supported magnetic ferrite nanoparticles (Fe3O4@g‐C3N4) were synthesized for the catalytic transfer hydrogenation of furfural (FF) into furfuryl alcohol (FFA) using ethanol as a source of hydrogen donor and solvent. The unique feature of high nitrogen content and locally conjugated structure of the g‐C3N4 have made it excellent support for loading of small sized ferrite nanoparticles. Excellent furfural conversion of 95.6 % was obtained with 100 % selectivity of the required product furfuryl alcohol over this Fe3O4@g‐C3N4 nanoparticles having mass ratio 0.2 of Fe3O4@g‐C3N4. The high surface properties, uniform dispersion of ferrite and very high ability of adsorption of furfural over g‐C3N4 attributed to the effective catalytic activity. The effect of iron content, catalyst amount, solvent, temperature and reaction time on the CTH of furfural were studied. The synthesized catalysts were characterised by various physic‐chemical, spectroscopic and microscopic techniques.

Synergetic effect of Cu0 −Cu+ derived from layered double hydroxides toward catalytic transfer hydrogenation reaction

As a safe and environmentally friendly selective hydrogenation method, catalytic transfer hydrogenation (CTH) has aroused great interest in preparation of high-value-added products from biomass derived resources. Herein, a Cu-based catalyst (Cu/CuAl-MMO-400) was prepared by structural topological transformation of layered double hydroxides (LDHs) precursor, which displayed promising catalytic behavior toward CTH reaction of furfural (FAL) with 2-propanol (2-POL) as the hydrogen donor. Notably, the reaction rate is as high as 0.125 mol g−1 h−1, which is superior to previously reported non-noble metal catalysts. A combination investigation based on XPS, XANES and Bader charge confirms the co-existence of Cu0 and Cu+ sites on the surface of Cu nanoparticles. Both experimental studies (in situ DRIFTS and isotope labelling MS) and DFT calculations reveal that the Cu0−Cu+ synergistic effect plays a vital role in determining catalytic behavior: the Cu+ species acts as both dehydrogenation and hydrogenation active site; while the Cu0 site promotes the transfer of H atoms between adsorbed substrates. This work substantiates a Cu0 −Cu+ synergetic catalysis by establishing structure-property correlation and revealing reaction pathway, which could be extended to other CTH reactions in the upgrading processes of biomass.