Catalysts For Hydrogenolysis Research Articles

Ru-WOX-doped biochar for selective ethylene glycol production from cellulose hydrogenolysis: Unravelling the role of WOX in adjusting acid-metal balance

Ru-WOX composites are usually bi-functional catalysts for cellulose hydrogenolysis, but the proportion/synergism of Ru (metal) and WOX (acidity) are mismatched/unclear, this leads to low ethylene glycol (EG) yield. In this work, we doped Ru‑WOX on low-costed biochar for cellulose hydrogenolysis. The acid-metal balance was adjusted by change the WOX load, and our results show that the activity and EG yield have the order of Ru-30WOX-C > Ru-40WOX-C > Ru-20WOX-C > Ru-10WOX-C, and it is interesting found that a linear relationship between acid/metal ratio and EG yield. Under the optimum conditions (240 °C, 3 MPa and 3 h), Ru-30WOX-C catalyst can achieve 100% cellulose conversion and 61.3% EG yield. 30%WOX facilitates Ru dispersion/reduction, and provides rich acid sites, accompanied by a large number of acid centers (oxygen vacancies), this more easily adsorbed cellulose monomer and activated glucose to glycolaldehyde, and benefit to EG productive. This work provides a guidance to design new bio-functional catalysts for biomass conversion.

Selective Control of Catalysts for Glycerol and Cellulose Hydrogenolysis to Produce Ethylene Glycol and 1,2-Propylene Glycol: A Review

The bioconversion of cellulose and the transformation of glycerol can yield various diols, aligning with environmental sustainability goals by reducing dependence on fossil fuels, lowering raw material costs, and promoting sustainable development. However, in the selective hydrogenolysis of glycerol to ethylene glycol (EG) and 1,2-propylene glycol (1,2-PG), challenges such as low selectivity of catalytic systems, poor stability, limited renewability, and stringent reaction conditions remain. The production of diols from cellulose involves multiple reaction steps, including hydrolysis, isomerization, retro-aldol condensation, hydrogenation, and dehydration. Consequently, the design of highly efficient catalysts with multifunctional active sites tailored to these specific reaction steps remains a significant challenge. This review aims to provide a comprehensive overview of the selective regulation of catalysts for producing EG and 1,2-PG from cellulose and glycerol. It discusses the reaction pathways, process methodologies, catalytic systems, and the performance of catalysts, focusing on active site characteristics. By summarizing the latest research in this field, we aim to offer a detailed understanding of the state-of-the-art in glycerol and cellulose conversion to diols and provide valuable guidance for future research and industrial applications. Through this review, we seek to clarify the current advancements and selective control strategies in diol production from glycerol or cellulose, thereby offering critical insights for future investigations and industrial scale-up.

Propylene Glycol from Biodiesel By-product

The enormous production of glycerol, a waste stream from biodiesel industries, as a low-value product has been causing a threat to both the environment and the economy. Therefore, it needs to be transformed effectively into valued products for contributing positively towards towards the biodiesel economy. In this study, propylene glycol was produced by hydrogenating glycerol with a highly selective hydrogenolysis catalyst. The effect of various reaction parameters on the product yield was evaluated. A two-step reaction process where, first, glycerol was dehydrated to form acetol, and then this acetol was hydrogenated in a further reaction step to produce propylene glycol gave higher conversion as compared to a one-step reaction process. The effects of reaction temperature and pressure on the product yield were also evaluated. Higher yields of propylene glycol were observed at higher pressures. At temperatures above 200 °C, more by-products may be formed as the selectivity on converting glycerol to propylene glycol dramatically decreased, eventhough the glycol content increased.

A significant enhancement for hydrogenolysis of glycerol to 1,3-propanediol over Pt/W-SiO2 catalyst by tungsten oxide and silica interaction

Pt-W based catalyst is one of effective catalysts for hydrogenolysis of glycerol to 1,3-propanediol (1,3-PDO), where the interaction between Pt and tungsten oxide (WOx) has been considered as a crucial factor for the activity, but interactions between WOx and supports are rarely studied. In this study, we investigated the SiO2-WOx interaction over Pt/W-SiO2 catalysts by adjusting silanols on the silica supports, and it is demonstrated that weaker WOx-SiO2 interaction benefits Pt-WOx interaction (larger Pt-WOx coordinations), which is helpful for glycerol hydrogenolysis to 1,3-PDO. For example, Pt/W-SiO2-700 (calcination at 700 °C for removing most of silanols in the silica support to have larger Pt-WOx coordinations) exhibits a glycerol conversion at 70.9 % with excellent 1,3-PDO selectivity of 61.3 % at a mild temperature of 140 °C. Experimental results and theoretical calculations support that larger Pt-WOx coordination favors hydrogen spillover to form more isolated WOx-H species, which are favorable for glycerol hydrogenolysis to 1,3-PDO.

Predicting hydrogenolysis reaction barriers of large hydrocarbons on metal surfaces using machine learning: Implications for polymer deconstruction

Calculating activation energies of chemical reactions for large reaction networks is computationally demanding. Traditional Brønsted-Evans-Polanyi (BEP) relationships are useful in this regard but are prone to substantial estimation errors. Here, we explore machine learning models to predict activation energies for hydrogenolysis reactions on transition metals, including Ru, Pt, and Rh. The curated dataset includes 380 DFT-calculated activation energies of C-C and C-H scission reactions ranging from C1 to C6 species. The mean absolute error of traditional BEPs is 0.30 eV, and published BEPs on smaller hydrocarbons give even larger errors. In comparison, an XGBoost model achieves a mean absolute error of 0.19 eV for the test set without needing additional DFT-calculated energies. The model selects the homologous series among reactions and the electronegativity and atomic mass of the metal atoms as key features. The model appears transferable across metals. This approach can provide accurate and rapid estimation of activation energies of large reaction networks, such as those in plastics recycling, to accelerate catalyst screening. We showcase the impact of hydrocarbon chain length and branching on the barriers, discuss implications for the depolymerization rate of isotactic polypropylene and low vs. high-density polyethylene, and demonstrate the feasibility of hydrogenolysis catalyst screening.

Hydrogenolysis of Poly(Ethylene-co-Vinyl Alcohol) and Related Polymer Blends over Ruthenium Heterogeneous Catalysts.

The hydrogenolysis of polymers is emerging as a promising approach to deconstruct plastic waste into valuable chemicals. Yet, the complexity of plastic waste, including multilayer packaging, is a significant barrier to handling realistic waste streams. Herein, we reveal fundamental insights into a new chemical route for transforming a previously unaddressed fraction of plastic waste - poly(ethylene-co-vinyl alcohol) (EVOH) and related polymer blends - into alkane products. We report that Ru/ZrO2 is active for the concurrent hydrogenolysis, hydrogenation, and hydrodeoxygenation of EVOH and its thermal degradation products into alkanes (C1-C35) and water. Detailed reaction data, product analysis, and catalyst characterization reveal that the in-situ thermal degradation of EVOH forms aromatic intermediates that are detrimental to catalytic activity. Increased hydrogen pressure promotes hydrogenation of these aromatics, preventing catalyst deactivation and improving alkane product yields. Calculated apparent rates of C-C scission reveal that the hydrogenolysis of EVOH is slower than low-density polyethylene. We apply these findings to achieve hydrogenolysis of EVOH/polyethylene blends and elucidate the sensitivity of hydrogenolysis catalysts to such blends. Overall, we demonstrate progress towards efficient catalytic processes for the hydroconversion of waste multilayer film plastic packaging into valuable products.

Understanding the catalytic performance and deactivation behaviour of second-promoter doped Pt/WOx/γ-Al2O3 catalysts in the glycerol hydrogenolysis for selective and cleaner production of 1,3-propanediol

The selective aqueous-phase glycerol hydrogenolysis is a promising reaction to produce commercially useful 1,3-propanediol (1,3-PDO). The Pt-WOx bifunctional catalyst can catalyse the glycerol hydrogenolysis but the catalyst deactivation via sintering, metal leaching, and coking can predominantly occur in the aqueous phase reaction. In this work, the effect of reaction temperature, pressure and second promoter (Cu, Fe, Rh, Mn, Re, Ru, Ir, Sn, B, and P) on catalytic performance and deactivation behaviour of Pt/WOx/γ-Al2O3 was investigated. When doped with Rh, Mn, Re, Ru, Ir, B, and P, the second promoter boosts catalytic activity by promoting great dispersion of Pt on support and increasing Pt surface area. The increased Brønsted acid sites lead to selective synthesis of 1,3-PDO than 1,2-propanediol (1,2-PDO). The characterization studies of fresh and spent catalysts reveal that the main cause of catalyst deactivation is the Pt sintering, as interpreted based on XRD, CO chemisorption, and TEM analyses. The Pt sintering is affected depending on the second promoter that can either or reduce the interaction between Pt, WOx, and Al2O3. As an electron acceptor of Pt in Pt/WOx/γ-Al2O3, Re and Mn as second promoters resulted in increased Pt2+ on the catalytic surface, which strengthens the contact between Pt and γ-Al2O3 and WOx, resulting in a decrease in Pt sintering. The metal leaching and coking are not affected by the presence of second promoter. The catalyst modified with a second promoter possesses improved catalytic activity and 1,3-PDO production, however the stability continues to remain a challenge. The present work unravelled the determining parameters of catalytic activity and deactivation, thus providing a promising protocol toward effective catalysts for glycerol hydrogenolysis.

High performance Pt/Nb2W3O14 catalyst for glycerol valorization to 1,3-propanediol

Glycerol hydrogenolysis to 1,3-propanediol (1,3-PDO) is of significance in promoting the biomass valorization. To achieve the efficient conversion, the selective activation of the secondary C–O bonds in the glycerol is vital. In this work, we comparatively investigated the catalytic performances of Pt/Nb2W3O14 catalyst for glycerol hydrogenolysis controlled at the reacting conditions of 140 °C and 40 bar. Compared to Pt/WO3 and Pt/NbOx, the space–time yield (STY) of 1,3-PDO over Pt/Nb2W3O14 catalyst can be improved by a factor of 13, reaching 596.4 mg gcat−1 h−1. The cation ordering of Nb and W on atomic-scale were fully synergized their unique advantages, showing preferential adsorption of the secondary C–O bond under in-situ DRIFTS tracking. The prepared Nb2W3O14 is a tetragonal tungsten bronze (TTB) type complex oxides which can effectively promote the dispersion and reduction of Pt nanoparticles. Such strong interaction between Nb2W3O14 and Pt can coordinate the precise adsorption and activation of the secondary C–O bond, simultaneously triggering subsequent hydrogenation. Pt/Nb2W3O14 affords an ultrahigh activity in glycerol hydrogenolysis to produce 1,3-PDO, tripling the record productivity that was previously reported of these Pt-W based catalysts. This study reported the development of highly synergistic catalyst based on efficient and selective activation of the secondary C–O bond, which can be extended to catalyst design for other biomass valorization.

Regulation of Pt Loading on Co/Al2O3 Catalysts for Selective Hydrogenation and Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Bis(hydroxymethyl)furan and 2,5‐Dimethylfuran

AbstractSelective hydrogenation and hydrogenolysis of 5‐hydroxymethylfurfural (HMF) to 2,5‐bis(hydroxymethyl)furan (BHMF) and 2,5‐dimethylfuran (DMF) were explored by regulating the nanosized Pt on Co/Al2O3 catalysts. Characterization results revealed that the catalyst acidity was influenced by adjusting the Co/Pt composition, while the addition of more Pt loading on Co/Al2O3 catalysts resulted in a facilitation of H2 reduction process. Lower size of catalyst particles was obtained for the Co−Pt system in comparison to the monometallic Co/Al2O3 catalyst. Additionally, the structural characterizations by XRD, XANES, and XPS established the co‐existences between metallic Pt0/Co0 and oxophilic PtO2/CoOx, acting as the active components for the reactions. Operated under a full HMF conversion, the Co1Pt0.050Al catalyst with high Pt loading gave >99.9 % BHMF selectivity at 40 °C; whereas, an 86.7 % of DMF selectivity was noticeable over low Pt loading of the Co1Pt0.013Al catalyst at 160 °C. This investigation evidenced that the selective production of BHMF or DMF towards hydro‐conversion of HMF was relied on the amount of Pt contents on Co/Al2O3 catalyst, in which the metal sizes and acidity had meaningful effects on the hydrogenation and hydrogenolysis processes.

Tailoring Cu immobilized MCM-41-based mesostructured catalysts for selective hydrogenolysis of biomass-derived furfural

The CuO-supported MCM-41 catalysts were prepared using a simple incipient wet impregnation method. The catalysts were investigated for hydrogenation of furfural to furfuryl alcohol synthesis. Among all the catalysts, the 2.5% CuO/MCM-41 catalyst shows the best catalytic performance with 92.5% conversion and 89% selectivity of furfuryl alcohol at 210 °C. The catalyst also demonstrated a high turnover frequency (TOF) of 154.4 h−1. The 2.5% CuO/MCM-41 catalyst remained stable for up to 20 h during the time on stream.

Rice husk-based biogenic silica-anchored Sn-Co bimetallic catalysts for cellulose hydrogenolysis: Structural regulation and mechanism study

The production of high value-added chemicals and materials from renewable biomass is significant for the sustainable development of chemical industry. Herein, rice husk-based biogenic silica-anchored Sn-Co catalysts with adjustable activity are successfully prepared for biomass valorization. By regulating the pretreatment method and carbothermal reduction temperature of catalysts, the interaction between Co, Sn and biogenic silica can be regulated, thereby regulating the catalytic activity of the catalyst for cellulose hydrogenolysis. 50.7 % yield of acetol and 63.4 % yield of C3 products can be obtained. A series of characterizations show that the hydrothermal pretreatment in CoCl2 solution promotes the combination of Co2+ and biogenic silica, which inhibits the excessive doping of Sn4+ and promotes the formation of Co3Sn2 alloy. The Sn-O-Si and Co3Sn2 species in 3Sn-5Co@RHC are the key active sites catalyzing glucose isomerization and fructose retro-aldol condensation. The intermediates experiments show that controlling the hydrolysis rate of cellulose to avoid excessive concentration of monosaccharide intermediates in the reaction system is crucial for inhibiting side reactions and improving the yield of acetol. The use of agroforestry waste-based catalytic materials for biomass conversion in this work can provide inspiration for exploiting the intrinsic characteristics of biomass to develop high value-added materials and chemicals.

Sustainable Production of Chemicals via Hydrotreating of CO2 and Biomass Derived Molecules Using Heterogeneous Noble Metal Oxide Catalysts

AbstractThe noble metals are widely used in heterogeneous catalysis and automobile industry. The limited natural sources and high cost of noble metals dictates improving the efficiency of modern industry. This review considers the applications of noble metal oxide as potential solutions to the sustainability issues, including biomass conversion, CO2 capture and conversion, green fuel production, etc. Noble metal oxides with their different compositions (monometallic and bimetallic) and structures exhibit a wide range of properties in heterogeneous catalysis. Although platinum metals in an oxidized form may not be the most common choice in hydroprocesses; recently, there have been studies indicating that they were highly active and selective catalysts in hydrogenation and hydrogenolysis. This review outlines the most established noble metal oxide catalysts used in hydrogenation catalysis and shed the light on the relation of noble metal oxide species to catalyst selectivity based on state‐of‐the‐art techniques. Finally, the perspectives on the application of noble metal oxide catalysts to produce value‐added chemicals are discussed.

Tailoring Cu/Hydroxyapatite Catalysts for Selective Hydrogenolysis of Biomass Derived Levulinic Acid to γ-Valerolactone Biofuel Additive

Background: Sustainable synthesis of γ-valerolactone (GVL) from levulinic acid (LA) offers a sustainable approach to converting biomass-derived feedstocks into valuable chemicals and fuel additves. Cu-Hydroxyapatite (Cu-HAp) catalysts are potential candidates for vapor-phase hydrogenation of LA to GVL due to their enhanced catalytic activity and selectivity through Cu nanoparticle support. Objective: This study aimed to investigate the catalytic performance of Cu-HAp catalysts in the hydrogenation of levulinic acid to γ-valerolactone. The primary goal was to optimize reaction conditions and assess the enhanced catalytic activity and selectivity Methods: The influence of copper loading, reaction temperature, and catalyst stability was evaluated. Moreover, the effect of time on stream (TOS) on LA conversion and GVL selectivity was examined by the best optimised Cu/HAp catalyst. Results: Cu-HAp catalysts exhibited favorable catalytic performance, with optimal conditions at approximately 5wt% copper loading. At this loading, maximum LA conversion (60%) and GVL selectivity (90%) were achieved after 8 hours on the stream at 265°C and 0.1 MPa conditions. Conclusion: The study demonstrates the efficacy of Cu-HAp catalysts for the hydrogenation of levulinic acid to γ-valerolactone. The findings indicate that as the copper loading increases from 2 to 20 wt%, the conversion of LA and the selectivity to GVL both decline. The analysis further implies that the dispersion of Cu species corresponds directly to the activity observed during the LA hydrogenation. The conversion of LA rises with a higher reaction temperature ranging from 250-320°C, although the selectivity of GVL decreases above 265°C. The catalyst's stability is crucial for maintaining efficient catalytic activity over time, with observed deactivation attributed to Cu metal particle aggregation and coke formation on active sites. The findings contribute to the development of robust catalyst systems for biomass-derived chemical transformations.

Study of promoted Cu/ZnO and Cu/ZrO2 catalysts for dimethyl adipate hydrogenolysis

Two supports (ZnO, ZrO2) and four promoters (Al2O3, ZnO, CoOx, NiO) were investigated to design environmentally-friendly Cu-based hydrogenolysis catalysts. Both catalyst characterization and activity in dimethyl adipate hydrogenolysis were described....

Nickel aluminate spinel-derived catalysts for aqueous-phase hydrogenolysis of glycerol with in-situ hydrogen production: Effect of molybdenum doping

The correlation between the physico-chemical properties of bare and Mo-doped nickel aluminate derived catalysts and product distribution during hydrogenolysis of glycerol with in situ produced hydrogen in continuous was investigated. Stoichiometric nickel aluminate spinel was synthesized via citrate sol-gel in a one-pot synthesis and subsequently doped it with 1 wt% Mo, using both sol-gel one-pot and impregnation methods. Catalytic runs were performed at 235 ºC/ 45 bar for 4 h TOS. The results indicate that Mo-doping increased the number of both metal and acid sites, leading to more selectivity towards deoxygenated products. 1,2-propylene glycol was the major liquid product, Mo/NiAl catalyst exhibited the highest yield (27%) and selectivity (39%). Post-reaction characterization revealed that leaching and oxidation of metals could potentially cause catalyst deactivation. 1 wt% Mo-doped nickel aluminate-derived catalysts possess potential for the selective production of 1,2-PG in a eco-friendly process through one-pot coupling H2 generation and hydrogenolysis reactions.

Isoreticular Metal-Organic Frameworks Confined Mononuclear Ru-Hydrides Enable Highly Efficient Shape-Selective Hydrogenolysis of Polyolefins.

Upcycling nonbiodegradable plastics such as polyolefins is paramount due to their ever-increasing demand and landfills after usage. Catalytic hydrogenolysis is highly appealing to convert polyolefins into targeted value-added products under mild reaction conditions compared with other methods, such as high-temperature incineration and pyrolysis. We have developed three isoreticular zirconium UiO-metal-organic frameworks (UiO-MOFs) node-supported ruthenium dihydrides (UiO-RuH2), which are efficient heterogeneous catalysts for hydrogenolysis of polyethylene at 200 °C, affording liquid hydrocarbons with a narrow distribution and excellent selectivity via shape-selective catalysis. UiO-66-RuH2 catalyzed hydrogenolysis of single-use low-density polyethylene (LDPE) produced a C12 centered narrow bell-shaped distribution of C8-C16 alkanes in >80% yield and 90% selectivity in the liquid phase. By tuning the pore sizes of the isoreticular UiO-RuH2 MOF catalysts, the distribution of the products could be systematically altered, affording different fuel-grade liquid hydrocarbons from LDPE in high yields. Our spectroscopic and theoretical studies and control experiments reveal that UiO-RuH2 catalysts enable highly efficient upcycling of plastic wastes under mild conditions owing to their unique combination of coordinatively unsaturated single-site Ru-active sites, uniform and tunable pores, well-defined porous structure, and superior stability. The kinetics and theoretical calculations also identify the C-C bond scission involving β-alkyl transfer as the turnover-limiting step.

Advances in Heterogeneous Catalysts for Lignin Hydrogenolysis.

Lignin is the main component of lignocellulose and the largest source of aromatic substances on the earth. Biofuel and bio-chemicals derived from lignin can reduce the use of petroleum products. Current advances in lignin catalysis conversion have facilitated many of progress, but understanding the principles of catalyst design is critical to moving the field forward. In this review, the factors affecting the catalysts (including the type of active metal, metal particle size, acidity, pore size, the nature of the oxide supports, and the synergistic effect of the metals) are systematically reviewed based on the three most commonly used supports (carbon, oxides, and zeolites) in lignin hydrogenolysis. The catalytic performance (selectivity and yield of products) is evaluated, and the emerging catalytic mechanisms are introduced to better understand the catalyst design guidelines. Finally, based on the progress of existing studies, future directions for catalyst design in the field of lignin depolymerization are proposed.

Recent Progress in Catalyst Development of the Hydrogenolysis of Biomass-Based Glycerol into Propanediols-A Review.

The use of biomass-based glycerol to produce chemicals with high added value is of great significance for solving the problem of glycerol surplus and thus reducing the production cost of biodiesel. The production of 1,2-propanediol (abbreviated as 1,2-PDO) and 1,3-propanediol (abbreviated as 1,3-PDO) via the hydrogenolysis of glycerol is one of the most representative and highest-potential processes for the comprehensive utilization of biomass-based glycerol. Glycerol hydrogenolysis may include several parallel and serial reactions (involving broken C-O and C-C bonds), and therefore, the catalyst is a key factor in improving the rate of glycerol hydrogenolysis and the selectivities of the target products. Over the past 20 years, glycerol hydrogenolysis has been extensively investigated, and until now, the developments of catalysts for glycerol hydrogenolysis have been active research topics. Non-precious metals, including Cu, Ni, and Co, and some precious metals (Ru, Pd, etc.) have been used as the active components of the catalysts for the hydrogenolysis of glycerol to 1,2-PDO, while precious metals such as Pt, Rh, Ru, Pd, and Ir have been used for the catalytic conversion of glycerol to 1,3-PDO. In this article, we focus on reviewing the research progress of the catalyst systems, including Cu-based catalysts and Pt-, Ru-, and Pd-based catalysts for the hydrogenolysis of glycerol to 1,2-PDO, as well as Pt-WOx-based and Ir-ReOx-based catalysts for the hydrogenolysis of glycerol to 1,3-PDO. The influence of the properties of active components and supports, the effects of promoters and additives, and the interaction and synergic effects between active component metals and supports are also examined.

Synergy of electronic and steric effects of Br-Ni catalysts for selective hydrogenolysis of diphenyl ether to phenol

Selective hydrogenolysis of 4-O-5 bond in lignin under relatively mild conditions is an important strategy for the production of valuable aromatic products, e.g. phenols, from renewable carbon resources. However, the easy saturation of benzene rings under reductive conditions over metal catalyst reduces the selectivity to aromatics. In this work, we investigated the effect of bromination of supported Ni nanoparticles on the phenol selectivity during the hydrogenolysis of diphenyl ether (DPE), a commonly used lignin model compound. Compared with the unmodified catalysts, Br-Ni/Al2O3 catalyst derived from Ni-Al layered double oxides exhibits enhanced phenol selectivity (37% vs. 15%) under similar DPE conversions (60%). Various characterizations including transmission electron microscopy (TEM), in-situ X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS), and CO-Fourier transform infrared spectroscopy (FTIR) indicate that Br preferentially located at the terrace site of Ni nanoparticles, deactivating the continuous Ni sites for benzene ring hydrogenation. In addition, the electron-withdrawing effect of Br creates positively charged Ni sites at the corners, facilitating the hydrogenolysis of C–O aryl ether bonds. During the hydrogenation of real lignin, the selective poisoning and electronic effects introduced by Br synergistically increased the yield of phenols from 12.20% on the initial Ni/Al2O3 to 30.47% over the Br-Ni/Al2O3 catalyst. This work provides an advanced strategy for the catalytic valorization of lignin by halogen modified metal-based catalysts.

Anchoring Co on CeO2 nanoflower as an efficient catalyst for hydrogenolysis of 5-hydroxymethylfurfural

Developing economical and efficient catalysts to accelerate sustainable fabrication of value-added chemicals and fuels from biomass remains a challenging task. Herein, Co species anchored on CeO2 nanoflowers catalyst, Co/CeO2-NF, were synthesized for catalyzing the efficient selective hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF). Co/CeO2-NF exhibited high 2,5-dimethylfuran (DMF) yield of 99 % at 160 °C, 2 MPa H2 within 5 h, and afforded excellent catalytic performance and stability after 5 times of reuse. The combination of various structural characterization and catalytic experiments reveals that the outstanding activity of Co/CeO2-NF stems from the unique nano-flower structure with high content oxygen vacancies, desired acid property, the high dispersed cobalt species and strong metal-support interaction. This study not only provides insight into the selective HDO of HMF, but also inspires the design of cheap heterogeneous catalysts for the HDO of renewable biomass to high-value-added chemicals.