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Proposed reaction pathways for the hydrogenolysis of HMF. Reproduced with permission.[⁸⁹] Copyright 2021, Elsevier.
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2,5-Dimethylfuran (DMF) is considered one of the most promising liquid transport fuels due to its high energy density, high boiling point, high octane number, and immiscibility with water. It can be obtained mainly by hydrogenolysis of biomass-derived 5-hydroxymethylfurfural (HMF) over metal catalysts. This review describes the latest research prog...
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Alkyl levulinates (AL), which are important biomass derivatives, have the potential of conversion into different valuable compounds. This study addressed the production of alkyl levulinate from xylose by applying mesoporous zirconium phosphates (AL-MZP-Pr-SO3H, MZP-Pr-SO3H), which served as good heterogeneous catalysts. The characterization of thes...
Citations
... HMF is a highly reactive chemical that can be used to synthesize numerous chemicals with high value-added through oxidation, hydrogenation, and other chemical reactions and is widely used in the fields of chemical engineering, energy, materials, and medicine [8][9][10][11][12][13][14][15][16]. BHMF, as a biomass-based furan derivative, is a chemical intermediate with very broad potential applications in biomass-based polymer materials, pharmaceuticals and flavors, etc. [17,18]. In recent years, BHMF has received increasing attention from both the academic and industrial communities. ...
The development of biodegradable materials from biomass is a crucial strategy for leveraging biomass resources. A key component in this process is 2,5-bis(hydroxymethyl)furan (BHMF), a significant biomass-derived platform chemical. However, producing BHMF with high selectivity through the selective hydrogenation of 5-hydroxymethylfurfural, while avoiding the creation of unwanted byproducts, is a complex challenge. In our research, we have developed a novel catalyst featuring a magnetic core. This catalyst, which consists of platinum loaded onto a graphene-like shell, has been applied to the catalytic hydrogenation of HMF in an aqueous environment. Under the optimized conditions of 373 K, 3 MPa H2, and 1 h reaction time, a BHMF yield exceeding 99% was achieved. This method presents a promising and effective approach for the high-value conversion of biomass waste into polymer materials and pharmaceutical chemicals.
Graphical Abstract
... Although fundamental research in related fields has made great progress, there are still many problems that limit the practical industrial application of renewable energy. 1,2 For example, selective hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) can produce 2,5-dimethylfuran (DMF), which is more charming as a biofuel compared with the well-known ethanol because DMF possesses higher energy density (by 40%), higher boiling point (by 20 K), and lower solubility in water. 3 In this reaction, researchers have gained deep insights into the composition and surficial/ interfacial structure of supported catalysts to achieve high DMF yield. ...
... Generally speaking, Ni can better promote the hydrogenation of the C C bond because of its narrow d-band width, [16][17][18] but it leads to more side reactions and is not conducive to the formation of products. 1 It has been shown that Cu-based catalyst is a good active metal for 5-HMF hydrogenation because of its inherent repulsion of C atoms and its inhibition of C C hydrogenation and C C cracking. [19][20][21] However, compared with Ni and other hydrogenated active metals, Cu has a poor ability to dissociate H 2 , and its ability to hydrodissociate C O bond is also low. ...
Reducing catalyst costs and reaction energy consumption is a potent way to advance biorefinery energy from fundamental research to industrial implementation. Herein, we developed a series of low‐cost CuCo/Al2O3 catalysts for hydrodeoxygenation of 5‐hydroxymethylfurfural to biofuel 2,5‐dimethylfuran (DMF). Combined characterizations showed CuCo alloy and Co@CuCo core–shell structures were successfully constructed by reducing layered double hydroxides (LDHs) at different temperatures. Detailed catalytic performance studies found that Co@CuCo catalyst achieved a decent DMF yield of 91.7% under 130°C and 1 MPa H2, which is milder than most literatures. While the CuCo alloy catalyst only gave 23.2% yield. H2‐TPD and in situ‐IR indicated the CuCo‐alloy shell can prevent oxidation of Co core, so that maintain its high H2 dissociation capacity. Moreover, the electronic structure changes in the Cu–Co alloy promote the hydrolysis of CO bond. Hence, the local atomic arrangement and corresponding electronic structure in the Co@CuCo structure jointly strengthened the low‐temperature reactivity.
... The removal of oxygen via catalytic hydrodeoxygenation (HDO) is one of the most effective processes to upgrade biomass derivatives [9][10][11][12]. Due to its high energy density, high boiling point, high octane number, and immiscibility with water, 2,5-dimethylfuran (DMF), as a HDO product of HMF, is considered one of the most promising liquid transport fuels [13]. Additionally, ethylbenzene (EB), γ-valerolactone (GVL), and 2methylfuran (2-MF), as HDO products of AP, LA and FF, respectively, have been extensively adopted in the production of polymers, pharmaceuticals, and other fine chemicals [14][15][16]. ...
... There is an urgent need for development of non-noble metal catalysts, such as Ni, Zn, and Cu, because of their economic sustainability [22]. Among those mentioned, Ni with narrow d-band width can promote the hydrogenation of C--C bonds, which will lead to the formation of more byproducts [13]. Zn species have low catalytic activity for C -O bond cleavage [23]. ...
The efficient hydrodeoxygenation (HDO) of biomass derivatives to yield specific products is a significant yet challenging task. In the present study, a Cu/CoOx catalyst was synthesized using a facile co-precipitation method, and subsequently used for the HDO of biomass derivatives. Under optimal reaction conditions, the conversion of 5-hydroxymethylfurfural reached 100% with a selectivity of ∼99% to 2,5-diformylfuran. In combination with the experimental results, systematic characterizations revealed that CoOx, as the acid site, tended to adsorb CO bonds, and the metal sites of Cu+ were inclined to adsorb CO bonds and enhance CO bond hydrogenation. Meanwhile, Cu0 was the main active site for 2-propanol dehydrogenation. The excellent catalytic performance could be attributed to the synergistic effects of Cu and CoOx. Further, by optimizing the ratio of Cu to CoOx, the Cu/CoOx catalysts exhibited notable performance in HDO of acetophenone, levulinic acid, and furfural, which verified the universality of the catalysts in the HDO of biomass derivatives.
... Biomass-derived 5-hydroxymethylfurfural (HMF), containing C-O, C=O, and furan ring, has received much attention for its desirable functional constituents, which not only permits flexible access to bio-polymer and biofuel production, but also can be employed as an example to illustrate mechanism of hydrogenation [10,11]. Among HMF hydrogenation products, 2,5-dimethylfuran (DMF) has been recognized as a promising biofuel due to its higher energy density, high research octane number, and lower water solubility, and 2,5-dihydroxymethylfuran (DHMF) is a crucial versatile intermediate to high value polyesters product [12,13]. ...
Much attention has been attracted on the production of renewable biofuels through efficient catalytic transfer hydrogenation (CTH) reaction. In this study, a series of Cu/CoCeOx catalysts were synthesized by a facile coprecipitation method for CTH of 5-hydroxymethylfurfural (HMF) to different products with 2-propanol as a hydrogen donor, and the dual active sites of CuCo and CoCeOx were tuned via H2-reduction temperature. A 92.2% yield of 2,5-dihydroxymethylfuran (DHMF) was achieved at 150 °C over the Cu4Co8Ce4-300 catalyst, and a 95.4% yield of 2,5-dimethylfuran (DMF) was obtained over the Cu4Co10Ce2-600 catalyst at 170 °C. The roles of the dual active sites were further investigated, and the results showed that Cu species were identified as the major active sites of 2-propanol dehydrogenation, CoCeOx sites were responsible for the conversion of HMF to DHMF, and CuCo bimetallic nanoparticles promoted the cleavage of C-O in DHMF to obtain DMF. XRD, Raman, and HAADF-STEM analysis confirmed the existence of these sites. XPS and H2-TPR verified the formation of CuCo bimetallic nanoparticles, and NH3-TPD was employed to evaluate the acidity of the surface. Furthermore, in situ DRIFT of furfuryl alcohol and performance test experiments were conducted to understand the synergistic mechanism of dual active sites in hydrogen transfer from 2-propanol to HMF. This work provides a strategy to obtain different target products via tuning dual active sites.
... In this regard, the utilization of renewable biomass resources for environmentally friendly products is attracting more and more attention [1][2][3][4]. For example, Diol [5][6][7][8], dibasic acid [9][10][11][12] and diamine [13][14][15] as polymer monomer and cyclopentanone derivatives [16][17][18][19][20] as high value-added fine chemicals could be obtained from biomass; 2,5-dimethylfuran [21][22][23], which originated from carbohydrates, was a promising fuel candidate. Millions of tons of biodiesel were produced from the transesterification of fatty acids with methanol every year [24,25]. ...
The production of methyl lactate as a degradable polymer monomer from biomass was an important topic for a sustainable society. In this manuscript, glycerol was oxidated to methyl lactate catalyzed by the combination of Au-CuO and Sn-Beta. The influence of Sn content, Sn source, and the preparation conditions for Sn-β was studied. The Au content in Au/CuO was also investigated by varying the Au content in Au/CuO. The catalysts were characterized by XRD, FTIR spectroscopy of pyridine adsorption, and TEM to study the role of Sn and the influence of different parameters for catalyst preparation. After the optimization of reaction parameters, the yield of methyl lactate from glycerol reached 59% at 363 K after reacting in 1.6 MPa of O2 for 6 h.
Designing highly efficient non-noble metal catalyst for the selective hydrogenolysis of biomass derivatives to fuels and fine chemicals is a key pursuit for sustainable chemical industry but substantially challenging. In this contribution, we report, for the first time, the construction of amorphous bimetal Ni–Fe borides for efficient catalytic hydrogenolysis of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dimethylfuran (DMF) as a promising biofuel candidate. The as-prepared Ni1.52Fe0.36BOx catalyst afforded a near-quantitative DMF yield using ethanol as a green solvent under relatively mild operating conditions (1 MPa H2, 160 °C and 1 h), leading to an excellent DMF formation rate of 16.5 mmolDMF·gcat⁻¹·h⁻¹, which is 1.7–16.5 folds higher than the state-of-art nickel-based catalysts. Mechanistic investigations demonstrated that the Fe intervention is conductive to the generation of electron-enriched metal sites and powerful acidic sites in Ni1.52Fe0.36BOx catalyst, which favored the activation of hydrogen and the cleavage of C–O bond to accelerate the hydrogenolysis process. Moreover, Ni1.52Fe0.36BOx catalyst exhibited good recyclability as well as universality in the hydrogenolysis of various biomass-derived unsaturated aldehydes. This finding opens a new avenue for highly selective hydrodeoxygenation of renewable biomass feedstock to value-added chemicals with non-noble bimetal hybrids in a green and straightforward manner.
trans-Anethole (trans-AN) is widely applied in food, daily necessities, and pharmaceuticals and is typically available from inefficient natural oil extraction or complex organic transformations over mineral acid or noble metals. Here, a green and sustainable route was developed to stereoselectively produce trans-AN (ca. 90% selectivity) over an organic polymeric phosphonate-hafnium catalyst (PAS-Hf) through the cascade transfer hydrogenation and dehydration of biomass-based 4'-methoxypropiophenone (4-MOPP), with an environmental impact factor (E-factor) of 47.73. The porous structure and the enhanced hydrophobicity of the spherical catalyst PAS-Hf ensured the formation of more accessible and stable Lewis (Hf4+) and Brønsted (SO3H) acid active sites, which could be used for rapid conversion of biomass-based 4-MOPP to AN (100% conversion, 97.2% yield) in 0.5-2 h (TOF: 9.3 h-1). Density functional theory (DFT) calculations elucidated that the addition of PAS-Hf could remarkably facilitate the overall conversion process by decreasing the reaction energy barrier (151.33 to 48.27 kJ mol-1) of the rate-determining step. The good thermal stability and heterogeneity of the bifunctional catalyst were responsible for its constant activity during at least five consecutive cycles. The synergistic/relay catalysis of Lewis acid-base and Brønsted acid species could be extended to more than ten kinds of aldehydes and ketones. This acid-base multi-catalytic protocol has considerable potential in cascade biomass conversion via heterogeneous catalysis without any base additive.
The hydrodeoxygenation (HDO) 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 heterogeneous catalytic HCOOH-mediated HDO 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 literatures. 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.
With increasing concern for reducing CO2 emission and alleviating fossil resource dependence, catalytic transformation of 5‐hydroxymethylfurfural (HMF), a vital platform compound derived from C6 sugars, holds great promise for producing value‐added chemicals. Among several well‐established catalytic systems, hydrogenation and oxidation processes have been efficiently adopted for upgrading HMF. This Review covers recent advances in the development of thermocatalytic conversion of HMF into value‐added chemicals. The advances of metal‐catalyzed hydrogenation, hydrogenolysis, ring‐opening, decarbonylation, and oxidation involving selective activation of C−O, C=O, and C=C groups are described. The roles played by nature of metals, supports, additives, synergy of metal–acid sites, and metal–support interaction are also discussed at the molecular level. Finally, an outlook is provided to highlight major challenges associated with this huge research area.
