Hydrodeoxygenation Of 5-Hydroxymethylfurfural Research Articles

Tuning ligand-vacancies in Pd-UiO-66 to boost biofuel production from 5-hydroxymethylfurfural hydrodeoxygenation

The hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) to biofuel 2,5-dimethylfuran (DMF) serves as a vital reaction in biomass refineries. Herein, Pd-UiO-66 catalysts with controlled contents of ligand-vacancies were developed for the HMF-to-DMF conversion. Strikingly, a volcano-like relationship between defect level and HDO activity was obtained. The DMF yield was promoted ∼3 times, reaching 92.2 % at 160 °C and 15 bar H2, which refers to a high-level turnover frequency value of 42.66 h−1 among the reported candidates. The Pd-UiO-66 catalysts also afforded >80 % yield for the HDO of 5-methyl furfural, furfural, and vanillin. Besides, high HDO activity could be retained in five recycles. Manipulating the contents of ligand-vacancies was confirmed to create more Pd0 species and Bronsted acid sites, leading to remarkable performance. This work provides significant inspiration for tuning structural defects in MOFs to realize the efficient HDO of platform molecules in biomass valorization.

Recent Progress in the Selective Hydrodeoxygenation of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran With Metal‐Containing Catalysts

AbstractLiquid fuel, such as 2,5‐dimethylfuran (DMF), from biomass, is an efficient, potential alternative to fossil‐based fuels due to its exceptional properties, including lower volatility, a remarkable octane number, heightened energy density, and immiscibility with water. DMF can be the starting substrate for producing bio‐based p‐xylene through the Diels‐Alder reaction with ethylene to produce biobased polyethylene terephthalate (PET). This review, thus, discusses the catalytic role of various precious and non‐precious metals on different supports, such as carbon, metal‐oxide, zeolite, and hydrotalcite, for the production of DMF via catalytic hydrodeoxygenation (HDO) of 5‐hydroxymethylfurfural (HMF) based on the previously reported literature. Various characteristic properties of the employed catalytic materials, such as particle size, metal‐support and substrate interaction, surface area, porosity, and acidic and basic sites, are delineated, playing a crucial role in the HDO of HMF to DMF. The influence of various reaction parameters, such as hydrogen atmosphere, solvents‐ including hydrogen donor solvents‐ and temperature are also discussed.

Selective hydrodeoxygenation of 5-hydromethylfurfural to 2,5-dimethylfuran over PtFe/C catalyst

2,5-dimethylfuran (DMF), a promising biomass-derived fuel, is synthesized via the hydrodeoxygenation of 5-hydroxymethylfurfural (HMF). This study focuses on the inherent activity of a 5Pt5Fe/C catalyst for HMF hydrodeoxygenation to DMF. The catalyst exhibited exceptional performance, achieving a remarkable DMF yield of 99.6 %. It displayed specific selectivity for C = O bond hydrogenation and CO bond cleavage in diverse substrates, producing high yield of 2-methylfuran from furfural and furfury alcohol, and high yield of toluene from benzaldehyde, benzyl alcohol. In-depth characterizations unveiled valuable insights into the 5Pt5Fe/C catalyst's properties, emphasizing a harmonious balance between metal and acid sites due to the interactive synergy between Pt and Fe species, enhancing hydrodeoxygenation activity. Additionally, the catalyst demonstrated satisfactory stability, maintaining a commendable DMF yield over five reaction cycles despite observed changes.

Process integration and systems optimization for the hydrodeoxygenation of 5-hydroxymethylfurfural to dimethylfuran

Most biomass reaction studies have focused on optimizing product yield without considering cost and emissions as key metrics; they consider pure feeds without accounting for process integration resulting from separation and recycling and often change one parameter at a time to maximize yield. Here, we propose a framework to overcome the above issues. We demonstrate it for the hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) to produce 2,5-dimethylfuran (DMF), a crucial reaction in making lignocellulosic biomass-based platform chemicals. We consider the impact of water in the feed stemming from the sugar dehydration reactor on the HDO in 2-pentanol over a Ru/C catalyst, guided by an active learning experimental design (NEXTorch toolkit), combined with Aspen Plus process flowsheet simulation, techno-economic analysis and life cycle assessment. We demonstrate that Bayesian optimization of process flowsheets significantly reduces production costs by 26% and greenhouse gas emissions by 15% after striking a balance between raw material usage, solvent loss, and utility consumption. Such reductions are strongly correlated to the product yield due to the dominant cost of the feed. Interestingly, a slight amount of water negatively impacts greenhouse gas emissions more than production costs, requiring relatively high purity in process integration.

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.

Efficient and Selective Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran by a Bimetallic Copper‐Palladium Catalyst on a Carbon‐Doped Boron Nitride Support

AbstractIn the present world, 2,5‐dimethylfuran (DMF), as a renewable liquid fuel, is valuable for maintaining ecological stability. Therefore, it is quite necessary to enhance the selectivity of DMF during the hydrodeoxygenation (HDO) of 5‐hydroxymethylfurfural (HMF) to DMF. In this paper, a copper‐palladium bimetal supported on carbon‐doped boron nitride (BCN) catalyst was prepared as a class of catalyst for HDO. Notably, under the combined action of Cu−Pd alloy and support, the catalyst of 10Cu3Pd/BCN showed remarkable activity with high selectivity (99.2 %) for DMF. In addition, the packing and dispersion of the alloy particles by the carrier improved the cycling performance of the catalyst. Therefore, the selection of 10Cu3Pd/BCN as a catalyst for HDO has excellent application prospects.

Nitrogen-doped carbon for selective pseudo-metal-free hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran: Importance of trace iron impurity

Heteroatoms-doped carbon materials have recently emerged as effective catalysts for various chemical and electrochemical reactions. The free of metals especially noble metals reduces cost and eliminates issues like sintering or leaching of metals at elevated temperatures in solvents. In this work, selective hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) is for the first time achieved over simple nitrogen-doped carbon (N-C) catalysts. At optimal reaction conditions, a 91% yield of DMF is obtained with excellent catalyst stability. Extensive characterization, including extended X-ray absorption fine-structure (EXAFS) and soft X-ray absorption spectroscopy (sXAS), model reactions, basic data science analysis, and DFT calculations suggest that ppm of Fe in particular FeN3 sites formed in pyrolysis, rather than non-metallic elements, drive key steps such as H2 activation and deoxygenation of –OH during HMF HDO.

Selective hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) over carbon supported copper catalysts using isopropyl alcohol as a hydrogen donor

Selective hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural to 2,5-dimethylfuran is of great importance. We reveal a simple pathway for green and efficient HDO using readily available copper with in-situ hydrogen generation. A highly dispersed Cu/PBSAC catalyst consisting of small metallic Cu0 nanoparticles carries out isopropyl alcohol (IPA) dehydrogenation and subsequent HDO of HMF. Density functional theory calculations reveal that the dehydrogenation of IPA is more favorable on Cu(211) with a lower energy barrier of ~0.6 eV. This facet exists in a higher ratio on nanosized catalysts. Batch reactions using Cu/PBSAC at 190 °C exhibited 91.9% HMF conversion and 71.7% DMF selectivity in 6 hr, and > 96% DMF yield in 10 hr. The mechanical strength of the carbon support is ideal for continuous processing for increased productivity; we demonstrate a > 90% DMF yield at 1/WHSV of 2.4 hr. The process demonstrated here can be integrated with upstream HMF separation utilizing carbon adsorbents.

Crystal-phase engineering of PdCu nanoalloys facilitates selective hydrodeoxygenation at room temperature

Selective hydrodeoxygenation of biomass-derived aromatic alcohols to value-added chemical or fuel is of great importance for sustainable biomass upgrading, and hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) is one of the most attractive reactions. Achieving the conversion of HMF to DMF using H2 at ambient temperature is challenging. In this work, we used PdCu nanoalloys to catalyze the selective hydrodeoxygenation reaction of HMF to DMF using H2 as the reducing agent. The reaction path and the product selectivity are governed by the crystallographic phase of the PdCu nanoalloys. It was discovered that body-centered cubic (BCC) PdCu nanoalloys supported on activated carbon (AC) exhibited outstanding performance with 93.6% yield of DMF at room temperature (PdCu/AC-BCC). A combination of experimental and density functional theory (DFT) studies showed that the tilted adsorption modes of furanic intermediates on PdCu-BCC nanoalloy surfaces accounted for the high selectivity of DMF; however, furan ring was activated on PdCu face-centered cubic (FCC) nanoalloy surfaces. Furthermore, PdCu/AC-BCC could also catalyze the hydrodeoxygenation of other aromatic alcohols at room temperature while maintaining the aromatic structures. This work opens the way for selective hydrodeoxygenation of the aromatic alcohols at room temperature with the aromatic ring intact.

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

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

Dual Metal–Acid Pd-Br Catalyst for Selective Hydrodeoxygenation of 5-Hydroxymethylfurfural (HMF) to 2,5-Dimethylfuran at Ambient Temperature

Supported metal catalysts have found broad applications in heterogeneous catalysis. In the conventional bifunctional catalyst, the active metal sites are associated with the metal nanoparticles, while the acid sites are usually localized over the oxide support. Herein, we report a novel type of supported metal bifunctional catalyst, which combined the advantages of the promotion and bifunctionality. The catalyst was designed by the pretreatment of supported palladium catalysts with bromobenzene. The promotion with bromine creates Bronsted acid sites, which are localized directly on the surface of metal nanoparticles. An intimacy between metal and acid functions in this bifunctional catalyst generates unique catalytic properties in hydrodeoxygenation of 5-hydroxymethylfurfural to dimethylfuran, occurring with the yield up to 96% at ambient temperature under 5 bar of H-2. The catalyst exhibits stable catalytic performance.

Selective Hydrodeoxygenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Alloyed Cu−Ni Encapsulated in Biochar Catalysts

Alloyed Cu−Ni encapsulated in carbon was prepared by loading Ni and Cu onto biochar (BC) through an initial wetness impregnation method under mild conditions. The bimetallic catalysts were exploited to perform selective hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF). 2,5-Dimethylfurfural (DMF), a promising liquid fuel/fuel additive, could be obtained from HMF with the highest yield of 93.5% under the optimized conditions. During HMF HDO, two key intermediates, 5-methylfurfural (MFF) and 2,5-dihydroxymethylfuran (DHMF), dominating two distinct conversion pathways were systematically investigated by Arrhenius kinetics analysis. In addition, the turnover frequencies (TOFs) of HDO reaction over Cu−Ni/BC corresponding with Cu amount were thoroughly discussed, finding that the electron transfer from Cu to Ni in the alloy structure was beneficial to the HDO reaction and the conversion pathways can be regulated by reaction temperature variation. Importantly, the synergy of HDO of HMF by alloyed Cu−Ni m...

Selective Hydrodeoxygenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Ni Supported on Zirconium Phosphate Catalysts.

Crystal α-zirconium phosphate (α-ZrP) was prepared by a hydrothermal method and exfoliated into a layered structure by n-hexylamine (C6H13NH2). Ni-based catalyst (Ni/ZrP) was promoted by loading nickel on the layered α-ZrP via ion exchange. The catalyst was performed to catalyze hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF), and a 68.1% yield of DMF and 100% conversion of HMF were achieved at 240 °C, 5 MPa H2, and 20 h. The DMF yield can still retain 52.8% after five cycles. The characteristics of the catalyst were investigated via N2 adsorption–desorption, X-ray diffraction, field emission scanning electron microscopy, high-resolution transmission electron microscopy, pyridine-adsorbed Fourier transform infrared (FTIR) spectra, FTIR spectra, inductively coupled plasma mass spectrometry, and thermogravimetric analysis–mass spectrometry, as well as Raman spectroscopy. A pathway from HMF to DMF was found with MF as the intermediate product, and DMF production was preferable via the −CH2OH group hydrogenolysis of HMF over Lewis acidic sites of Ni/ZrP, which is caused by the zirconium vacant orbits.

Selective Hydrodeoxygenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran over Heterogeneous Iron Catalysts.

This work provided the first example of selective hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) over heterogeneous Fe catalysts. A catalyst prepared by the pyrolysis of an Fe-phenanthroline complex on activated carbon at 800 °C was demonstrated to be the most active heterogeneous Fe catalyst. Under the optimal reaction conditions, complete conversion of HMF was achieved with 86.2 % selectivity to DMF. The reaction pathway was investigated thoroughly, and the hydrogenation of the C=O bond in HMF was demonstrated to be the rate-determining step during the hydrodeoxygenation, which could be accelerated greatly by using alcohol solvents as additional H-donors. The excellent stability of the Fe catalyst, which was probably a result of the well-preserved active species and the pore structure of the Fe catalyst in the presence of H2 , was demonstrated in batch and continuous flow fixed-bed reactors.

Base metal-Pt alloys: A general route to high selectivity and stability in the production of biofuels from HMF

Hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) was examined over well-defined and uniform, Pt-Ni, Pt-Zn and Pt-Cu alloyed nanocrystals (NCs) supported on carbon, at 33bar and between 160 and 200°C. Pt-Ni alloy catalysts were prepared in three different Pt:Ni ratios, Pt6Ni, Pt3Ni, and PtNi. While all of the Pt-Ni alloys were more selective for producing 2,5-dimethylfuran (DMF) than were Pt or Ni monometallic catalysts, the Pt3Ni catalyst was superior to the other compositions, exhibiting a yield of 98% due to its optimum surface composition. Similarly high yields were obtained on catalysts prepared from Pt2Zn and PtCu NCs. Possible reasons are given for why each of the Pt-alloy catalysts is highly selective.

Mechanisms for High Selectivity in the Hydrodeoxygenation of 5-Hydroxymethylfurfural over PtCo Nanocrystals

Carbon-supported, Pt and PtCo nanocrystals (NCs) with controlled size and composition were synthesized and examined for hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF). Experiments in a continuous flow reactor with 1-propanol solvent, at 120 to 160 °C and 33 bar H2, demonstrated that reaction is sequential on both Pt and PtCo alloys, with 2,5-dimethylfuran (DMF) formed as an intermediate product. However, the reaction of DMF is greatly suppressed on the alloys, such that a Pt3Co2 catalyst achieved DMF yields as high as 98%. XRD and XAS data indicate that the Pt3Co2 catalyst consists of a Pt-rich core and a Co oxide surface monolayer whose structure differs substantially from that of bulk Co oxide. Density functional theory (DFT) calculations reveal that the oxide monolayer interacts weakly with the furan ring to prevent side reactions, including overhydrogenation and ring opening, while providing sites for effective HDO to the desired product, DMF. We demonstrate that control over metal nanopart...

Comparison of HMF hydrodeoxygenation over different metal catalysts in a continuous flow reactor

The three-phase hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) and hydrogenation of 2,5-dimethylfuran (DMF) were studied over six carbon-supported metal catalysts (Pt, Pd, Ir, Ru, Ni, and Co) using a tubular flow reactor with 1-propanol solvent, at 180°C and 33bar. By varying the space time in the reactor, the reaction of HMF is shown to be sequential, with HMF reacting first to furfuryl ethers and other partially hydrogenated products, which then form 2,5-dimethylfuran (DMF). Ring-opened products and 2,5-dimethyltetrahydrofuran (DMTHF) were produced only from reaction of DMF. Rate constants for the pseudo-first-order sequential reactions were obtained for each of the metals. The selectivities for the reaction of DMF varied with the metal catalyst, with Pd forming primarily DMTHF, Ir forming a mixture of DMTHF and open-ring products, and the other metals forming primarily open-ring products. Catalyst stabilities followed the order Pt∼Ir>Pd>Ni>Co>Ru. Since the stability order correlated with carbon balances in the product (>93% for Pt; <75% for Ru), deactivation appears to be caused by deposition of humins on the catalyst.