To Tetrahydrofurfuryl Alcohol Research Articles

Highly Efficient and Selective Hydrogenation of Biomass-Derived Furfural Using Interface-Active Rice Husk-Based Porous Carbon-Supported NiCu Alloy Catalysts.

A series of bimetallic NixCuy catalysts with different metal molar ratios, supported on nitric acid modified rice husk-based porous carbon (RHPC), were prepared using a simple impregnation method for the liquid-phase hydrogenation of furfural (FFA) to tetrahydrofurfuryl alcohol (THFA). The Ni2Cu1/RHPC catalyst, with an average metal particle size of 9.3 nm, exhibits excellent catalytic performance for the selective hydrogenation of FFA to THFA. The 100% conversion of FFA and the 99% selectivity to THFA were obtained under mild reaction conditions (50 °C, 1 MPa, 1 h), using water as a green reaction solvent. The synergistic effect of NiCu alloy ensures the high catalytic activity. The acid sites and oxygen-containing functional groups on the surface of the modified RHPC can enhance the selectivity of THFA. The Ni2Cu1/RHPC catalyst offers good cyclability and regenerability. The current work proposes a simple method for preparing an NiCu bimetallic catalyst. The catalyst exhibits excellent performance in the catalytic hydrogenation of furfural to tetrahydrofurfuryl alcohol, which broadens the application of non-noble metal bimetallic nanocatalysts in the catalytic hydrogenation of furfural.

Selective hydrogenation of furfural over supported nickel and nickel phosphide catalysts

Supported Ni (60 wt% Ni) catalysts were prepared and phosphided into corresponding Ni2P catalysts. They were used for the hydrogenation of furfural as well as for the probe reactions (the hydrogenation of furan and propanal). The results demonstrated that the acidic support promoted the adsorption and hydrogenation of furan ring and aldehyde group over the nickel sites while the basic support played the opposite role. The IR spectra demonstrated that the aldehyde group was more easily hydrogenated than the furan ring at room temperature, implying the sequential hydrogenation of furfural to furfuryl alcohol (FA) and then to tetrahydrofurfuryl alcohol (THFA) over Ni. The microcalorimetric studies revealed that both the aldehyde group and furan ring were strongly adsorbed on Ni so that the Ni catalysts were highly active to hydrogenate the two groups, i.e., the Ni catalysts favored the formation of THFA. On the other side, although the adsorption heats of aldehyde group were much lower on Ni2P than on Ni, the adsorption heats were significantly higher for aldehyde group than for furan ring on Ni2P, implying the high selectivity to FA on Ni2P.

Reticular Coordination Induced Interfacial Interstitial Carbon Atoms on Ni Nanocatalysts for Highly Selective Hydrogenation of Bio-Based Furfural under Facile Conditions.

A rational design of transition metal catalysts to achieve selective hydrogenation of furfural (FFR) to tetrahydrofurfuryl alcohol (THFA) under facile conditions is a promising option. In this work, a series of Ni catalysts were synthesized by controlled thermal treatment of Ni-based metal-organic frameworks (MOFs), with the purpose of modulating the interface of nickel nanoparticles by the reticular coordination in MOF precursors. The catalytic performance indicates that Ni/C catalyst obtained at 400 °C exhibits efficient conversion of FFR (>99%) and high selectivity to THFA (96.1%), under facile conditions (80 °C, 3 MPa H2, 4.0 h). The decomposition of MOF at low temperatures results in highly dispersed Ni0 particles and interfacial charge transfer from metal to interstitial carbon atoms induced by coordination in MOF. The electron-deficient Ni species on the Ni surface results in an electropositive surface of Ni nanoparticles in Ni/C-400, which ameliorates furfural adsorption and enhances the hydrogen heterolysis process, finally achieving facile hydrogenation of FFR to THFA.

Immobilized highly dispersed Ni nanoparticles over porous carbon as an efficient catalyst for selective hydrogenation of furfural and levulinic acid

Sustainable catalysis is the key for the future progress toward biorefinery and bioeconomy. In this work, we designed and developed an inexpensive and eco-friendly Ni@C catalyst for selective hydrogenation of biomass-based platform molecules. A facile synthesized Ni nanoparticles encapsulated in a stabilized carbon support derived from a sacrificial agent copolymer-gel was investigated in the hydrogenation of furfural (FA) to tetrahydrofurfuryl alcohol (THFOL) and levulinic acid (LA) to γ-valeralactone (GVL). The aim is to study the two different reactions over a highly stabilized Ni nanoparticles embedded in the carbon matrix. The Ni@C was found to be active and selective in multi-catalyzed hydrogenation reactions. The Ni nanoparticles with small and ultra-fine sizes are highly dispersed over the carbon matrix. This was concluded through high-resolution micrography images (SEM, TEM) and XRD patterns. In both reactions, a complete conversion of furfural and levulinic acid was achieved with maximum selectivity over the Ni@C catalyst. The effect of reaction temperature, solvent type, reaction time, and H2 pressure were also studied. Overall, optimized reaction conditions were determined, and the Ni@C is easily reusable and exceptionally durable in the studied reaction cycles. The apparent activation energies for FA hydrogenation to THFOL and LA hydrogenation to GVL are 15.4 kJ/mol and 33.6 kJ/mol, respectively.

Catalytic hydrogenation of furfural to tetrahydrofurfuryl alcohol using competitive nickel catalysts supported on mesoporous clays

Nickel catalysts supported on mesoporous clays with different acid properties, such as montmorillonite MK-10, Al-pillared montmorillonite, mesoporous Na-saponite and mesoporous H-saponite, were prepared, characterized and tested for the hydrogenation of furfural to tetrahydrofurfuryl alcohol (THFA). Clays were also modified introducing basicity through magnesium oxide in different amounts. Catalysts with higher acidity or low amounts of metallic centres favoured deactivation and/or selectivity to the non-desired products. Interestingly, the addition of MgO both neutralized the acidity of the montmorillonite supports and improved the hydrogenation of the furanic ring, resulting in higher selectivity to THFA. The best catalyst was the one prepared with montmorillonite MK-10 covered by 30 wt% of magnesium oxide and with 8.8 % of the Ni metal phase achieving total conversion and total selectivity to THFA. The activity of this catalyst was maintained after several reuses.

Selective hydrogenolysis of furfuryl alcohol to 1,5- and 1,2-pentanediol over Cu-LaCoO3 catalysts with balanced Cu0-CoO sites

Selective hydrogenolysis of biomass-derived furfuryl alcohol (FFA) to 1,5- and 1,2-pentanediol (PeD) was conducted over Cu-LaCoO3 catalysts with different Cu loadings; the catalysts were derived from perovskite structures prepared by a one-step citrate complexing method. The catalytic performances of the Cu-LaCoO3 catalysts were found to depend on the Cu loading and pretreatment conditions. The catalyst with 10 wt% Cu loading exhibited the best catalytic performance after prereduction in 5%H2-95%N2, achieving a high FFA conversion of 100% and selectivity of 55.5% for 1,5-pentanediol (40.3%) and 1,2-pentanediol (15.2%) at 413 K and 6 MPa H2. This catalyst could be reused four times without a loss of FFA conversion but it resulted in a slight decrease in pentanediol selectivity. Correlation between the structural changes in the catalysts at different states and the simultaneous variation in the catalytic performance revealed that cooperative catalysis between Cu0 and CoO promoted the hydrogenolysis of FFA to PeDs, especially to 1,5-PeD, while Co0 promoted the hydrogenation of FFA to tetrahydrofurfuryl alcohol (THFA). Therefore, it is suggested that a synergetic effect between balanced Cu0 and CoO sites plays a critical role in achieving a high yield of PeDs with a high 1,5-/1,2-pentanediol selectivity ratio during FFA hydrogenolysis.

Supported Ultrafine NiCo Bimetallic Alloy Nanoparticles Derived from Bimetal–Organic Frameworks: A Highly Active Catalyst for Furfuryl Alcohol Hydrogenation

Highly dispersed NiCo bimetallic alloy nanoparticles have been successfully immobilized on the SiO2 frameworks by using heteronuclear metal–organic frameworks (MOFs) as metal alloy precursors. Catalyst characterizations revealed that the average size of NiCo alloy particles was less than 1 nm, with a total metal loading of about 20 wt %. As compared to individual Ni or Co MOF-derived catalysts and the catalysts prepared by the conventional impregnation method, the ultrafine NiCo/SiO2-MOF catalyst showed a much better catalytic performance in the catalytic hydrogenation of furfuryl alcohol (FA) to tetrahydrofurfuryl alcohol (THFA) under mild conditions, giving 99.8% conversion of FA and 99.1% selectivity to THFA. It was found that a significant synergistic effect existed between Co and Ni within the subnanometer NiCo/SiO2-MOF catalyst, which was 2 and 20 times more active than Ni/SiO2-MOF and Co/SiO2-MOF, respectively.

Short channeled Ni-Co/SBA-15 catalysts for highly selective hydrogenation of biomass-derived furfural to tetrahydrofurfuryl alcohol

Liquid phase and one-step reaction for furfural (FFR) hydrogenated to tetrahydrofurfuryl alcohol (THFA) was conducted by employing noble metal-absence and toxicity-free, bimetallic Ni-Co catalysts. The bimetallic Ni-Co catalysts with different molar ratio of Ni to Co and two monometallic catalysts (Ni, Co) were synthesized by conventional incipient-wetness impregnation method with short channeled SBA-15 as support. Among these catalysts, highly selective hydrogenation of FFR to THFA was attained over Ni-Co/SBA-15 catalysts. The impact of molar ratio of Ni/Co was studied with a fixed Ni loading (10 wt %) in bare support. The samples were characterized by N2 sorption, XRD, XPS, H2-TPR, SEM, TEM and CO chemisorption. The results confirmed that the reducibility of Ni-catalysts can be improved by incorporating Co metal and revealed that appropriate amount of spinel NiCo2O4 oxides is favorable to uniform and high dispersion of Ni0 and CoO over short channeled SBA-15, which would be benefit for the catalytic performance. For catalytic activity investigation, other four mesoporous SiO2 materials (MCM-41, MCM-4, MCF-2 and common SBA-15) were employed as supports to investigate the effect on the hydrogenation of FFR and the reaction parameters including the reaction temperature, initial of H2 pressure, reaction time and the reusability of the catalysts were also studied. 100% of FFR conversion and 92.1% of THFA selectivity were achieved at 90 °C, 50 bar of initial H2 and 2.0 h over catalyst Ni-Co/SBA-15 when the molar ratio of Ni to Co was 0.67.

Efficient and versatile CuNi alloy nanocatalysts for the highly selective hydrogenation of furfural

The development of efficient and environmental benign non-noble bimetallic nanocatalysts is highly desirable and attractive in the upgrading of biomass-derived platform compounds to high-valued chemicals. A series of highly dispersed and versatile CuxNiy (x/y=7:1, 3:1, 1:1, 1:3, 1:7) alloy supported nanocatalysts derived from layer double hydroxides (LDHs) precursors were fabricated and used for the selective hydrogenation of furfural to tetrahydrofurfuryl alcohol (THFA) and furfuryl alcohol (FOL). It was found that the chemical composition, preparation method and especially the reduction temperature of LDHs precursors greatly affected the properties of the resultant CuxNiy/MgAlO catalysts. Systematic characterizations revealed that the reduction temperature of catalyst precursor was closely related to the dispersion and homogeneous composition of CuNi alloy nanoparticle as well as the surface basicity of catalysts, which played crucial roles in achieving excellent catalytic performances. The optimized CuNi/MgAlO and Cu1Ni3/MgAlO nanocatalysts showed high activity and selectivity for the hydrogenation of furfural to THFA in ethanol compared with the monometallic Ni and the CuNi supported catalysts prepared with other methods, such enhanced catalytic performance was investigated to be enabled by the synergistic effect within the CuNi alloy nanoparticles. Interestingly, our bimetallic nanocatalysts could also realize efficient production of FOL from the selective hydrogenation of furfural at its aldehyde group by simply changing the solvent to methanol. Moreover, the bimetallic nanocatalysts showed good recyclability in the liquid phase hydrogenation. Our efficient and versatile CuNi alloy nanocatalysts not only provide promising candidates for effective upgrading of furfural but also broaden the application of non-noble bimetallic nanocatalysts for hydrogenative transformations.

Selective hydrogenation of furfural to tetrahydrofurfuryl alcohol over Ni/CNTs and bimetallic Cu[sbnd]Ni/CNTs catalysts

A series of Ni, Cu and bimetallic CuNi catalysts with different metals loadings supported on CNTs were prepared by impregnation methods for liquid-phase hydrogenation of furfural to tetrahydrofurfuryl alcohol (THFA). Various effects of reaction parameters such as, reaction temperature, reaction time, hydrogen pressure, different supports and different loading amount of Ni over both monometallic and bimetallic catalysts were fully studied. Among the catalysts investigated, 10 wt% Ni/CNT and bimetallic CuNi catalysts showed high conversion of furfural and selectivity towards THFA. Bimetallic CuNi catalysts exhibit the best catalytic performance of 100% conversion of furfural and up to 90.3% selectivity towards THFA at mild condition of 130 °C, 40 bar hydrogen and 10 h reaction time. CuNi bimetallic synergistic effect has been interpreted through XPS measurement and a possible hydrogen-transfer mechanism is proposed. The features of the CNTs supported catalysts were investigated via XRD, XPS, TEM, H2-TPR and the N2 adsorption–desorption isotherms. The Ni and bimetallic CuNi catalysts prepared in this work is inexpensive and simple, which makes them a promising candidate for the conversion of furfural to THFA.

Catalytic Conversions of Furfural to Pentanediols

Catalytic conversion processes of furfural to 1,5- and 1,2-pentanediols are reviewed. There are two reaction paths. One is the combination of total hydrogenation of furfural to tetrahydrofurfuryl alcohol (THFA) and selective hydrogenolysis of THFA to 1,5-pentanediol. The former reaction is catalyzed by noble metal catalysts such as Pd-based ones at low temperature (≤313 K), and the latter reaction is catalyzed by M–M′Ox catalysts (M = Rh or Ir; M′ = V, Mo, W or Re) at higher temperature (≥373 K). Another path has the ring-opening of furfuryl alcohol as a key step, and noble metal catalysts with basic supports such as hydrotalcite are effective. 1,2-Pentanediol can be produced via this path.

Single-Pot Formation of THFAL via Catalytic Hydrogenation of FFR Over Pd/MFI Catalyst

Furfural (FFR) was selectively hydrogenated in a single pot to tetrahydrofurfuryl alcohol (THFAL) over a Si–MFI molecular sieve supported Pd catalyst. Studies on catalyst screening revealed that both the metal function and the support were critical for directing the selectivity to the ring-hydrogenated product, THFAL. The structural feature of MFI as shown by XRD was completely retained in the used sample of the 3% Pd/MFI catalyst confirming its stability under reaction conditions. XRD, along with SEM characterization of the used samples, established retention of morphology of the structured silicate, suggesting a strong interaction between hexagonal porous silicate and Pd particles. The complete conversion of FFR with an enhanced selectivity of 95% to THFAL could be achieved by recycling the crude of the first hydrogenation experiment over the same 3% Pd/MFI catalyst.

Highly Selective Decarbonylation of 5‐(Hydroxymethyl)furfural in the Presence of Compressed Carbon Dioxide

Less is more: The integrated development and optimization of catalysts and reaction media led to a highly selective decarbonylation of 5-(hydroxymethyl)furfural (HMF) to furfuryl alcohol (FFA) with an iridium/phosphine catalyst in the presence of compressed carbon dioxide. Subsequent hydrogenation over ruthenium nanoparticles (RuNPs) led to tetrahydrofurfuryl alcohol (THFA), a possible solvent for the decarbonylation reaction (see scheme). Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Preparation and Catalytic Performance of Ni-B Amorphous Alloy Supported by Chitosan/SiO 2

Ni-B amorphous catalyst supported by chitosan (CS)-modified silica (Ni-B/CS/SiO 2) was prepared using impregnation-reduction method. The as-prepared catalysts were characterized using X-ray powder diffraction (XRD), fourier transform infrared (FTIR) spetra, inductively coupled plasma (ICP) spectrometer, Brunauer-Emmett-Teller (BET) method, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). The results showed that the particle sizes, the surface content of Ni active species, and catalytic activity were improved by introducing chitosan to the surface of silica. In the hydrogenation of furfuryl alcohol (FA) to tetrahydrofurfuryl alcohol (THFA), the amorphous Ni-B/CS/SiO 2 catalyst exhibited superior catalytic activity to the corresponding traditional Ni-B/SiO 2 amorphous catalyst and Raney Ni.

Hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol on NiB/SiO2 amorphous alloy catalyst

NiB/SiO2 amorphous alloy catalyst was prepared by power electroless plating method and characterized by induction coupled plasma (ICP), Brunauer-Emmett-Teller method (BET), transmission electron microscope (TEM) and X-ray diffraction (XRD) techniques. The catalytic performance of NiB/SiO2 was investigated for the hydrogenation of furfuryl alcohol (FA) to tetrahydrofurfuryl alcohol (THFA). The effects of operational conditions, such as reaction temperature, pressure, and stirring rate were carefully studied. The proper conditions were determined as the following: pressure 2.0 MPa, temperature 120°C and stirring rate 550 r/min. A typical result with FA conversion of 99% and THFA selectivity of 100% was obtained under such conditions, which was close to that over Raney Ni.

Experimental study for liquid phase selective hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol on supported Ni catalysts

The liquid phase hydrogenation of furfuryl alcohol (FA) to tetrahydrofurfuryl alcohol (THFA) on a series of new special supported Ni catalyst was experimentally studied while the raw material and the product were analyzed by a set of on-line GC. The reactor used in the experiment was a continuous stirred autoclave with volume of 500 mL. The operating conditions studied in the experiments were opted as the following ranges: temperature within 433–453 K, pressure within 3.0–4.0 MPa, catalyst loading 20 g/L and the stirring rate at about 1000 rpm. The experimental results show that, under the operation conditions mentioned above, the hydrogenation of FA in the presence of the catalyst QD3 can lead to a high FA conversion above 99.9% and a high selectivity of THFA higher than 98.3% within 3.5 h.