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FUEL · 2025 · IF 7.5

TiO2 layer coated MoO3 nanorod supported Ni catalyst for selective hydrogenolysis of cellulose to ketones and alcohols

Jie Wang,Quanxing Zheng,Hongliang Lu,Jianqiang Fan,Xiaohua Deng,Wenjing Song,Pengfei Ma,Weikun Lai

Selective aqueous hydrogenolysis of cellulose to valuable ketones and alcohols is attractive for biomass utilization. This work developed a TiO 2 layer coated MoO 3 nanorod supported Ni catalyst for the hydrogenolysis of cellulose to ketones and alcohols, which achieved a maximum hexacarbon keto-alcohols yield of 71.2 % with a complete cellulose conversion at 220 °C and 3 MPa H 2 . The interaction of Ni and TiO 2 -MoO 3 oxides provided effective channels for hydrogen transfer, thereby boosting the reduction of MoO 3 to form MoO 2 species. More Lewis acid sites were created which facilitated the isomerization of glucose and retro -aldol condensation of fructose. The cleavage of C O bonds in hydroxyl-containing intermediates thus promoted their selective hydrogenolysis to form ketones and alcohols. Particularly, Ni TiO 2 /MoO 3 catalyst demonstrated excellent reusability due to the protective coating of TiO 2 layer and could be widely used in selective hydrogenolysis of various oxygen containing compounds.

研究领域: 化学工程 · 可再生能源 · 催化科学
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Reaction Kinetics Mechanisms and Catalysis · 2018 ·Vol. 124 ·期 2 ·683-699 · IF 1.515

Hydrogenolysis of glycerol to 1,3-propanediol over Li2B4O7-modified tungsten–zirconium composite oxides supported platinum catalyst

Zhu Min,Chen Changlin

A series of Pt–yLi 2 B 4 O 7 /WO x /ZrO 2 (y = 0, 0.5, 1, 2 wt%) catalysts were prepared by varying the content of Li 2 B 4 O 7 through the method of coimpregnation-calcination. The obtained catalysts were used for the selective hydrogenolysis of glycerol to 1,3-propanediol. Meanwhile, these catalysts were characterized by N 2 adsorption and desorption (BET), CO chemisorption, X-ray diffraction (XRD), NH 3 -temperature programmed desorption (NH 3 -TPD), H 2 -temperature programmed reduction (H 2 -TPR), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The results showed that Pt–1Li 2 B 4 O 7 /WO x /ZrO 2 achieved the highest activity with glycerol conversion of 90.7% at 150 °C and 4 MPa and exhibited excellent stability over 200 h. Pt/WO x /ZrO 2 catalyst modified with Li 2 B 4 O 7 was able to enhance catalytic activity and stability, since Li 2 B 4 O 7 promoted the dispersion of Pt, increased the acid amount of the catalyst and strengthened the interaction between active components and support.

CAS / MDL: 16941-12-1 12007-60-2
研究领域: 化学工程 · 催化科学
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JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS · 2025 · IF 6.2

Synergistic effect of Pd and Mo catalysts on the biomass hydropyrolysis vapor upgrading for aromatic hydrocarbons

Wanchen Zhu,Zhongyang Luo,Feiting Miao,Longyi Liu

Biomass hydropyrolysis vapor upgrading (HPVU) is a promising approach for biofuel production, where metallic catalysts play a key role in oxygen removal and aromatic hydrocarbon formation. In this study, Pd/HZSM-5 and Mo/γAl 2 O 3 catalysts were prepared and utilized individually or in combination to investigate their effects on poplar HPVU in a continuous-flow reactor. Meanwhile, the influence of upgrading temperature on hydrodeoxygenation (HDO) reactions was studied. At an upgrading temperature of 400 ℃, combination of Pd/HZSM-5 and Mo/γAl₂O₃ resulted in an organic phase yield of 9.19 wt%. The mass yield and selectivity of aromatic hydrocarbons reached 8.13 wt% and 93.4 %, respectively, with selectivity of C8 + monocyclic aromatic hydrocarbons accounting for 56.7 %. The overall mass balance was 96.2 %. The presence of Pd promotes hydrogenation and hydroalkylation reactions, while Mo/γAl₂O₃ enhances deoxygenation. Additionally, its mesoporous structure facilitates reactant diffusion. The density functional theory calculations confirmed that Pd could efficiently activate H 2 and thus provide hydrogen radicals for HDO on Mo/γAl₂O₃ surface, which revealed the synergistic effect of these two catalysts. This study highlights that noble-metal catalyst aided by oxophilic metal catalyst can make a significant contribution to biomass HPVU.

CAS / MDL: 207596-32-5
研究领域: 能源与催化 · 化学工程
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FUEL PROCESSING TECHNOLOGY · 2019 · IF 4.507

Catalytic conversion of cellulose to C5/C6 alkanes over Ir-VOx/SO2 combined with HZSM-5 in n-dodecane/water system

Lele Jin,Wenzhi Li,Qiying Liu,Longlong Ma,Song Li,Yang Liu,Baikai Zhang,Qi Zhang

The liquid fuel (made of C 5 /C 6 alkanes) was obtained directly from the hydrogenolysis of microcrystalline cellulose (MCC) with Ir-VO x /SiO 2 combined with HZSM-5 as the composite catalyst in a biphasic system (n-dodecane + H 2 O). The performance of the catalyst was investigated by carrying out a series of experiments using various V/Ir molar ratios , catalyst dosages, reaction temperatures, reaction time, hydrogen pressure and substrates. At the optimized conditions, the cellulose was almost completely converted, and at the same time, a high C 5 /C 6 yield of 85.1% was obtained at 210 °C for 24 h and 6 MPa with the V/Ir molar ratio being 0.13. These results not only proved that Ir-VO x /SiO 2 (V/Ir = 0.13) has excellent performance for the hydrogenolysis of MCC to liquid alkanes, but also indicated that vanadium is a good metal promoter for iridium . In addition, it was proven the C5/C6 alkanes were obtained via sorbitol through the combined effect of Ir-VO x /SiO 2 and HZSM-5.

研究领域: 催化化学 · 可再生资源转化
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INDUSTRIAL CROPS AND PRODUCTS · 2024 · IF 5.6

Efficient lignin hydrogenolysis over N-doped macroporous carbon supported Ru catalyst

Wenwei Zhang,Tianjin Li,Xinping Ouyang,Xueqing Qiu

To cope with the challenge of insufficient interaction between lignin macromolecules and catalytic active sites in heterocatalysis systems which hindered the efficient hydrogenolysis of lignin, a lignin-derived N-doped macroporous carbon supported Ru catalyst (Ru/LNPC) was prepared via the pyrolysis of alkali lignin with potassium hydroxide as the activator and ammonium oxalate as the pore forming agent. The LNPC carrier featured a hierarchical porous structure with the diameter of macropores ranging from 50 nm to 10 μm, enhancing the adequately contact between the lignin macromolecules and Ru NPs. The doping nitrogen in the carbon carrier led to well dispersed Ru nanoparticles with average size of 1.08 nm, providing abundant active metallic centers. Therefore, Ru/LNPC exhibited excellent catalytic activity and stability to hydrogenolysis of lignin. Under the condition of 1.0 MPa H 2 at 280 ºC for 2 h, Ru/LNPC contributed to the yield of 45.6 % aromatic monomers from the depolymerization of lignin. After five recycling, Ru/LNPC still showed significant activity. This work provided a new strategy for designing catalysts for efficient hydrogenolysis of lignin and further facilitating its high-value utilization.

研究领域: 化学工程 · 材料科学 · 可再生能源
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Reaction Kinetics Mechanisms and Catalysis · 2015 ·Vol. 117 ·期 1 ·239-251 · IF 1.17

Hydrogenolysis of glycerol to propanediols on Cu–Ca–Al hydrotalcites derived catalysts

Geng Gaoli,Wei Ruiping,Liang Ting,Zhou Minghao,Xiao Guomin

A series of Cu–Ca–Al hydrotalcite derived catalysts were prepared by the co-precipitation method. Their catalytic activities were evaluated in the hydrogenolysis of glycerol. The catalysts were characterized by XRD, SEM, TEM, ICP, NH 3 -TPD, CO 2 -TPD and H 2 -TPR. It was observed that the incorporation of calcium and aluminum in the Cu–Ca–Al catalyst improved the conversion of glycerol and promoted the generation of 1,3-PDO. This is due to the appropriate acidity and basicity of the catalyst, which is confirmed by NH 3 -TPD and CO 2 -TPD. The conversion of glycerol over the catalyst with a Cu–Ca–Al mole ratio of 1:3:5 was up to 73.2 % with 42.6 % selectivity to 1,2-PDO and 9.1 % selectivity to 1,3-PDO. Effects of the reaction time, reaction temperature and initial hydrogen pressure on the conversion and selectivity were systematically investigated.

研究领域: 化学工程 · 催化材料科学
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JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL · 2013 · IF 3.187

Efficient synthesis of ethylene glycol from cellulose over Ni–WO3/SBA-15 catalysts

Yueling Cao,Junwei Wang,Maoqing Kang,Yulei Zhu

Ni–WO 3 /SBA-15 catalysts were prepared by an impregnation way and applied to the hydrogenolysis of cellulose in aqueous solution. The effect of nickel and WO 3 loading, catalysts reduction temperature and time on cellulose conversion were investigated. Up to 70.7% ethylene glycol yield was obtained over 3%Ni–15%WO 3 /SBA-15 catalysts. Several physicochemical methods such as XRD, Raman spectroscopy, NH 3 -TPD, H 2 -TPR and XPS were used to determine the character of catalysts. Based on these studies, it was found that there was a strong electronic interaction between NiO and WO 3 , which not only promoted the reduction of WO 3 , but restrained the reduction of NiO. Together with the experimental results, it can be concluded that the WO 3− X , which may be the active species for the selective cleavage of C C bond, was formed after catalysts pretreatment process. Additionally, a possible catalytic mechanism was proposed.

CAS / MDL: 9004-34-6
研究领域: 化学工程 · 催化材料科学
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CHINESE JOURNAL OF CATALYSIS · 2018 · IF 3.525

Pt/Nb-WOx for the chemoselective hydrogenolysis of glycerol to 1,3-propanediol: Nb dopant pacifying the over-reduction of WOx supports

Man Yang,Xiaochen Zhao,Yujing Ren,Jia Wang,Nian Lei,Aiqin Wang,Tao Zhang

Selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PD) is an important yet challenging method for the transformation of biomass into value-added chemicals due to steric hindrance and unfavorable thermodynamics. In previous studies, chemoselective performances were found demanding and sensitive to H 2 pressure. In this regard, we manipulate the chemical/physical characteristics of the catalyst supports via doping Nb into WO x and prepared 1D needle-, 2D flake-, and 3D sphere-stack mesoporous structured Nb-WO x with increased surface acid sites. Moreover, Nb doping can successfully inhibit the over-reduction of active W species during glycerol hydrogenolysis and substantially broaden the optimal H 2 pressure from 1 to 5 MPa. When Nb doping is 2%, supported Pt catalysts showed promising performance for the selective hydrogenolysis of glycerol to 1,3-PD over an unprecedentedly wide H 2 pressure range, which will guarantee better catalyst stability in the long run, as well as expand their applications to other hydrogen-related reactions.

CAS / MDL: 10026-12-7 13283-01-7
研究领域: 催化化学 · 生物质转化 · 材料科学
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FUEL · 2024 · IF 6.7

Deep eutectic solvents promote in-situ hydrogenolysis of Evodia lepta residue in preparing small aromatic phenol ketones

Shutian Chen,Yating Jian,Yaowei Liu,Zhanying Zhang,Xinlong Li,Qiang Yu

A deep eutectic solvent (DES) system of ChCl-MeOH-AlCl 3 ·6H 2 O was developed for simultaneous dissolution of lignin from Evodia lepta residue and in-situ hydrogenolysis of lignin to aromatic phenol ketones using a Ru-C catalyst. The use of this DES led to a delignification of reached 93.1 % and cellulose and hemicellulose retentions of 95.3 % and 47.8 % respectively at the molar ratio of 1:12:0.2. While the total aromatic phenol ketones yield reached 92.4 % under 130 °C for 3 h with 17.2 % yields of vanillyl methyl ketone, 9.1 % syringylacetone, 25.4 % dihydroeugenol, and 40.7 % 4-propyl-2,6-dimethoxyphenol. The improved Ru-C properties in the DES system like thermal stability, the specific surface area and reduction potential contributed on the exceptional high product yields. The aromatic phenol ketones were 312.5 % higher than the reported yields of hydrogenolysis of aromatic monomers by ethanol/1,4-dioxane/formic acid under 300 °C–2 h conditions.

研究领域: 化学工程 · 可再生资源利用 · 催化化学
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ACS Sustainable Chemistry & Engineering · 2023 · IF 8.4

Unraveling the Dependence of Critical Active Sites of WOx on Rh/WOx Catalysts in Tetrahydrofurfuryl Alcohol Hydrogenolysis

Man Yang,Yuxiang Jiao,Jianglin Duan,Keying Wu,Hailiang Song,Shaodong Sun,Yujing Ren

Taking the background of the ambiguous role of oxophilic metal oxide in metal-acid bifunctional catalysts for the important field of tetrahydrofurfuryl alcohol (THFA) hydrogenolysis, a linear relationship between the W═O/W–OH content in sub-nano-Rh-supported WOx and 1,5-pentanediol (1,5-PeD) yields from THFA hydrogenolysis has been established. It reveals that the higher reduction temperature promotes the surface Rh/W ratio. Thus, hydrogen spillover is facilitated, leading to more surface W═O structures and thereby more in-situ-reduced W–OH generation. W–OH structures work as the active sites to provide in situ Brønsted acid, resulting in enhanced selective activation for secondary C–O bonds of THFA. This discovery reveals the unique role of the surface structure on oxophilic metal oxide in chemoselective hydrogenolysis of the secondary C–O bond in polyols.

研究领域: 催化化学 · 材料科学
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Journal of Renewable and Sustainable Energy · 2017 ·Vol. 9 ·期 2 · IF 1.135

One-pot selective conversion of cellulose into low carbon polyols on nano-Sn based catalysts

Xiao Zhuqian,Mao Jianwei,Jiang Chengjun,Xing Chuang,Ji Jianbing,Cheng Yongjie

The direct hydrogenolysis of cellulose on bimetallic catalysts represented a promising route for polyols' production. The development of a catalyst system that could control the promotion of the selectivity of polyols for the conversion cellulose into polyols was highly desirable. In this work, we realized the production of ethylene glycol (EG) and 1,2-propylene glycol (1,2-PG) by adopting nano-Sn species with different valences in combination with Ni catalysts, and the catalysts were prepared by the incipient-wetness impregnation method. The catalyst 10%Ni–15%Sn/SBA-15 achieved the highest yield of C 2 -C 3 polyols, yielding up to 67.2% with a higher selectivity to 1,2-PG. The Ni and Sn species and some NiSn alloys were found to be the active sites for the EG and PG as evidenced by control experiments and characterization including X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. The catalytic particles were located on the outer surface of SBA-15 (pore size = 6–10 nm) on a nanoscale with sizes of 11.1 ± 1.9 nm. The effects of the supports and hydrogenating species were investigated for cellulose conversion. The experimental results disclosed that the Sn species with different valences possessed obvious functions for the retro-aldol condensation, and the Ni components boomed the hydrogenation process. The other detailed analyses on the formation of polyols were described. As a consequence, controlling the EG and PG product distribution could be realized using Sn based catalysts.

研究领域: 化学工程 · 催化科学
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Energy & Environmental Science · 2013 ·Vol. 6 ·期 3 ·994-1007 · IF 11.653

Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process

Qi Song,Feng Wang,Jiaying Cai,Yehong Wang,Junjie Zhang,Weiqiang Yu,Jie Xu

Valorization of native birch wood lignin into monomeric phenols over nickel-based catalysts has been studied. High chemoselectivity to aromatic products was achieved by using Ni-based catalysts and common alcohols as solvents. The results show that lignin can be selectively cleaved into propylguaiacol and propylsyringol with total selectivity >90% at a lignin conversion of about 50%. Alcohols, such as methanol, ethanol and ethylene glycol, are suitable solvents for lignin conversion. Analyses with MALDI-TOF and NMR show that birch lignin is first fragmented into smaller lignin species consisting of several benzene rings with a molecular weight of m/z ca. 1100 to ca. 1600 via alcoholysis reaction. The second step involves the hydrogenolysis of the fragments into phenols. The presence of gaseous H2 has no effect on lignin conversion, indicating that alcohols provide active hydrogen species, which is further confirmed by isotopic tracing experiments. Catalysts are recycled by magnetic separation and can be reused four times without losing activity. The mechanistic insights from this work could be helpful in understanding native lignin conversion and the formation of monomeric phenolics via reductive depolymerization.

研究领域: 生物化学 · 催化化学
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