JOURNAL OF THE ENERGY INSTITUTE
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2021
·
IF 6.186
Riyang Shu,Zhuojie Zhong,Hongyun You,Zhipeng Tian,Ying Chen,Longlong Ma
Hydrodeoxygenation (HDO) is an important pathway for lignin-oil upgradation to produce high quality liquid fuels, in which the high-active catalyst is the key point to achieve a high HDO efficiency. In this study, Ru/TiO 2 , Ru/CeO 2 and Ru/TiO 2 –CeO 2 catalysts were synthesized by a novel photochemical method with a high Ru dispersion and used for the HDO of lignin-derived phenolic compounds. Among these three catalysts, Ru/TiO 2 –CeO 2 showed a better performance than Ru/TiO 2 and Ru/CeO 2 . And guaiacol was transformed into cyclohexane with conversion and product selectivity close to 100 % at 230 °C under 1 MPa hydrogen atmosphere. Ru/TiO 2 –CeO 2 took the advantages of Ru/TiO 2 and Ru/CeO 2 , namely high Ru metal dispersion, plenty of medium strength acid sites and abundance of oxygen vacancy , which promoted the guaiacol adsorption and the HDO catalytic activity . Moreover, Ru/TiO 2 –CeO 2 catalyst showed an effective upgrading of other lignin-derived phenolic compounds. And the lignin-oil also enabled to be upgraded efficiently, producing a high content of hydrocarbons and alkylphenols.
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高影响因子
FUEL
·
2021
·
IF 6.609
Zier Jin,Hong Xia,Wenxin Yang,Mingen Liu,Xiaoyu Liu,Jiao Xiang,Abdul Qayum,Liangsheng Hu,Lianfeng Duan,Wenhua Gao,Zhi Liu,Fushen Lu
Ammonia borane (NH 3 BH 3 , AB) has been considered as one of the most attractive candidates for chemical hydrogen-storage materials. Development of low-cost and high-performance catalysts for hydrogen generation from AB is highly desirable, which is still a huge challenge. Herein, Ru-Ni bimetallic nanoparticles were fabricated on (3-aminopropyl) triethoxysilane-functionalized reduced graphene oxide nanosheet (APTS-rGO) by a facile one-step in situ co-reduction strategy. The newly developed Ru 1 Ni 4 /APTS-rGO catalyst with hydrophilic interface and narrow particle size-distribution presented a remarkably enhanced catalytic activity for hydrolytic H 2 generation from AB, affording an ultra-high TOF value of 1559 min −1 . The APTS-rGO support was effective to minimize the aggregation of Ru-Ni nanoparticles, achieving the immobilization of ultrasmall Ru-Ni nanoparticles (2.0 nm) on support surface. The change in local charge density of catalyst surface caused by Ru-Ni synergistic effect and metals-support interaction improved the catalytic performance of Ru 1 Ni 4 /APTS-rGO. Hydrophilic NH 2 -containing interface ensured high dispersibility of catalysts in reaction solution, increasing the contact opportunities between active sites and AB molecules. These factors contributed together to the exceptional catalytic performance of Ru 1 Ni 4 /APTS-rGO. This catalytic system has potential applications in various catalytic fields due to its obvious advantages of the facile preparation method, good hydrophilicity, and the outstanding catalytic performance.
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高影响因子
GREEN CHEMISTRY
·
2020
·Vol. 22
·期 3
·850-859
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IF 9.48
Yang Qian,Ze-Jun Li,Xian-Long Du,Qi Zhang,Yi Zhao,Yong-Mei Liu,Yong Cao
Development of a highly efficient and robust catalyst with reduced usage of noble metals is extremely desirable for selective hydrogenations of furan-containing bio-based feedstocks, which represents an attractive and sustainable alternative to petrochemical resources. Herein, we describe a new type of well-dispersed Ru subnanoclusters (ca. 0.50 wt%) supported on commercial P25 TiO2 material obtained from a facile and effective amino acid-assisted deposition–precipitation strategy. The as-synthesized catalyst exhibits superior catalytic activity and selectivity for direct hydrogenation of industrially important furfural as well as a range of structurally diverse bio-based furanic compounds to their corresponding fully hydrogenated derivatives. An average turnover frequency (ATOF) value as high as 367 h−1 at 80 °C and 4 MPa H2 is obtained, which is the highest reported value. This catalyst also shows stable furfural total hydrogenation in 5 reaction cycles conducted at 80 °C (52 mmol-scale, turnover number up to 12 500). In terms of the kinetic and structural characterizations, the key performances of the ultrasmall Ru clusters are proposed to mainly originate from an enhanced number of unsaturated surface Ru atoms and change in local coordination environment. Our work highlights the importance of the subnanometric size of Ru clusters in the advancement of efficient and affordable approaches towards bio-based chemical production.
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高影响因子
Journal of Materials Chemistry A
·
2019
·Vol. 7
·期 6
·2780-2786
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IF 10.733
Zhen Zhang,Ping Li,Qi Wang,Qi Feng,Youkun Tao,Jiaoyan Xu,Cheng Jiang,Xiner Lu,Jiantao Fan,Meng Gu,Hui Li,Haijiang Wang
As a cheaper Pt-group metal, ruthenium (Ru) is a highly competitive alternative to Pt for commercialization towards the hydrogen evolution reaction (HER). Herein, we report the modulation effect on the Gibbs free energy (ΔGH*) of hexagonal-close-packed (hcp) Ru resulting from heteroatom Mo doping. In particular, for the first time the hcp MoRu3 crystal structure is theoretically predicted with pretty high intrinsic HER activity. Meanwhile, the Mo hetero-dopant could act as a new active site with Pt-like ΔGH*. Motivated by the prediction, we report a novel metal organic framework (MOF)-assisted synthetic strategy to prepare a Mo-doped hcp Ru electrocatalyst. Accordingly, the hcp MoRu3 catalyst exhibits an ultralow overpotential of 30.5 mV at 10 mA cm−2, ensuring excellent Pt-like intrinsic HER activity. More importantly, the excellent electrochemical performance measured with a proton exchange membrane (PEM) electrolyzer further highlights the promising potential of the hcp MoRu3 catalyst for hydrogen production.
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高影响因子
GREEN CHEMISTRY
·
2019
·Vol. 21
·期 10
·2739-2751
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IF 9.405
Naseeb Ullah,Atheer Hameid Odda,Kuang Liang,Miza Ali Kombo,Shafaq Sahar,Liu-Bo Ma,Xiao-Xiang Fang,An-Wu Xu
The catalytic fractionation of lignin in a native lignocellulose matrix is crucial to the comprehensive achievement of sustainable and green chemicals. Herein, we prepared a novel metal–acid bifunctional nanocomposite of finely scattered metallic Ru nanoclusters (NCs) sustained on porous hafnium phosphate nanoplates (α-HfP NPs) to effectively depolymerise lignocellulosic biomass. A native lignin fraction of pine lignocellulose was promptly depolymerised into 19.86 wt% yield (lignin based) of valuable phenolic monomers (with dihydroeugenol as the main compound with high selectivity) and few cyclic ketones through one-pot catalytic reductive fractionation under mild conditions (190 °C, 3.5 MPa H2). Detailed scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption ammonia investigation correlated with the obtained results revealed that the metal–acid synergistic influence and the presence of Brønsted acid sites in the support for dehydration and the well-dispersed metallic role of Ru NCs for hydrodeoxygenation were responsible for the cleavage of lignin–carbohydrate (ester and ether linkages) bonds. Moreover, treating commercial lignin as a substrate in an organic solvent generated 4-hydroxy-3-methoxybenzaldehyde (vanillin) in high yield, as well as other functionalised phenolic monomers up to 85% selectivity, illustrating the high susceptibility of Ru/α-HfP NPs towards C–O bond cleavage through reductive fractionation. Multiple recycling tests of the catalyst were performed without any apparent loss of activity. Overall, this report highlighted the potential of the synthesis strategy of the metal–acid supported catalyst to immediately depolymerise untreated biomass and can thus encourage the green, cost-efficient, large-scale production of intermediate chemicals.
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高影响因子
CELLULOSE
·
2019
·Vol. 26
·期 13
·8059-8071
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IF 3.917
Xie Congxia,Qu Li,Yu Hailong,Yu Fengli,Yuan Bing,Yu Shitao,Nie Shuangxi
Abstract Ruthenium (Ru) nanoparticles synthesized using hydroxyethyl cellulose (HEC-Ru) were used to hydrogenate α-pinene in an aqueous medium. The results showed that HEC had a good dispersion effect on Ru nanoparticles and most of the particle sizes were ranged from 4 to 6 nm. The micelles formed with HEC appeared to act as “microreactors” in which the Ru nanoparticles had good stability and uniform distribution. In addition, α-pinene was loaded into the HEC micelles through hydrophobic interaction, resulting in good contact with Ru nanoparticles. Thereby, HEC-Ru nanoparticles significantly improved the hydrogenation of α-pinene, and 99.6% of α-pinene conversion and 98.6% of cis-pinane selectivity were obtained. Compared with the Pd/C, Ru/H 2 O, and HEC-Ru/ethanol catalyst systems, the HEC-Ru/H 2 O system had the maximum α-pinene conversion. In addition, considerable α-pinene conversion could be obtained after 10 times reuse with no fresh addition. Graphic abstract
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高影响因子
APPLIED CATALYSIS A-GENERAL
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2019
·
IF 4.63
Wei Qian,Lina Lin,Yunxiang Qiao,Xiuge Zhao,Zichen Xu,Honghui Gong,Difan Li,Manyu Chen,Rong Huang,Zhenshan Hou
The N-doped carbon layer coated SBA-15 support has been accomplished via a pyrolysis process . The ultra-low loading Ru nanoparticles ( ca. 0.1 wt.%) was incorporated into the support by impregnation and the sequential reduction. The images of HAADF-STEM revealed that the Ru particles with sub-1-nm size (0.2-0.7 nm) were uniformly dispersed on the support. The ultrafine Ru particles displayed the excellent activity for the hydrogenation of olefins , arenes, phenol derivatives and heteroarenes in aqueous phase. The aliphatic or alicyclic compounds were produced selectively without the hydrogenolysis of C O and C N bonds. The high turnover frequency (TOF) values can reach up to 10,000 h −1 . Notably, the activity of these catalysts improved dramatically with decreasing the sizes of Ru particles. Meanwhile, the N-doped carbon layer coating endowed the high stability of the Ru catalysts and prevented the leaching of the Ru species owning to the strong interaction between doped-N atoms and the ultrafine Ru particles. Overall, this work provides a highly attractive strategy to construct the supported sub-1-nm Ru particles utilized for the aqueous hydrogenation.
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高影响因子
Molecular Catalysis
·
2019
·
IF 2.938
Haibin Wang,Shaodong Liu,Tingting Sun,Zhanao Lv,Zhen Zhan,Guochuan Yin,Zhuqi Chen
In catalytic double bond migration reaction, E -configuration olefins were normally generated as the dominant product because E -configuration was thermodynamically favored. However, Z-configuration products are sometimes desired in pharmaceutical chemistry owing to the structure-activity relationship. In this paper, we have demonstrated a new strategy that Lewis acid promoted an widely employed and convenient ruthenium(II) complex for the catalytic isomerization of O-allylethers, leading to thermodynamic-unfavored Z-product under mild conditions. The model substrate of allyl phenyl ether can be simply scaled up to 20 mmol to produce Z-product with TON of 2453 and TOF of 13,430 h −1 at 40–60 °C. The system of Ru(II)/Lewis Acid catalysts was suitable for various substituted O -allylethers and other types of substrates. Through mechanism study including kinetic study, ligand inhibition effect and molecular spectroscopy, the dissociation of PPh 3 ligand by the addition of Lewis acid, and the formation a five-membered Ru complex from anchimeric assistance were both recognized as essential steps to improve the reactivity and to control the stereoselectivity of catalytic double bond migration reaction through metal hydride addition-elimination mechanism. This new strategy may provide a new opportunity to produce thermodynamic-unfavored product in heterocyclic compounds for pharmaceutical chemistry.
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高影响因子
Molecular Catalysis
·
2019
·
IF 2.938
Chenglong Dong,Hongtao Wang,Haochen Du,Jiebang Peng,Yang Cai,Shuai Guo,Jianli Zhang,Chanatip Samart,Mingyue Ding
Furfurylamine converted from biomass-based platform molecules furfural was proven a significant intermediate in the synthesis of different valuable compounds. The combination of Ruthenium with HZSM-5 was acted as an excellent selective and reusable catalyst for the reduction amination of furfural with environmentally friendly ammonia and hydrogen. Incorporation of Ru species into HZSM-5 had a significant enhancement to the acid sites of Ru/HZSM-5. The Ru/HZSM-5(46) catalyst with optimized acid sites and interaction of the Ru-O-Al bond displayed an excellent catalytic performance, producing 76 % yield of furfurylamine at only 15 min, and could be recycled five times without loss of performance. Synergistic effect between RuO 2 and metallic Ru in the Ru/HZSM-5 catalyst facilitated the reduction amination of furfural.
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高影响因子
ChemCatChem
·
2018
·Vol. 10
·期 18
·4090-4099
·
IF 4.674
Hang Li,Botao Wu,Fumin Wang,Xubin Zhang
Graphical No DMPUing ground : Efforts are made to design mercury-free catalysts from both technical and economic aspects. Here, a Ru-based catalyst with a low Ru content is prepared by adding DMPU as an efficient stabilizer. The catalyst shows high activity and stability. A new Ru-based catalyst system based on N,N′-Dimethylpropyleneurea (DMPU) was developed for the acetylene hydrochlorination reaction in this study. The optimal 1 % Ru-10 %DMPU/AC catalyst exhibits the best activity with the acetylene conversion of 87.6 % under 170 °C and the GHSV (C 2 H 2 ) of 900 h −1 . Additionally, the Ru-10 %DMPU/AC with lower Ru content (0.2 wt%) displayed excellent activity and stability with acetylene conversion of 81.3 % after 200 h under the conditions of 170 °C and C 2 H 2 GHSV of 180 h −1 . The characterization results indicate that the presence of DMPU could improve the dispersion of the catalytic species and provide full protection to prevent the sintering of the ruthenium particles and to inhibit the reduction of active ruthenium oxide component. Moreover, the catalytic property, characterizations and theoretical calculation results reveal that the ability to adsorb and activate HCl reactant with the addition of DMPU via its strong hydrogen bonding plays a significant role on the high stability of the Ru-DMPU/AC catalyst system.
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高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
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2018
·
IF 5.667
Jing Wang,Tingting Li,Haigang Li,Gongke Li,Shixin Wu,Liansheng Ling
AuNPs-DNA probes remain a challenge to recognize the double-stranded DNA (dsDNA) from routine PCR product despite its success in the recognition of the single-stranded (ssDNA) DNA of asymmetry-PCR product. Here, a universal colorimetric PCR biosensor is established with oligonucleotide modified AuNPs by recognizing the dsDNA of PCR product based on triplex DNA formation with the assistance of a triplex DNA intercalator Ru(phen) 2 dppx 2+ . The strategy was applied to detect different length dsDNA, including short dsDNA 1 (49 bp) and long dsDNA 2 (321 bp), both of which had the good linear relationship between the absorbance and the logarithm of the concentration of the targets. Moreover, the limit of detection (LOD) for short and long length dsDNA was 0.5 pM and 0.05 fg, lower than those of the previously reported methods, respectively. This strategy also displayed high selectivity against dsDNA 1 and dsDNA 2. These results demonstrate a potential strategy to detect all length of dsDNA, providing new opportunities in the life science, diagnosis, and medicine.
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高影响因子
ACS Applied Materials & Interfaces
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2018
·
IF 8.097
Fangman Chen,Fangnan Xiao,Weibing Zhang,Chentao Lin,Yunkun Wu
Herein, new near-infrared (NIR) luminescent ruthenium complexes were prepared for detecting Cu2+ ions. Then, ruthenium complex hybrid nanomaterials (Ru–LPMSNs) were fabricated successfully by imbedding the ruthenium complex into mesoporous silica nanoparticles. Benefiting from the novel large-pore mesoporous structure and good adsorbility of LPMSNs, Ru–LPMSN hybrid materials showed a significantly enhanced fluorescence intensity and stability. NIR fluorescence of Ru–LPMSNs was rapidly quenched by Cu2+ ions. Ru–LPMSNs also showed high Cu2+ ion selectivity and sensitivity as a sensor. The detection limit of Cu2+ ions was 10 nM with a wide linear relationship between the fluorescence intensity of Ru–LPMSNs and the concentration of Cu2+ ions. The mechanism of fluorescence quenching might be that the combination of the ruthenium complex and Cu2+ ions constrained the photoinduced electron-transfer process. Furthermore, Ru–LPMSNs dramatically increased the fluorescence signals in cells and achieved Cu2+-ion detection. Ru–LPMSNs had different tissue affinities and could monitor distribution of exogenous Cu2+ ions in vivo. Moreover, Ru–LPMSNs realized direct and rapid detection of Cu2+-ion content in serum. These results indicated the potential applications of the prepared nanomaterials as Cu2+ detection agents.
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PubMed
高影响因子
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