Chemical Science
·
2019
·Vol. 10
·期 16
·4458-4468
·
IF 9.556
Liang Jiang,Haiwei Guo,Changzhi Li,Peng Zhou,Zehui Zhang
Selective hydrogenolysis of the Caryl–O bonds in lignin is a key strategy for the generation of fuels and chemical feedstocks from biomass. Currently, hydrogenolysis has been mainly conducted using hydrogen, which is flammable and not sustainable or economical. Herein, an external hydrogen-free process for aryl ethers hydrogenolysis in lignin models and dioxasolv lignin over nickel nanoparticles supported on Al2O3, is reported. Kinetic studies reveal that the transfer hydrogenolysis activity of the three model compounds decreased in the following order: benzyl phenyl ether (α-O-4), 2-phenylethyl phenyl ether (β-O-4) and diphenyl ether (4-O-5), which linearly corresponds to their binding energies and the activation energies. The main reaction route for the three model compounds was the cleavage of the ether bonds to produce aromatic alkanes and phenol, and the latter was further reduced to cyclohexanol. Dioxasolv lignin depolymerization results exhibit a significant Caryl–O decrease over the Ni nanoparticles supported on Al2O3 with iso-propanol as the hydrogen source through 2D-HSQC-NMR analysis, which confirmed the transfer hydrogenolysis conclusion in the model study. This work provides an economical and environmentally-friendly method for the selective cleavage of lignin and lignin model compounds into value-added chemicals.
研究领域:
化学工程
·
可再生资源利用
✓ 已验证
DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
·
2023
·
IF 4.6
Weizuo Li,Jing Shi,Dafang He,Haiqun Chen
Catalysts with an open hollow structure can enhance the mass transfer capability of the catalyst during the reaction process, thereby further improving the catalytic performance. In this work, uniform and monodisperse flying-squircher-shaped Al-MOFs were synthesized via a solvothermal method. Furthermore, a hollow structure Al2O3-supported metallic Ni catalyst (termed Ni–Al2O3–HFA) was synthesized via the Kirkendall effect for the hydrogenation–alkylation cascade reaction by employing as-synthesized Al-MOFs as a carrier for impregnation of Ni(NO3)2·6H2O through further calcination and reduction. Various characterizations (e.g., XRD, HADDF-STEM, H2-TPR) were conducted to reveal the superior performance of the developed Ni–Al2O3–HFA catalyst compared to Ni/Al2O3–IWI (Al2O3 obtained from calcination of Al-MOFs) in cascade reaction between nitroarenes and alcohols. We hope to use the MOF template method via the Kirkendall effect to prepare hollow structure nanocatalysts, which can provide a guideline for the preparation of other hollow materials.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
ChemistryOpen
·
2025
·
IF 3.1
Chenyun Zhang,Jiahao Wang
Graphical A deep eutectic solvent (DES) prepared by mixing tetraalkylphosphonium chloride ([ P4444 ]Cl) and glycerol is applied in the synthesis of P-doped Ni materials. The DES not only serves as the reaction medium but also participates in the catalyst preparation. The synthesized P-doped Ni catalyst exhibits excellent performance in HER in both acidic and alkaline environments. A deep eutectic solvent (DES) was prepared by mixing tetraalkylphosphonium chloride ([P 4444 ]Cl) and glycerol in a 1:2 molar ratio. Nickel nitrate was dissolved in this DES, and then the mixture was heated at 350 °C to obtain phosphorus-doped nickel catalysts. In this system, the DES plays multiple crucial roles. (1) It serves as a reaction medium, providing a suitable solvent environment for the synthesis of Ni-based catalysts. (2) It actively participates in the catalyst preparation as a reactant. [P 4444 ]Cl acts as a P source, while glycerol effectively promotes the formation of nickel metal as a reducing agent. (3) It exhibits a templating effect, inducing the morphology of product to be a unique thin sheet with angular edges. The synthesized P-doped Ni material exhibits excellent hydrogen evolution performance in water splitting. In an acidic environment, when the current densities reached 10 and 20 mA cm −2 , the overpotentials were only 90.2 and 115.9 mV, with a Tafel slope as low as 55.6 mV dec −1 . In an alkaline environment, the P-doped Ni also performed well. The η 10 and η 20 values were 107.0 and 145.4 mV, respectively. The Tafel slope was 57.0 mV dec −1 .
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2025
·
IF 4.1
Qi Wang,Yi Shen
Electrochemically converting nitrate (NO 3 − ) to ammonia (NH 3 ) powered by renewable energy sources offers a sustainable alternative pathway for NH 3 synthesis. Herein, bimetallic Cu Ni nanoparticles supported by carbon paper (CP) were synthesized using a facile electrodeposition method. The structures of the resulting samples were characterized by scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The activity of the samples toward nitrate reduction reaction (NO 3 RR) was evaluated by linear sweep voltammetry, electrochemical impedance spectroscopy and chronoamperometry tests. The products from NO 3 RR were also determined. Compared to the counterpart catalysts including Cu/CP and Ni/CP, the CuNi/CP catalyst with bimetallic phases showed much higher faraday efficiency (FE) and yield for the NO 3 RR. The NO 3 RR catalyzed by CuNi/CP catalyst suggested a tandem mechanism in which Cu is responsible for the reduction of NO 3 − into NO 2 − , while Ni is favorable for the generation of H atoms (H*), which subsequently promotes the further conversion of NO 2 − and other intermediates to NH 3 .Benefiting from the synergistic effects of Cu and Ni, the optimal CuNi/CP catalyst efficiently converted NO 3 − to NH 3 with a high FE of 90.36 % and NH 3 yield of 3.53 mg h −1 mg −1 at −0.6 V vs. RHE in 0.5 M Na 2 SO 4 + 0.1 M NaNO 3 solutions.
研究领域:
环境科学
·
材料科学
·
电化学工程
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Quanzhou Xu,Xing Fei,Xueqing Qiu,Xiaofei Wang,Tiejun Wang,Xuliang Lin,Sha Li,Yanlin Qin
The selective conversion of biomass-derived ethanol into higher alcohols is a desirable but challenging process for the efficient production of value-added chemicals from alternative carbon sources. However, the current catalysts used in ethanol coupling exhibit low conversion rates and yields towards the formation of higher alcohols, necessitating significant improvements in their efficiency for practical applications. In this work, a lignin-derived N-doped carbon- supported Ni catalyst for ethanol coupling was designed and synthesized. The Ni@NC catalyst, synthesized using diethylenetriamine as the nitrogen source with a mass ratio of nitrogen source to lignin of 2:1 and a molar ratio of metal to lignin of 20:1, demonstrated excellent performance, with an ethanol conversion rate of 81.1% and a yield of C 4+ alcohols reaching 35.3%. Experimental results and density functional theory (DFT) calculations suggest that nitrogen-doped lignin, in appropriate quantities, along with the metal active component, forms a Ni-N-C structure that controls charge redistribution between the support and the Ni catalyst. This structure hinders the interaction of reaction intermediates and inhibits the production of by-products in the decomposition reaction, resulting in a higher yield of C 4+ alcohols. This study presents a more cost-effective and efficient approach for developing ethanol-coupling catalysts and holds promise for expanding the utility of lignin-derived catalysts.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2024
·
IF 6.5
Huali Zhang,Xiaoxiao Chen,Jiajia Cheng,Xintuo Yang,Wei Lin,Yidong Hou,Guigang Zhang,Xinchen Wang
The integration of heterogeneous photocatalysts with nickel catalysis is garnering considerable interest for their capacity to enable distinct metal-photoredox processes for organic synthesis. However, the challenge about robustness and recyclability of the photocatalyst persists. Herein, a crystalline carbon nitride (MCN-B) photocatalyst with intentionally introduced defects and a dedicated designed active site has been presented. Results reveal by incorporating the deprotonated cyano-group (N - –CN) sites, this host material could provide stable binding sites for Ni (II) ions through the Hard-Soft Acid-Base (HSAB) effect, thereby facilitating charge transmission between semiconductor and metal centers. Consequently, the integrated carbon nitride nickel (Ni/MCN-B) heterogeneous photocatalyst demonstrates high effectiveness in diverse photocatalytic C-N coupling reactions (21 examples, up to 93% yield) under conditions free from organic ligands and additives, which shows competent performance to the homogeneous catalysts. Moreover, the Ni/MCN-B catalyst demonstrates remarkable recyclability, maintaining its photoredox efficiency after 10 cycles with minimal loss of activity and a diminished metal leaching rate, which signifies a substantial advancement in the field of photocatalytic system design.
研究领域:
有机化学
·
材料科学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2025
·
IF 8.5
Cuiping Zhu,Mingmei Jing,Zhenjie Guo,Xiaojin Shi,Yang Hu,Zhuohong Yang,Zhuangzhuang Chu
Based on the amino-functionalized corn straw cellulose-based porous material, a structurally stable and high-performance straw-based metal catalyst (PPCS@Ni) was prepared by depositing metal particles on the surface of porous straw (PCS) using an economical and environmentally friendly polymer-assisted metal deposition (PAMD) method. Due to the excellent structural stability of the metal material and the catalytic performance of nickel, PPCS@Ni exhibited outstanding catalytic efficiency, cyclic regeneration ability, and stability in the catalytic hydrogenation of oleic acid. Furthermore, after experimental screening and optimization (8 g oleic acid, 34.73 % Ni, 100 mg PPCS@Ni, 180 °C, 3 MPa H 2 , 6 h), PPCS@Ni demonstrated a yield and selectivity for stearic acid reaching 100 %. Finally, density functional theory calculations revealed the mechanism of PPCS@Ni in the hydrogenation reaction of oleic acid as well as elucidated the key role of the catalyst surface and selectivity trend of products. With these advantages, it is anticipated that the straw-based metal catalysts developed in this study will provide a new effective pathway for vegetable oil hydrogenation processes.
研究领域:
催化材料
·
化学工程
·
可再生资源利用
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2020
·
IF 4.939
Dewen Sima,Haojin Wu,Koukou Tian,Shijun Xie,Joel Jie Foo,Shuirong Li,Duo Wang,Yueyuan Ye,Zhifeng Zheng,Yun-Quan Liu
Ammonia decomposition is an effective way for high purity hydrogen production , yet the increase of catalytic activity at low temperatures remains a big challenge for this process. In this paper, a CeO 2 –ZrO 2 composite with Al as the secondary dopant was synthesized by the co-precipitation method, which was used as the carrier of nickel metal for ammonia decomposition. The experimental results showed that an obvious increase in catalytic activity of the ammonia decomposition at the relatively low temperature range of 450–550 °C was achieved over the nickel catalyst with CeO 2 –ZrO 2 composite as the metal carrier. Specifically, the complete decomposition of ammonia was achieved at 580 °C for Ni/Al–Ce 0.8 Zr 0.2 O 2 catalyst, while only 92% of ammonia was decomposed at 600 °C over the reference Ni/Al 2 O 3 catalyst. The characterization results indicated that the introduction of Al as the secondary dopant of ceria not only increases the specific surface area and oxygen defects on the surface, but also enhances the nickel metal dispersion and metal-support interaction, thus enhances the catalytic performance of Ni/Al–Ce 0.8 Zr 0.2 O 2 catalyst in the ammonia decomposition.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2017
·
IF 7.504
Xin Ning,Yiyuan Lu,Heyun Fu,Haiqin Wan,Zhaoyi Xu,Shourong Zheng
Supported Ni catalysts on three mesoporous SiO2 supports (i.e., SBA-15, MCM-41, and HMS) were prepared using a solid-state reaction between Ni(NO3)2 and organic template-occluded mesoporous SiO2. For comparison, supported Ni catalysts on mesoporous SiO2 synthesized by the conventional impregnation method were also included. The catalysts were characterized by scanning electron microscopy, X-ray diffraction, UV–vis diffuse reflectance spectroscopy, N2 adsorption, X-ray photoelectron spectroscopy, H2 temperature-programmed reduction, transmission electron microscopy, and transmission electron microscopy–energy-dispersive X-ray. The catalytic properties of the catalysts were evaluated using gas-phase catalytic hydrodechlorination of 1,2-dichloroethane. The results showed that upon grinding Ni(NO3)2 with template-occluded mesoporous SiO2, strong coordination between Ni2+ and dodecylamine was identified in the Ni(NO3)2–HMS system. Additionally, the results of H2 temperature-programmed reduction revealed that NiO in calcined NiO/HMS was reduced at higher temperature than those in calcined NiO/SBA-15 and NiO/MCM-41, reflecting the presence of a strong interaction between NiO and mesoporous SiO2 in NiO/HMS. Consistently, the average particle sizes of metallic Ni were found to be 2.7, 3.4, and 9.6 nm in H2-reduced Ni/HMS, Ni/SBA-15, and Ni/MCM-41, respectively, indicative of a much higher Ni dispersion in Ni/HMS. For the catalytic hydrodechlorination of 1,2-dichloroethane, Ni/MCM-41 synthesized by the solid-state reaction method exhibited a catalytic activity similar to that prepared by the impregnation method, while higher catalytic activities were observed on Ni/HMS and Ni/SBA-15 than on their counterparts prepared by the impregnation method. Furthermore, a higher conversion was identified on Ni/HMS than on Ni/SBA-15 and Ni/MCM-41, highlighting the importance of template type for the preparation of highly dispersed metal catalysts on mesoporous SiO2.
研究领域:
材料科学
·
催化化学
✓ 已验证
DOI
高影响因子
GREEN CHEMISTRY
·
2018
·Vol. 20
·期 15
·3634-3642
·
IF 8.586
Bin Zhang,Bin Chen,Mark Douthwaite,Qiang Liu,Chao Zhang,Qifan Wu,Ruhui Shi,Peixuan Wu,Fengyu Zhao,Graham Hutchings
Carbon based materials are some of the most commonly studied catalysts for the conversion of cellulose to polyols. The catalytic performance of these materials, however, is typically limited by the access of the substrate to the active sites, which is governed by the poor solubility of cellulose in aqueous solutions. In an attempt to resolve this, we presented a novel hierarchical carbon material which was synthesized by a dual-templating method. Transmission electron microscopy and porosity measurements confirmed that the resultant materials consisted of both spherical macropores and well-defined mesoporous channels. Additional characterisation of this material revealed that it has an exceptionally high surface area (>1110 m2 g−1) and a high concentration of acidic sites, which are considered to be crucial for the hydrolysis of cellulose. Ni nanoparticles were subsequently immobilised onto this material and some additional carbon supports. It was determined that the high surface area and porosity of the synthesised carbon material assisted with the dispersion of the Ni nanoparticles. This Ni catalyst was found to be highly efficient for the one-pot conversion of cellulose to polyols, which is proposed to be a consequence of both the high number of acid sites and excellent Ni dispersion. This approach to catalyst design, offers a novel method for the valorisation of cellulose.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED ENERGY
·
2019
·
IF 8.426
Haowei Li,Hongwei Ma,Weijie Zhao,Xuehui Li,Jinxing Long
Biofuel production from renewable resources is becoming an increasingly attractive option given the depletion of fossil fuels and the environmental problems caused by the excessive use of unsustainable energy resources. In this study, an efficient approach is provided for high-quality oxygen-containing fuel production from renewable lignin bio-oil. The results demonstrate that the calcination temperature has a remarkable effect on the catalyst structure, surface Ni content and physico-chemical properties of the Ni/MgO material, all of which result in significantly different performances in the upgrading of lignin bio-oil. At 160 °C for 4 h and 3 MPa of hydrogen, a 98% lignin bio-oil model compound of guaiacol is converted with 97% cyclohexanol selectivity in the presence of 15% Ni/MgO-850. Furthermore, the optimized catalytic system is reusable and shows good catalytic performance in the upgrading of both light and heavy lignin bio-oils, indicating that it is a promising strategy for renewable lignocellulosic biomass valorization.
研究领域:
能源化学
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2017
·Vol. 7
·期 13
·2813-2818
·
IF 5.773
Yaping Lin,Yifeng Zhu,Xiulian Pan,Xinhe Bao
We demonstrate that the methanation activity of Ni catalysts is modulated by the crystal phase of the TiO2 support. The rutile TiO2 (r-TiO2)-supported Ni catalyst gives a turnover frequency almost two orders of magnitude higher than the anatase TiO2 (a-TiO2)-supported catalyst although the two catalysts exhibit a similar mean Ni particle size. Characterization by H2-TPR, H2-TPD, XPS and IR reveals a stronger interaction between Ni and r-TiO2, leading to a higher capability of CO activation and hydrogenation activity of Ni although Ni is partially covered by TiOx overlayers during reaction. Interestingly, the modulating effects of the titania crystal phases are much more pronounced on the activity of Ni in CO2 methanation.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）