Journal of Environmental Chemical Engineering
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2024
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IF 7.4
Xiaoting Xing,Wenlong Cao,Jinliang Yan,Yuchun Zhang,Payam Ghorbannezhad,Zhiyu Li,Peng Fu
Cyclohexanol is a crucial intermediate in the synthesis of nylon and other chemical industry materials. However, directly hydrogenating phenol to cyclohexanol presents challenges, including harsh reaction conditions and low selectivity for the desired product. To address these issues, a two-step method was proposed, involving the mild catalytic decoupling and hydrogenation of lignin, which enables the efficient production of cyclohexanol. Lignin was initially depolymerized into 18.08 % phenol and 60.63 % guaiacol in a dilute alkaline aqueous solution at 200°C under atmospheric nitrogen. Subsequently, the effects of catalytic hydrogenation of phenol in different solvents were examined. When water was used as the solvent, phenol conversion reached 100 % within 2 hours at 30°C, with a selectivity of 94.69 % to cyclohexanol. The hydrogenation process, catalyzed by 5 wt% Pd/AC, was studied under these conditions. It was found that phenol was first partially hydrogenated to cyclohexenol, which quickly isomerized to cyclohexanone and was further hydrogenated to cyclohexanol. The two steps create a low-temperature and low-pressure pathway for efficiently converting lignin to cyclohexanol, thereby enhancing lignin's potential value.
研究领域:
化学工程
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生物质转化
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催化科学
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
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2015
·Vol. 18
·期 8
·2435-2442
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IF 8.02
Chaofeng Zhang,Jianmin Lu,Mingrun Li,Yehong Wang,Zhe Zhang,Haijun Chen,Feng Wang
We present an experimental and computational study of the elementary steps of hydrazine hydrogen transfer on crystalline MoO2, and demonstrate its unique bifunctional metallic-basic properties in a catalytic hydrogenation reaction. Density functional theory (DFT) calculations suggest that the stepwise hydrogen transfer via the prior cleavage of the N–H bond rather than the N–N bond, is the key step to create the dissociated hydride and proton species on the dual Mo and O sites, marking its difference with common oxides. Crystalline MoO2 shows exceptionally high chemoselectivity toward the nitro reduction over CC, CC, and CN groups at room temperature and lower, down to 0 °C, rendering it as a promising catalytic material for hydrogenation reactions.
研究领域:
化学
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材料科学
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DOI
高影响因子
ACS Applied Materials & Interfaces
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2020
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IF 8.758
Hairus Abdullah,Yu-Rou Ko,Dong-Hau Kuo,Noto Susanto Gultom
La–Sn-codoped Zn(O,S) catalysts were synthesized with different amounts (0%, 2.5%, 5%, and 10%) of Sn and a constant amount (10%) of La to improve the photocatalytic hydrogenation reaction (PHR) of azobenzene to aniline. The as-prepared catalysts were carefully characterized and tested for a hydrogenation reaction. The incorporation of Sn significantly enhanced the PHR activities since the incorporated Sn in the Zn(O,S) lattices could increase the conductivity of the catalysts to improve the charge transfer during the catalytic reaction as indicated with EIS measurement. Further measurement with a photoresponse of La–Sn-codoped Zn(O,S) catalysts also exhibited relatively higher intensities as compared to those of La-doped Zn(O,S) and Sn-doped Zn(O,S) catalysts. On the basis of the measurement results of EIS and transient photo current, the La–Sn-codoped Zn(O,S) with the best properties was further utilized for PHR to convert azobenzene to aniline. GC–MS measurement confirmed that 15 ppm azobenzene could be totally converted to aniline in only 60 min which was achieved with a catalyst that was prepared with 5%-Sn and 10%-La doping. The relatively short reaction time indicated that the as-prepared catalyst had a strong reduction capability able to cleave the strong bonding of N═N in azobenzene. The reaction kinetic of the N═N bond cleavage was elucidated based on solvation, adsorption, pinning, and photocatalytic hydrogenation processes on the catalyst surfaces.
研究领域:
材料科学
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环境科学
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化学工程
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产品关联
DOI
PubMed
高影响因子
MOLECULES
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2022
·Vol. 27
·期 21
·7431
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IF 4.927
Caimei Zhang,Wenjuan Zhang,Yiran Wu,Bo Peng,Chunyuan Tian,Feng Luan,Wen Sun,Xuming Zhuang,Lijun Zhao
With several major polarity and weak optical properties, the sensitive detection of HCOOH remains a major challenge. Given the special role of HCOOH in assisting in the catalytic hydrogenation process of Ir complexes, HCOOH (as a hydrogen source) could rapidly activate Ir complexes as catalysts and further reduce the substrates. This work developed a facile and sensitive HCOOH fluorescence sensor utilizing an optimal catalytic fluorescence generation system, which consists of the phenyl-pyrazole-type Ir-complex PP-Ir-Cl and the coumarin-type fluorescence probe P-coumarin. The sensor demonstrates excellent sensitivity and specificity for HCOOH and formates; the limits of detection for HCOOH, HCOONa, and HCOOEt3N were tested to be 50.6 ppb, 68.0 ppb, and 146.0 ppb, respectively. Compared to previous methods, the proposed sensor exhibits good detection accuracy and excellent sensitivity. Therefore, the proposed HCOOH sensor could be used as a new detection method for HCOOH and could provide a new design path for other sensors.Keywords:HCOOH detection;Ir complexes;catalytic hydrogenation;fluorescence probe
研究领域:
分析化学
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催化
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传感器
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产品关联
DOI
PubMed
高影响因子
FUEL
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2023
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IF 7.4
Hai-Xu Zou,Xiang Bai,Xing Fan,Min-Hua Wang,Yang-Yang Xu,Feng-Yun Ma,Xian-Yong Wei,Peter N. Kuznetsov
Three biomass (rice straw, rice husk and wheat straw) and three coal samples (lignite, subbituminous coal and bituminous coal) were extracted via a thermal dissolution (TD) process, and the TD extracts were treated by catalytic hydrogenation to obtain reaction products. To reveal the similarity in molecular information among the samples and elucidate their chemical reactivity, four machine learning algorithms were applied to analyze the Fourier transform infrared spectra of both TD extracts and catalytic hydrogenation products. Functional groups were used as variables and the difference in peak area can be treated as the basis for sample classification. Aromatic C H, C O C, aliphatic CH 2 or CH 3 and aromatic C O or C C bonds were the main characteristic variables in principal component analysis algorithm to classify biomass- and coal-derivated samples. These samples were also grouped into four clusters by hierarchical clustering analysis algorithm according to the similarity and difference in the distribution of functional groups. For artificial neural network algorithm, aliphatic C H and OH bonds are the most important variables to classify these samples into four groups, and aromatic C H, OH, and C O C groups are the main variables contributed to the classification trees in random forest algorithm. Machine learning algorithms will provide methodological guidance for the data mining of the spectra of complex organic systems.
研究领域:
化学工程
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数据科学
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产品关联
DOI
高影响因子
Inorganic Chemistry Frontiers
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2021
·Vol. 8
·期 21
·4712-4719
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IF 6.569
Tianxing Wu,Hanqi Meng,Rui Dang
Electrocatalytic hydrogenation is a competing reaction for hydrogen evolution that occurs in the presence of organic compounds containing unsaturated chemical bonds using water as the hydrogen donor. Here, we propose a simple method to synthesize amorphous Ta2O5 loaded amorphous Ru with poor crystallinity. The amorphous composite (Ta2O5/Ru-4.0-400) with an ultra-low Ru loading amount (2.16 wt%) exhibits 69.8% conversion of cinnamaldehyde with 29.1% FE and 100% selective formation of half-hydrogenated hydrocinnamaldehyde under a constant potential of −1.1 V vs. RHE for 5 h. Detailed experimental studies revealed that the amorphous structure with poor crystallinity offers structural flexibility and rich defects for electrochemical hydrogenation reactions, and the Ta2O5 substrate serves as a bridge to effectively facilitate electron transfer from Ru to CAL molecules. This work presents a new strategy for designing highly efficient electrocatalysts with an amorphous structure for the hydrogenation of organic compounds containing unsaturated chemical bonds.
研究领域:
材料科学
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电化学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Zhi-Yuan Zheng,Zhi-Feng Jiao,Ji-Xiao Zhao,Xin-Chao Liu,Cai-Dong Song,Jia-Hang Li,Xiang-Yun Guo
In the hydrogenation of polyfunctional compounds, achieving high selectivity for specific functional groups remains challenging. Herein we report that SiC quantum dots (QDs) can selectively adsorb C = O in cinnamaldehyde, significantly increasing the activity and selectivity of Pt/SiC for hydrogenating cinnamaldehyde to cinnamyl alcohol. A 10 wt% QDs-modified Pt/SiC catalyst showed a turnover frequency 3.5 times higher than Pt/SiC under mild conditions. Further studies reveal that the defect-rich surface of SiC QDs facilitates the adsorption of C = O bond in cinnamaldehyde and enhances the spillover of active hydrogen from Pt to SiC QDs. During the catalysis process, Pt is responsible for the generation of reactive hydrogen species while the QDs undertake the activation of C = O bond, and the hydrogen species react with cinnamaldehyde via spillover. This work demonstrates the promise of SiC QDs in heterogeneous catalysis and provides a reference for designing novel hydrogenation catalysts.
研究领域:
材料科学
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催化化学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2021
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IF 19.503
Meng Jin,Yanyan Liu,Xian Zhang,Jialu Wang,Shengbo Zhang,Guozhong Wang,Yunxia Zhang,Huajie Yin,Haimin Zhang,Huijun Zhao
We report ultrafine Cu x Pt y alloying nanoparticles anchored on carbon black (Cu x Pt y /C) for selective electrocatalytic hydrogenation of nitrobenzene (Ph-NO 2 ) at ambient conditions. The experimental and theoretical studies reveal that as electrocatalyst, the optimal Cu 3 Pt/C with adjusted electronic structure can effectively facilitate the adsorption and activation of Ph-NO 2 . The results indicate that the acidic media is favorable for the production of aminobenzene irrelevant to the applied potential, while the electrocatalytic hydrogenation products are highly dependent on the reduction potential in the alkaline media. As a result, the Cu 3 Pt/C can afford almost 100 % conversion of Ph-NO 2 into azoxybenzene with ∼99 % selectivity at 0.3 V (vs. RHE) and aminobenzene with ∼99 % selectivity at -0.3 V (vs. RHE) in 1.0 M KOH, respectively. The theoretical calculations provide a comprehensive understanding of the selective electrocatalytic hydrogenation mechanisms of Ph-NO 2 relative to electrolyte pH and applied potential, matched well with the experimental results.
研究领域:
化学
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材料科学
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电化学
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DOI
高影响因子
ACS Applied Nano Materials
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2024
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IF 5.3
Wenjing Li,Weichen Wang,Mingyue Zhu,Peiao Cong,Daowei Gao,Rongyao Wang,Guozhu Chen
Metal oxides@metal–organic framework (MOFs)-based core/shell nanostructures demonstrate promising potential in catalytic hydrogenations. However, the direct nucleation and growth of MOFs on the topologically diverse surfaces of metal oxides face significant challenges due to the high interfacial energy resulting from topological mismatches. Herein, we present a facile in situ growth strategy for directly assembling an MIL-53(Al) layer on the surface of CeO2 nanospheres at low temperatures by mixing and stirring CeO2 nanospheres and MIL-53(Al) precursors without requiring sacrificial templates or additional surface modifications. Moreover, key factors such as reaction time, temperature, and the types of aluminum salts and ligands are systematically explored to comprehensively understand the nucleation behavior of MOFs shells. Notably, when active Pt nanoparticles are sandwiched between the CeO2 core and the MIL-53(Al) shell, the MIL-53(Al) effectively stabilizes the Pt nanoparticles and enhances the selectivity of hydrocinnamaldehyde in cinnamaldehyde hydrogenation. CeO2/Pt@MIL-53(Al) achieved more than twice the selectivity for HCAL compared to CeO2/Pt and even outperformed Pt/MIL-53(Al). Undoubtedly, this study provides distinctive insights into the nucleation and growth mechanisms of MOFs on metal oxides, expands the strategies for fabricating metal oxides@MOFs core/shell nanostructure, and proposes innovative ideas and possibilities for broadening the application domains of MOFs-based materials.
研究领域:
材料科学
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催化化学
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产品关联
DOI
高影响因子
Biomass Conversion and Biorefinery
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2024
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IF 3.5
Yang Mingzhu,Li Liangli,Shi Jingjing,Xia Haian,Xu Junming
Lignin is an important source of biomass energy and chemical raw material. The combination of lignin depolymerization and electrocatalytic hydrogenation (ECH) is a very important pathway to convert lignin to high-value chemicals or bio-fuels, which has important economic and environmental significance. It remains great challenges to control the conversion pathways and modulate the desired product selectivity. In additions, in-depth understanding of the hydrodeoxygenation mechanism of lignin pyrolysis oil in ECH has not yet been revealed. Herein, we report the results of ECH of various typical lignin models using Pt/C in a fluid electrocatalytic system. Common phenolic model compounds with different functional groups and varying chain lengths were chosen as the reaction substrates, such as guaiacol, 2,6-dimethoxyphenol, eugenol, phenol, vanillin. The effects of the types and positions of functional groups such as hydroxyl, methoxyl and alkyl groups on the ECH performances were investigated. The electrolytic hydrogenation system employed phosphotungstic acid (PW12) and phosphoric acid as the electrolyte, NaBH 4 as a partial hydrogen source and PW12 reducing agent, and Pt/C as the catalyst directly added to the electrolyte. Results demonstrated that the production of cyclohexane from the ECH of the phenolic model compounds, which have undergone complete deoxygenation. For phenolic compounds containing alkyl substituents, the conversion decreases with increasing chain length, but the selectivity of alkyl cyclohexane increases. These findings contribute to advancing the understanding of lignin utilization and pave the way for sustainable development and energy transformation.
研究领域:
生物质化学
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催化化学
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可再生能源
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产品关联
DOI
高影响因子
ENERGY & FUELS
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2024
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IF 5.2
Bo Wang,Wen Cai,Huai Liu,Rui Zhang,Wenlong Jia,Junhua Zhang,Lincai Peng
Catalytic hydrogenation of carbohydrates over the Raney Ni catalyst is an important industrial process to produce valuable polyols. However, this process generally encounters challenges such as harsh reaction conditions, low catalytic activity, and catalyst deactivation. In this contribution, metallic nickel-rich nickel borides (NiBO-nKH2PO4) were successfully constructed via a simple chemical reduction method with potassium dihydrogen phosphate (KH2PO4) as the buffering agent and sodium borohydride (NaBH4) as the reducing reagent. Especially, the obtained NiBO-10KH2PO4 afforded quantitative sorbitol yield from the catalytic hydrogenation of glucose under mild reaction conditions within 1 h (80 °C and 1 MPa H2). Compared with the reported literature for the production of sorbitol from glucose, the developed NiBO-10KH2PO4 catalyst circumvents the use of a high hydrogen pressure and reaction temperature while delivering excellent catalytic performance and stability. Moreover, the experimental analysis demonstrated that the obtained nickel borides, with the assistance of KH2PO4, possessed abundant metallic nickel species, which favored the adsorption and activation of hydrogen molecules and thus largely promoted the hydrogenation of glucose. This work provides new insights into the rational design of practical nickel-based catalysts for the efficient catalytic hydrogenation of carbohydrates.
研究领域:
化学工程
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催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2022
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IF 7.139
Yunfei Zhang,Yi Shen
Converting levulinic acid (LA) to fuel precursors such as gama-valerolactone (GVL) and valeric acid (VA) via an efficient and low-cost method is of great significance. Herein, a series of free-standing electrodes consisting of metallic metals supported by carbon felts (CFs) were fabricated via a facile electro-deposition process. The resulting M/CFs (M = Pb, Cd, Co, Ni, Cu and Bi) electrodes were evaluated for electrocatalytic hydrogenation (ECH) of LA. The electrocatalytic activity of the electrodes was extensively studied by various electrochemical methods including cyclic voltammetry , linear sweep voltammetry and chronoamperometry measurements. The products of the ECH processes were analyzed by gas chromatography-mass spectrometry. Of all the prepared samples, the Pb/CFs and Cd/CFs electrodes showed superior performance for ECH of LA. The selectivity of VA reached up to 91.7% when the Pb/CFs was used and the conversion of LA reached to 57.2% using the Cd/CFs electrode, rendering them as one of the best electrodes for ECH reported in the literature. The effects of applied potentials on the ECH process were investigated. To further optimize the ECH performance of the Pb/CFs electrodes, several key parameters including deposition time , pH value of the electrolyte and reaction time were studied. When the electrodeposition time was 600 s and the concentration of sulfuric acid in the electrolyte was 0.5 M, the complete transformation of 0.2 M of LA was achieved after 6 h. This study may afford an alternative way to the conversion of LA to GVL or VA.
研究领域:
化学工程
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电化学
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催化材料
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）