ChemistryOpen
·
2019
·Vol. 8
·期 1
·87-96
·
IF 2.205
Chunshan Lu,Xuejie Zhang,Yani Qi,Haoke Ji,Qianwen Zhu,Hao Wang,Yebin Zhou,Zhenlong Feng,Xiaonian Li
Graphical On the surface : The surface-group-oriented nitrogen-doping strategy for activated carbon-supported Pd catalysts and the potential selective hydrogenation mechanism of p-chloronitrobenzene are presented. A nitrogen-carbon framework with the thickness of several molecules was fabricated through a straightforward nitrogen-doping strategy, in which specially designed surface-oxygen-containing groups (SOGs) first introduced onto the porous carbon support were used to guide the generation of a surface-nitrogen-containing structure through condensation reactions between SOGs and the amidogen group of organic amines under hydrothermal conditions. The results indicate that different kinds of SOGs generate different types and abundances of N species. The CO-releasing groups are apt to form a high proportion of amino groups, whereas the CO 2 -releasing groups, especially carboxyl and lactones, are mainly transformed into pyrrolic-type nitrogen. In the framework with dominant pyrrolic-type nitrogen, an electron-rich Pd activated site composed of Pd, pyrrolic-type N and C is built, in which electron transfer occurs from N to C and Pd atoms. This activated site contributes to the formation of electron-rich activated hydrogen and desorption of p-chloroaniline, which work together to achieve the superior selectivity about 99.90 % of p-chloroaniline and the excellent reusable performance. This strategy not only provides low-cost, nitrogen-doped carbon materials, but also develops a new method for the fabrication of different kinds of nitrogen species structures.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2021
·
IF 5.816
Xiang Gong,Shuyi Guo,Zhao Jiang,Bolun Yang,Tao Fang
Hydrogen is a promising candidate to substitute the fossil fuels. However, the efficient hydrogen storage technologies restrict the commercial applications. Developing new catalysts with high activity and selectivity is important for the dehydrogenation reaction in N-ethylcarbazole/dodecahydro-N-ethylcarbazole (NECZ/12H-NECZ) hydrogen storage system. In this work, a series of Pd-M/Al 2 O 3 (M = Co, Ni and Cu) bimetallic catalysts are synthesized successfully and show good performance in the dehydrogenation reaction of 12H-NECZ than the commercial Pd/Al 2 O 3 catalyst. The Pd 1 Co 1 /Al 2 O 3 catalyst (Practical Pd content = 2.4136 wt%) showed the highest catalytic performance with 95.34% H 2 release amount, TOF of 230.5 min −1 and 85.4% selectivity of NECZ. Combined with the characterization analysis, it can be proposed that the dehydrogenation performance of 12H-NECZ is dependent on the alloy phases , reasonable electronic structures and nanoparticle size of catalysts. The fine-tuned alloy degree and appropriate nanoparticle size of Pd 1 Co 1 /Al 2 O 3 bring the 17.7% increase of H 2 release amount and 99.5% increase of NECZ selectivity than those of Pd/Al 2 O 3 . For the bimetallic catalysts, the enhancement of selectivity of NECZ is mainly from the increase of the kinetic constant of rate-limiting step.
研究领域:
催化化学
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材料科学
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能源存储
✓ 已验证
DOI
高影响因子
Catalysis Science & Technology
·
2022
·Vol. 12
·期 8
·2519-2530
·
IF 6.177
Lixue Qi,Jiajun Dai,Yichen Liao,Jian Tian,Daohua Sun
The low olefin selectivity of Pd-based catalysts is a long-term challenge for the selective hydrogenation of 1,3-butadiene. Hybrid Pd/metal–organic framework (MOF) catalysts may help tackle this problem as they can stabilize Pd nanoparticles and regulate their electronic property. Herein, both surface-supported Pd/ZIF-67 and encapsulated Pd@ZIF-67 catalysts were prepared to explore the synergy between Pd and ZIF-67 and the structure–performance relationship of the catalysts. SEM and TEM reveal the different spatial positions of Pd on the two catalysts. Interestingly, encapsulated Pd@ZIF-67 shows excellent catalytic performance in the 40 h test, with a conversion of 100% and a butene selectivity of 98%, outperforming the surface-supported Pd/ZIF-67 catalyst. XPS, CO-IR and DFT calculations indicate that the encapsulated structure promotes the synergistic interaction between the ZIF-67 and Pd sites. Furthermore, in situ DRIFTS of 1-butene reveals that the enhanced synergistic interaction weakens the adsorption of 1-butene on the catalyst surface while inhibiting its isomerization and further hydrogenation. The presented strategy together with the mechanistic results clarify the relationship between the structure and the synergistic interaction and provide a promising approach for the application of synergistic interactions in hydrogenation catalysts.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2021
·
IF 7.92
Zhi-Feng Jiao,Ya-Ming Tian,Xiao-Ning Guo,Udo Radius,Holger Braunschweig,Todd B. Marder,Xiang-Yun Guo
A highly efficient photocatalytic protocol for borylation of alkyl bromides and chlorides with graphene supported Cu/Pd alloy nanoparticles as a heterogeneous catalyst is reported. This photocatalytic system operates with visible light in air, providing a wide range of primary and secondary alkyl halides with B 2 pin 2 or B 2 neop 2 in high yields at low temperatures, thereby demonstrating its broad utility and functional group tolerance. The high performance is attributed to a synergistic effect of localized surface plasmon resonance (LSPR) of Cu and charge transfer from Cu to Pd due to the alloy surface charge heterogeneity. Transfer of energetic electrons from Pd to electrophilic alkyl halides lead to the formation of the alkyl radicals, which quickly react with a nucleophilic adduct of a diboron compound with base adsorbed on the positively charged Cu sites to form the corresponding borylation product.
研究领域:
有机化学
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材料科学
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催化化学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2011
·
IF 3.384
Baosong Fu,Xiaowen Zhu,Guomin Xiao
High activity ultrafine Pd catalyst was synthesized by both functional polymer encapsulated and impregnation methods. Catalysts were characterized and used to catalyze solvent-free aerobic toluene oxidation. Reaction temperature, time, catalyst mass, air pressure and catalyst reusability were investigated. Catalyst synthesized by encapsulating and immobilizing Pd inside titanium oxide is more active and has a better reusability.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED ORGANOMETALLIC CHEMISTRY
·
2014
·Vol. 28
·期 8
·635-640
·
IF 2.017
Xiaohua Zhao,Xiang Liu,Ming Lu
Low-melting β-cyclodextrin/ N -methylurea (NMU) mixture, an efficient catalytic system for ligand-free Suzuki and Heck couplings in the presence of fresh native β-CD-capped Pd 0 nanoparticles, has been successfully reported. This natural and convenient system can be performed in air and could afford the corresponding cross-coupled products in good to excellent isolated yields after a simple workup under every low Pd loading (0.05 mol%). Remarkably, the catalytic system can be recycled and reused without loss of catalytic activity. Copyright © 2014 John Wiley & Sons, Ltd.
研究领域:
化学
·
材料科学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2015
·Vol. 5
·期 4
·2300-2304
·
IF 5.426
Gang Feng,Ping Chen,Hui Lou
Phenol is an important component of pyrolysis bio-oil, especially from lignin, and the conversion of phenol is crucial for the production of biofuel. A cost-effective and efficient catalyst is worth developing in the hydrogenation of phenol. Herein we report that supported palladium nanoparticles on carbon–nitrogen composites with high surface area are highly active for aqueous-phase hydrogenation of phenol. The conversion of phenol was 91.7% within 1 h at 80 °C. Higher activity was achieved at higher temperature. The synergy between palladium nanoparticles and the carbon–nitrogen composite support accelerated the hydrogenation of phenol, which clarified the crucial role played by the support. The hydrogenation of phenol highlights the potential of these catalysts for upgrading bio-oil.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2015
·
IF 3.942
Qunfeng Zhang,Wei Xu,Xiaonian Li,Dahao Jiang,Yizhi Xiang,Jianguo Wang,Jie Cen,Stephen Romano,Jun Ni
The preparation of supported palladium sulfides catalysts has attracted much attention due to their good sulfur-resistant properties in the hydrogenation of sulfur-containing compounds. In this work, we unambiguously demonstrated that Pd/C catalyst could be in situ sulfided by organic sulfur-containing reactant molecules and the sulfidation was highly dependent on temperature. The in situ sulfidation of Pd/C catalyst was composed of a reaction of Pd with the sulfur derived from the cleavage of C S bond of sulfur-containing reactant molecules, followed by a transformation to Pd x S y at high temperatures (around 120 °C). The sulfided Pd/C catalyst could be used for at least 18 recycles without a significant loss in its activity during the hydrogenation of sulfur-containing nitrobenzene at 180 °C with 3 MPa H 2 , which could be attributed to the stable presence of Pd 4 S and Pd 16 S 7 .
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2025
·
IF 4.7
Lina Guo,Ligang Yan,Ruijun Xie,Limin Han,Ning Zhu
In this work, we investigate a palladium complex exhibiting aggregation-induced emission enhancement (AIEE) properties and remarkable solvatochromism behavior driven by structural changes arising from solvent-solute interactions. Specifically, in polar aprotic solvents, the color of the Pd complex changes from blue to purple as solvent polarity increases, accompanied by a blue shift in the UV–Vis spectrum. Notably, this blue shift is even more pronounced in polar protic solvents, which also show a significant increase in fluorescence emission. These effects are likely driven by hydrogen-bond interaction between the protic solvents and the Pd complex. Density Functional Theory (DFT) calculations show that increased solvent polarity significantly alters the electronic distribution of the Pd complex. Higher solvent polarity leads to a higher orbital transition energy, resulting in a blue shift in the UV–Vis absorption spectrum. X-ray single-crystal structure analysis further reveals that hydrogen-bonding interactions between the Pd complex and methanol stabilize its planar structure. When water is introduced, the Pd complex undergoes aggregation through non-covalent interactions, which modify the stacking arrangement. This change weakens the π-π interactions between adjacent molecules, thereby minimizing energy loss in the system. Consequently, the Pd complex effectively utilizes the AIEE mechanism to detect water content in methanol.
研究领域:
化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Nano
·
2025
·
IF 16
Xiuling Guo,Chao Feng,Zihao Yang,Shingo Hasegawa,Ken Motokura,Yong Yang
Engineering the local coordination environment of single metal atoms is an effective strategy to improve their catalytic activity, selectivity, and stability. In this study, we develop an asymmetric Pd–Ag diatomic site on the surface of g-C3N4 for the selective electrocatalytic semihydrogenation of alkynes. The single Pd atom catalyst, which has a locally symmetric Pd coordination, was inactive for the semihydrogenation of phenylacetylene in a 1 M KOH and 1,4-dioxane solution at an applied potential of −1.3 V (vs RHE). In sharp contrast, doping Ag sites into single Pd atom catalyst to form paired Pd–Ag diatomic sites with asymmetric Pd coordination substantially enhanced the reaction, resulting in a high conversion (>98%) with exceptional time-independent selectivity to styrene under identical conditions. Characterization and theoretical calculations reveal that the introduction of a Ag site into single Pd atoms disrupts their symmetry coordination by forming Pd–Ag bonds with N2–Pd–Ag–N configuration, thereby modulating the electronic and geometric structures of Pd sites, which in turn benefits the adsorption and activation of substrate and lowers energy barrier for the rate-determining step of semihydrogenation, ultimately enhancing the electrocatalytic reaction. This work provides a facile and powerful strategy for the design of advanced catalysts by tuning the local coordination environment for selective catalysis.
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 Materials Chemistry A
·
2024
·
IF 10.7
Bin Zhang,Xulong Song,Zhiheng Wang,Binbin Xu,Wenkai Ye,Lilong Zhang,Han Lin,Tuo Ji,Xiaohua Lu,Jiahua Zhu
The construction of highly active hydrogen evolution electrocatalysts is necessary to improve the efficiency of water electrolysis devices. Pt-based precious metal catalysts have been reported to have high activity, but their high cost and scarcity limit their further application. Herein, we constructed a monolithic electrode containing both Pd nanoparticles (NPs) and Pd single atoms (SAs) anchored on carbonized wood (CW) via atomic layer deposition (ALD). The optimal electrode obtained by adjusting the number of ALD cycles exhibited a lower overpotential of 50.5 mV at 10 mA cm−2 and a smaller Tafel slope of 30.8 mV dec−1 in alkaline electrolyte. Moreover, the optimal CW-Pd20 electrocatalyst was found to possess fast HER kinetics and excellent stability. Theoretical calculations illustrate that Pd NPs facilitated the decomposition of water, while the Pd SAs promoted the adsorption of H, thus leading to excellent HER activity of CW-Pd20.
研究领域:
催化
·
电化学
·
材料科学
·
可再生能源
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Jie Gao,Yang Cao,Yitian Zhang,Gang Luo,Jiajun Fan,James H. Clark,Shicheng Zhang
The inherent structural rigidity of lignin poses a significant challenge to its direct hydrogenation to produce aromatic compounds, requiring harsh reaction conditions. In this study, microwave-assisted hydrothermal liquefication was employed to rapidly generate raw bio-oil under mild conditions, coupled with an in-situ hydrogenation strategy to upgrade its quality. A series of lignin substrates were characterized to establish the relationship between lignin characteristics and aromatic products. Grass lignin can produce low molecular weight bio-oil in high yields (50.4–60.7 %) within 30 min at 180 °C, which is attributed to the abundance of cleavable β-O-4 linkages in its uniform structure. In contrast, softwood lignin with abundant guaiacyl (G) units possessed a robust thermal stability, resulting in a low monomer yield, but a high selectivity to G-type products (97 %). The raw bio-oil was further upgraded through in-situ hydrogenation with Pd catalysts. Low reaction temperatures (60–100 °C) favored the hydrogenation of aromatic aldehydes and ketones to their alcohol products, while high temperatures (100–220 °C) promoted the deep hydrogenation of aromatic side chains to alkyl products. Besides, an upgraded bio-oil with a higher heating value (29.8 MJ/kg) was obtained. Furthermore, the hydrogenation mechanism was investigated through the kinetics of simulated bio-oils. The activation energy follows the order: dimer β-O-4 linkage < monomer aldehyde group < ketone group < C C linkage, which is consistent with the hydrogenation kinetics observed in real lignin bio-oil. Overall, this study highlights the impact of lignin characteristics on subsequent conversion and also enhances our understanding of the complex depolymerization/hydrogenation mechanisms during lignin upgrading.
研究领域:
化学工程
·
生物能源
·
催化
·
可再生能源
✓ 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）