CHINESE JOURNAL OF CHEMISTRY
·
2022
·Vol. 41
·期 3
·307-313
·
IF 5.56
Run-Ze Yuan,Peng-Fei Cui,Yue-Jian Lin,Guo-Xin Jin
Comprehensive Summary Herein, we describe the synthesis of a carborane-supported octanuclear palladacycle complex, Pd 8 ( o -C 2 B 10 H 10 CS 2 CH 3 ) 4 Cl 4 (CH 3 CN) 4 (complex 1 ), with B(3)–H activations on o -carborane ligand. The substitution reaction of 1 has been explored, and three of its substituted complexes Pd 8 ( o -C 2 B 10 H 10 CS 2 CH 3 ) 4 Cl 4 (L) 4 (L = t BuNC, 2 ; L = C 5 H 5 N, 3 ; L = C 4 H 8 S, 4 ) have been synthesized. The m - and p -carborane disubstituted ligands m - and p -C 2 B 10 H 10 (CS 2 CH 3 ) 2 (ligands 5 and 6 ) as well as their B—H activated carborane complexes [ m -C 2 B 10 H 9 (CS 2 CH 3 ) 2 PdCl] ( 7 ) and [ p -C 2 B 10 H 8 (CS 2 CH 3 ) 2 ][PdCl( t BuNC)] 2 ( 8 ) have also been synthesized by the similar method. All of these complexes have been characterized, including X-ray single crystal diffraction, NMR spectroscopy, IR spectroscopy and elemental analysis methods.
研究领域:
无机化学
·
材料科学
✓ 已验证
DOI
高影响因子
NANOTECHNOLOGY
·
2022
·Vol. 33
·期 45
·455401
·
IF 3.953
Hongjing Wang,Hongyong Chen,Shuli Yin,Qiqi Mao,Chunjie Li,You Xu,Xiaonian Li,Ziqiang Wang,Liang Wang
Nonmetal doping is a promising strategy to improve electrocatalytic performance of noble metal based catalysts for oxygen reduction reaction (ORR). Herein, we report a facile method to fabricate PdCuBP nanothorn assemblies (PdCuBP NTAs) by co-doping B and P into pre-synthesized PdCu NTAs using NaBH4 and NaH2PO2 as B source and P source, respectively. The metal-nonmetal structure and multi-branched morphology can optimize oxygen adsorption energy and avoid catalyst migration, agglomeration and Ostwald ripening. As such, the obtained PdCuBP NTAs exhibit efficient activity and excellent long-term stability for ORR. This research offers an excellent strategy for co-doping nonmetal elements into metal nanocrystals with controllable composition and structure to improve electrocatalytic ORR performance.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
POLYMERS FOR ADVANCED TECHNOLOGIES
·
2018
·Vol. 29
·期 6
·1870-1874
·
IF 2.137
Haibo Chang,Dongdong Li,Tingting Cao,Qingshuo Li,Zhanwei Bu,Wenshan Zhao,Tong Lin
In this study, we have for the first time demonstrated that palladium chloride (PdCl 2 ) is an efficient catalyst for ring-opening polymerization of cyclohexene oxide in a solvent-free condition. The polymerization product was in atactic structure, and reaction conditions, such as reaction temperature, time, and catalyst amount, showed effects on polymerization conversion yield, turnover number, and number-average molecular weight of the resulting poly(cyclohexene oxide). PdCl 2 catalysis follows a cationic ring-opening mechanism. The polymerization result is highly determined by the chemical structure of the monomers.
研究领域:
化学
·
高分子科学
✓ 已验证
DOI
高影响因子
Cell Reports Physical Science
·
2020
·
IF 0
Nating Yang,Yonghui Zhao,Hao Zhang,Weikai Xiang,Yuhan Sun,Shuai Yang,Yu Sun,Gaofeng Zeng,Kenichi Kato,Xiaopeng Li,Miho Yamauchi,Zheng Jiang,Tong Li
Sintering-induced aggregation of active metals is a major cause of catalyst deactivation. Catalysts that can operate above 800°C are rare. Here, we report an unusual noble metal catalyst with sintering-induced activation at temperatures up to 1,000°C. The catalyst consists of atomically dispersed palladium embedded in a reducible SnO 2 support designated for lean methane combustion. High temperature reaction simultaneously causes favorable changes of palladium ensemble state combining synergistically with lattice oxygen activation. Such changes lead to at least one order of magnitude improvement of the intrinsic reactivity, which compensates the surface area loss. Extensive characterizations such as atom probe tomography, X-ray absorption spectroscopy, and isotope tracking together with theoretical calculations illustrate the structure and surface chemistry changes and their impacts on the reaction mechanism. The catalyst also shows notable long-term stability and facile regeneration after poisoning. Our work may provide new insights into designing active and thermally stable catalysts.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2020
·
IF 3.99
Xiaoying Lu,Qian Yu,Xueqin Tao,Ting Wang,Kun Zhang,Benxia Li
Pd-based catalysts with high activity and recoverability are desirable for Suzuki coupling reactions which represent an important strategy for constructing carbon-carbon bonds in organic synthesis. Herein, a magnetic PdO x /NiFe 2 O 4 NFs catalyst consisting of PdO x nanoparticles (NPs) and NiFe 2 O 4 nanofibers (NFs) is synthesized by an electrospinning-calcination process. The microstructures and chemical compositions of PdO x /NiFe 2 O 4 NFs catalyst are well characterized. The optimized PdO x /NiFe 2 O 4 NFs exhibits high catalysis toward Suzuki coupling reactions under mild conditions, benefiting from the special electronic state of Pd δ+ (0 < δ < 2) active sites and the porous nanofiber structure of NiFe 2 O 4 support. The turnover frequencies (TOFs) for the reactions of iodo-, bromo- and chloro-benzene over the PdO x /NiFe 2 O 4 NFs catalyst reach up to 2064.79, 1366.74 and 215.28 h −1 , respectively, far exceeding those over the commercial Pd/C catalyst. The kinetic studies demonstrate that the PdO x /NiFe 2 O 4 NFs catalyst is more efficient to reduce the activation energy of Suzuki coupling reaction, which can be attributed to the superiority of Pd δ+ species in both charge-donating and charge-accepting steps of the reactions. Moreover, the PdO x /NiFe 2 O 4 NFs catalyst can be facilely separated and recycled in a long-term catalytic reaction owing to its distinct magnetic feature and good structural stability. This work affords a facile approach for the synthesis of heterogeneous catalyst with tunable compositions and porous structures as well as an attractive catalyst with superior catalytic activity, high stability and reusability.
研究领域:
化学
·
材料科学
·
有机合成
✓ 已验证
DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
·
2020
·
IF 7.1
Yaxu Zhao,Shaohua Wang,Wenjing Yuan,Shurui Fan,Zhongqiu Hua,Yi Wu,Xuemin Tian
Gas sensors based on In 2 O 3 were prepared and were found to be very sensitive to methane with Pd loading (Pd-In 2 O 3 ), even at a low temperature of 300 °C. However, Pd-In 2 O 3 sensors suffer from a high cross-sensitive response to NO 2 , CO and ethanol, which are typical interfering gases for the detection of CH 4 . In order to promote the selective response to CH 4 , a filter based on Pt-Al 2 O 3 catalyst film was printed onto the top of Pd-In 2 O 3 sensor layer. It was found that catalytic film coated sensors could selectively respond to methane even in the mixture of methane with CO, NO 2 , and ethanol. The cross-sensitive responses to the interference of VOCs, CO, NO 2 were almost eliminated. According to the catalytic conversion measurement, it was indicated that CO and ethanol were fully and selectively oxidized to CO 2 and H 2 O. In case of NO 2 , it was proposed that nitrogen dioxide molecules may be blocked on the surface of the catalyst film. Based on the oxygen adsorption behavior, it was suggested the printed catalyst film has no change on the basic sensing mechanism of In 2 O 3 based sensors following the general model that is the adsorption of oxygen and interaction with methane molecule and the resulted electron transfer process. Our investigation demonstrated that Pt-Al 2 O 3 printed Pd-In 2 O 3 sensor could be used for the detection of CH 4 leakage and monitor.
研究领域:
材料科学
·
环境监测
·
化学工程
✓ 已验证
DOI
高影响因子
ORGANOMETALLICS
·
2022
·
IF 3.837
Tongshun An,Chenwei Liu,Yanzhao Yin,Xiao-Feng Wu,Zhiping Yin
A general palladium and silver co-catalyzed denitrogenative carbonylation of benzotriazoles for the synthesis of benzoxazin-4-ones has been developed. Employing benzotriazoles as easily accessible substrates and Cr(CO)6 as bench-stable solid carbonyl sources, various benzoxazin-4-ones were synthesized through a ring-opening/denitrogenative/carbonylation cascade processes in moderate to good yields. Notably, this protocol avoids the use of toxic CO gas and special equipment and can also be applied to the late-stage functionalization of substrates derived from the uricosuric agent probenecid.
研究领域:
有机化学
·
药物化学
✓ 已验证
DOI
高影响因子
GREEN CHEMISTRY
·
2018
·Vol. 20
·期 11
·2588-2595
·
IF 8.586
Da Yang,Huan Liu,Dong-Liang Wang,Zhoujie Luo,Yong Lu,Fei Xia,Ye Liu
A bi-functional ligand (L1) containing a diphosphino fragment and sulfonic acid group (–SO3H) enabled PdCl2(MeCN)2 to efficiently catalyze the tandem bis-alkoxycarbonylation of terminal alkynes to produce aryl-/alkyl-substituted succinate (α,ω-diesters). It was found that the –SO3H incorporated in L1 indispensably assisted the Pd-catalyst in accomplishing this tandem reaction via intramolecular synergic effects. Co-catalysis over the L1-based Pd-catalyst was not due to the physical mixture of Xantphos and MeSO3H. In situ FTIR analysis verified that the formation and stability of Pd–H active species were facilitated by the presence of L1. The formation of stabilized diacylpalladium intermediate (F) was the critical driving force for the second-step methoxycarbonylation. DFT calculation was carried out to optimize the geometric structure of F, which indicated that the developed intramolecular O⋯H hydrogen bonds were an important structural feature to stabilize F. In addition, the L1-based Pd-catalyst could be recycled successfully for at least 3 runs in the ionic liquid [Bmim]NTf2 without obvious activity loss and detectable metal leaching.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
Molecular Catalysis
·
2018
·
IF 0
Wen-Yu Liang,Lei Liu,Qing Zhou,Da Yang,Yong Lu,Ye Liu
The Pd-catalyzed alkoxycarbonylation of alkenes using water as a promoter has been scarcely reported before. Herein, water instead of Brønsted/Lewis acid was found to effectively improve the catalytic performance of Pd(MeCN) 2 Cl 2 -Xantphos system for alkoxycarbonylation of alkenes. Under the optimal conditions, the best yield of 97% was obtained for the target products (methyl 3-phenylpropanoate and methyl 2-phenylpropanoate) with L/B of 4.3 and TON of 192. With the involvement of water, Pd(MeCN) 2 Cl 2 -Xantphos system also exhibited the moderate to good generality to alkoxycarbonylation of different kinds of alkenes with alcohols. The in situ high pressure FT-IR analysis verified that water played an important role in promoting formation and stability of Pd H active species which was responsible for the efficient alkoxycarbonylation of alkenes. In addition, the ligand effect of Xantphos on this reaction was discussed.
研究领域:
化学
·
催化反应
✓ 已验证
DOI
MOLECULES
·
2019
·Vol. 24
·期 4
·674
·
IF 3.06
Haodong Tang,Bin Xu,Meng Xiang,Xinxin Chen,Yao Wang,Zongjian Liu
Nitrogen-doped activated carbon (N-AC) obtained through the thermal treatment of a mixture of HNO3-pretreated activated carbon (AC) and urea under N2atmosphere at 600 °C was used as the carrier of Pd catalyst for both liquid-phase hydrodechlorination of 2,4-dichlorophenol (2,4-DCP) and gas-phase hydrodechlorination of chloropentafluoroethane (R-115). The effects of nitrogen doping on the dispersion and stability of Pd, atomic ratio of Pd/Pd2+on the surface of the catalyzer, the catalyst’s hydrodechlorination activity, as well as the stability of N species in two different reaction systems were investigated. Our results suggest that, despite no improvement in the dispersion of Pd, nitrogen doping may significantly raise the atomic ratio of Pd/Pd2+on the catalyst surface, with a value of 1.2 on Pd/AC but 2.2 on Pd/N-AC. Three types of N species, namely graphitic, pyridinic, and pyrrolic nitrogen, were observed on the surface of Pd/N-AC, and graphitic nitrogen was stable in both liquid-phase hydrodechlorination of 2,4-DCP and gas-phase hydrodechlorination of R-115, with pyridinic and pyrrolic nitrogen being unstable during gas-phase hydrodechlorination of R-115. As a result, the average size of Pd nanocrystals on Pd/N-AC was almost kept unchanged after liquid-phase hydrodechlorination of 2,4-DCP, whereas crystal growth of Pd was clearly observed on Pd/N-AC after gas-phase hydrodechlorination of R-115. The activity test revealed that Pd/N-AC exhibited a much better performance than Pd/AC in liquid-phase hydrodechlorination of 2,4-DCP, probably due to the enhanced stability of Pd exposed to the environment resulting from nitrogen doping as suggested by the higher atomic ratio of Pd/Pd2+on the catalyst surface. In the gas-phase hydrodechlorination of R-115, however, a more rapid deactivation phenomenon occurred on Pd/N-AC than on Pd/AC despite a higher activity initially observed on Pd/N-AC, hinting that the stability of pyridinic and pyrrolic nitrogen plays an important role in the determination of catalytic performance of Pd/N-AC.Keywords:activated carbon;hydrodechlorination;nitrogen doping;Pd
研究领域:
环境科学
·
催化化学
✓ 已验证
DOI
PubMed
高影响因子
ELECTROCHEMISTRY COMMUNICATIONS
·
2013
·
IF 4.425
Wei Hong,Jin Wang,Erkang Wang
A facile synthesis of PdAg alloyed bimetallic nanocrystals with flower-shaped porous morphology is demonstrated. The whole synthetic process is very simple just by mixing palladium nitrate, silver nitrate, polyvinylpyrrolidone and hydroquinone and heated at 70 °C for 15 min. The prepared flower-shaped porous PdAg nanoparticles exhibit superior electrocatalytic activity toward ethanol electrooxidation in alkaline condition, and the catalytic performance could be easily tuned by the Pd/Ag ratio.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
CATALYSIS COMMUNICATIONS
·
2016
·
IF 3.389
Longfei Geng,Yan Li,Zhengliang Qi,Haipeng Fan,Zhicheng Zhou,Rizhi Chen,Yong Wang,Jun Huang
Through Pd catalyzed C N coupling reaction, Pd nanoparticles and diadamantylphosphine ligand were immobilized in situ into the formed N contained polymers as heterogeneous Pd catalysts for Suzuki-Miyaura reaction. The Pd@NPad 2 -1.0 catalyst was found to be highly efficient and only 4 ppm of Pd (Pd@NPad 2 -1.0) was required for the coupling of aryl bromides with phenylboronic acid, and the corresponding products were obtained in good to excellent yields with high TON and TOF as 250,000 and 41,666 h − 1 respectively. Moreover, the coupling of various aryl chlorides with phenylboronic acids gave the corresponding products in high yields also. And the Pd@NPad 2 -1.0 catalyst is reusable at least 5 times with only slight deactivation.
研究领域:
化学
·
催化材料科学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）