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991.
Hydrogen Spillover Enhanced Hydroxyl Formation and Catalytic Activity Toward CO Oxidation at the Metal/Oxide Interface 下载免费PDF全文
Yuekang Jin Guanghui Sun Feng Xiong Liangbing Ding Prof. Dr. Weixin Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(11):4252-4256
H2‐promoted catalytic activity of oxide‐supported metal catalysts in low‐temperature CO oxidation is of great interest but its origin remains unknown. Employing an FeO(111)/Pt(111) inverse model catalyst, we herewith report direct experimental evidence for the spillover of H(a) adatoms on the Pt surface formed by H2 dissociation to the Pt?FeO interface to form hydroxyl groups that facilely oxidize CO(a) on the neighboring Pt surface to produce CO2. Hydroxyl groups and coadsorbed water play a crucial role in the occurrence of hydrogen spillover. These results unambiguously identify the occurrence of hydrogen spillover from the metal surface to the noble metal/metal oxide interface and the resultant enhanced catalytic activity of the metal/oxide interface in low‐temperature CO oxidation, which provides a molecular‐level understanding of both H2‐promoted catalytic activity of metal/oxide ensembles in low‐temperature CO oxidation and hydrogen spillover. 相似文献
992.
993.
This paper considers the problem of change point in single index models. In order to obtain asymptotically valid confidence intervals for the estimation of the change point, the convergence rate and asymptotic distribution of the change point estimate is studied. Some simulation results are presented which show that the numerical performance of our estimator is satisfactory. 相似文献
994.
995.
Yongho Shin Tae Yeon Kong Jae Cheol Cheong Jin Young Kim Jae Il Lee Hye Suk Lee 《Biomedical chromatography : BMC》2019,33(9)
A liquid chromatography–tandem mass spectrometric method for the simultaneous determination of 75 abuse drugs and metabolites, including 19 benzodiazepines, 19 amphetamines, two opiates, eight opioids, cocaine, lysergic acid diethylamide, zolpidem, three piperazines and 21 metabolites in human hair samples, was developed and validated. Ten‐milligram hair samples were decontaminated, pulverized using a ball mill, extracted with 1 mL of methanol spiked with 28 deuterated internal standards in an ultrasonic bath for 60 min at 50°C, and purified with Q‐sep dispersive solid‐phase extraction tubes. The purified extracts were evaporated to dryness and the residue was dissolved in 0.1 mL of 10% methanol. The 75 analytes were analyzed on an Acquity HSS T3 column using gradient elution of methanol and 0.1% formic acid and quantified in multiple reaction monitoring mode with positive electrospray ionization. Calibration curves were linear (r ≥ 0.9951) from the lower limit of quantitation (2–200 pg/mg depending on the drug) to 2000 pg/mg. The coefficients of variation and accuracy for intra‐ and inter‐assay analysis at three QC levels were 4.3–12.9% and 89.2–109.1%, respectively. The overall mean recovery ranged from 87.1 to 105.3%. This method was successfully applied to the analysis of 11 forensic hair samples obtained from drug abusers. 相似文献
996.
Yan‐Ping Zhang Yue Li Guan‐Cheng Xu Jin‐Yu Li Hua‐Ying Luo Jin‐Yao Li Li Zhang Dian‐Zeng Jia 《应用有机金属化学》2019,33(3)
Two new complexes, namely [Cu6L6] ( 1 ) and [Zn(HL)2] ( 2 ) (H2L = N‐(1‐phenyl‐3‐methyl‐4‐propenylidene‐5‐pyrazolone)‐2‐furancarboxylic acid hydrazide), have been synthesized and characterized. Single crystal X‐ray analysis indicates that complex 1 has a hexanuclear structure and complex 2 exhibits a mononuclear structure. The DNA/bovine serum albumin (BSA) binding properties of complexes 1 and 2 were investigated by absorption spectroscopy and fluorescence quenching. Both complexes could effectively intercalate to DNA with calculated quenching constants of 2.6 × 105 and 1.25 × 105 M?1, respectively. The quenching mechanism of the intrinsic fluorescence of BSA by the complexes was found to be a static one. The cytotoxicities of 1 and 2 were investigated in two human tumor cell lines, human esophageal cancer cells (Eca‐109) and cervical cancer cells (HeLa). Complex 1 exhibits higher antitumor activity than 2 . Furthermore, 1 can inhibit HeLa cells by inducing apoptosis and G0/G1 phase cell cycle arrest. All results demonstrate that 1 and 2 both have DNA/BSA binding capacity and antitumor activity. 相似文献
997.
Tae Hee Kim Hyun Mo Lee Hee Soo Park Sung Dong Kim Su Jin Kwon Atsushi Tahara Hideo Nagashima Bun Yeoul Lee 《应用有机金属化学》2019,33(4)
The original Sasol catalytic system for ethylene tetramerization is composed of a Cr source, a PNP ligand, and MAO (methylaluminoxane). The use of expensive MAO in excess has been a critical concern in commercial operation. Many efforts have been made to replace MAO with non‐coordinating anions (e.g., [B(C6F5)4]?); however, most of such attempts were unsuccessful. Herein, an extremely active catalytic system that avoids the use of MAO is presented. The successive addition of two equivalent [H(OEt2)2]+[B(C6F5)4]? and one equivalent CrCl3(THF)3 to (acac)AlEt2 and subsequent treatment with a PNP ligand [CH3(CH2)16]2C(H)N(PPh2)2 ( 1 ) yielded a complex presumably formulated as [ 1 ‐CrAl (acac)Cl3(THF)]2+[B(C6F5)4]?2, which exhibited high activity when combined with iBu3Al (1120 kg/g‐Cr/h; ~4 times that of the original Sasol system composed of Cr (acac)3, iPrN(PPh2)2, and MAO). Via the introduction of bulky trialkylsilyl substituents such as –SiMe3, –Si(nBu)3, or –SiMe2(CH2)7CH3 at the para‐position of phenyl groups in 1 (i.e., by using [CH3(CH2)16]2C(H)N[P(C6H4‐p‐SiR3)2]2 instead of 1 ), the activities were dramatically improved, i.e., tripled (2960–3340 kg/g‐Cr/h; more than 10 times that of the original Sasol system). The generation of significantly less PE (<0.2 wt%) even at a high temperature is another advantage achieved by the introduction of bulky trialkylsilyl substituents. NMR studies and DFT calculations suggest that increase of the steric bulkiness on the alkyl‐N and P‐aryl moieties restrict the free rotation around (alkyl)N–P (aryl) bonds, which may cause the generation of more robust active species in higher proportion, leading to extremely high activity along with the generation of a smaller amount of PE. 相似文献
998.
Bei-Bei Guo Dr. Yue-Jian Lin Prof. Guo-Xin Jin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(41):9721-9727
Four flexible ligands with different lengths, degrees of flexibility, and steric bulk were synthesized and used to prepare metal-directed assemblies. Interestingly, minor differences among the ligands led to products with dramatically different topologies: a binuclear D -shaped macrocycle, tetranuclear rectangles, and hexanuclear trefoil knots. The interconversion of the trefoil-shaped complexes was also investigated. This contribution introduces a rare ligand-controlled trefoil–rectangle shape transformation in solution. 相似文献
999.
Yingying Wang Yang Zhou Min Lei Jinjun Hou Qinghao Jin Dean Guo Wanying Wu 《Tetrahedron》2019,75(9):1180-1185
A straightforward and general method has been developed for the synthesis of phthalimide derivatives from 2-iodobenzamides and PPh3/I2/HCOOH in the presence of a catalytic amount of Pd(OAc)2. The reaction results demonstrate that PPh3/I2/HCOOH is a facile, efficient and safe CO source. The whole process is carried out in toluene at 80?°C and furnishes the desired products in good to excellent yields. 相似文献
1000.
International Journal of Theoretical Physics - We propose the scheme for cyclic controlled symmetry quantum teleportation by using one three-dimensional hyper-entangled state as the quantum... 相似文献