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11.
Dr. Xiaoyan Sun Prof. Dr. Shaodong Zhou Dr. Lei Yue Dr. Maria Schlangen Prof. Dr. Helmut Schwarz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(14):3550-3559
Thermal gas-phase reactions of the ruthenium-oxide clusters [RuOx]+ (x=1–3) with methane and dihydrogen have been explored by using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. For methane activation, as compared to the previously studied [RuO]+/CH4 couple, the higher oxidized Ru systems give rise to completely different product distributions. [RuO2]+ brings about the generations of [Ru,O,C,H2]+/H2O, [Ru,O,C]+/H2/H2O, and [Ru,O,H2]+/CH2O, whereas [RuO3]+ exhibits a higher selectivity and efficiency in producing formaldehyde and syngas (CO+H2). Regarding the reactions with H2, as compared to CH4, both [RuO]+ and [RuO2]+ react similarly inefficiently with oxygen-atom transfer being the main reaction channel; in contrast, [RuO3]+ is inert toward dihydrogen. Theoretical analysis reveals that the reduction of the metal center drives the overall oxidation of methane, whereas the back-bonding orbital interactions between the cluster ions and dihydrogen control the H−H bond activation. Furthermore, the reactivity patterns of [RuOx]+ (x=1–3) with CH4 and H2 have been compared with the previously reported results of Group 8 analogues [OsOx]+/CH4/H2 (x=1–3) and the [FeO]+/H2 system. The electronic origins for their distinctly different reaction behaviors have been addressed. 相似文献
12.
Chanho Pak Seung Woo Lee Chaekyung Baik Bong Ho Lee Dae Jong You Eunyoung You 《中国化学快报》2019,30(6):1186-1189
New approach for the reversal tolerant anode for polymer electrolyte membrane fuel cell is suggested by using the multifunctional IrRu alloy catalyst having concurrent superior activities towards hydrogen oxidation reaction and oxygen evolution reaction to mitigate the degradation of anode under the fuel starvation condition. 相似文献
13.
In this study, we present a versatile and easy procedure for modifying a cobalt ferrite nanoparticle step by step. A new nanocatalyst was prepared via CuII immobilized onto CoFe2O4@HT@Imine. The catalyst was fully characterized by Fourier‐transform infrared (FT‐IR), energy‐dispersive X‐ray spectroscopy (EDX), field emission scanning electron microscopy (FE‐SEM), X‐ray diffraction (XRD), and vibrating sample magnetometer (VSM) analyses. The current procedure as a green protocol offers benefits including a simple operational method, an excellent yield of products, mild reaction conditions, minimum chemical wastes, and short reaction times. Without any significant reduction in the catalytic performance, up to five recyclability cycles of the catalyst were obtained. The optimization results suggest that the best condition in the oxidation of benzyl alcohol derivatives is 0.003 g of the CoFe2O4@HT@Imine‐CuII catalyst, TEMPO, at 70°C under solvent‐free condition and air. 相似文献
14.
Shilin Jiang Dr. Yalan Liu Dr. Lin Wang Prof. Zhifang Chai Prof. Wei-Qun Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201145
The coordination chemistry of f-block elements (lanthanide and actinide) in molten salts has become a resounding topic in view of its great importance to the research and development (R&D) of molten salt reactors and pyroprocessing. In this Review article, a general overview of the coordination chemistry of f-block elements in molten salts is provided including past achievements and recent advances. Particular emphases are placed on the oxidation state, speciation, and solution structure of f-block metal ions in molten salts, as well as their relationships with the salt composition. Furthermore, this review briefly discusses the spectroscopic and theoretical methods that complement each other in revealing the coordination properties. 相似文献
15.
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
16.
Niloufar Afzali Reihaneh Kardanpour Farnaz Zadehahmadi Shahram Tangestaninejad Majid Moghadam Valiollah Mirkhani Adam Mechler Iraj Mohammadpoor‐Baltork Mehrnaz Bahadori 《应用有机金属化学》2019,33(11)
A novel heterogeneous nanocatalyst was established by supporting molybdenum (VI) on Zr6 nodes in the structure of the well‐known UiO‐66 metal–organic framework (MOF). The structure of the UiO‐66 before and after Mo (VI) immobilization was confirmed with XRD, DR‐FTIR and UV–vis spectroscopy, and the presence and amount of Mo (VI) was identified by X‐ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectroscopy. TEM imaging confirmed the absence of Mo clusters on the MOF surface, while SEM confirmed that the appearance of the MOF has not changed upon immobilizing the Mo (VI) catalyst. BET adsorption measurements were used to confirm the porosity of the catalyst. The catalytic activity of this heterogeneous catalyst was investigated in oxidation of sulfides with H2O2 in acetonitrile and oxidative desulfurization of dibenzothiophene. Easy work up, convenient and steady reuse and high activity and selectivity are prominent properties of this new hybrid material. 相似文献
17.
Two highly ordered isonicotinamide (INA)‐functionalized mesoporous MCM‐41 materials supporting indium and thallium (MCM‐41‐INA‐In and MCM‐41‐INA‐Tl) have been developed using a covalent grafting method. A surface functionalization method has been applied to prepare Cl‐modified mesoporous MCM‐41 material. Condensation of this Cl‐functionalized MCM‐41 with INA leads to the formation of MCM‐41‐INA. The reaction of MCM‐41‐INA with In(NO3)3 or Tl(NO3)3 leads to the formation of MCM‐41‐INA‐In and MCM‐41‐INA‐Tl catalysts. The resulting materials were characterized using various techniques. These MCM‐41‐INA‐In and MCM‐41‐INA‐Tl catalysts show excellent catalytic performance in the selective oxidation of sulfides and thiols to their corresponding sulfoxides and disulfides. Finally, it is found that the anchored indium and thallium do not leach out from the surface of the mesoporous catalysts during reaction and the catalysts can be reused for seven repeat reaction runs without considerable loss of catalytic performance. 相似文献
18.
Maurice Dörr Sebastian Lips Prof. Dr. Carlos Alberto Martínez-Huitle Dr. Dieter Schollmeyer Prof. Dr. Robert Franke Prof. Dr. Siegfried R. Waldvogel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7835-7838
We report an innovative, sustainable and straightforward protocol for the synthesis of N,N-diarylamides equipped with nonprotected hydroxyl groups by using electrosynthesis. The concept allows the application of various substrates furnishing diarylamides with yields up to 57 % within a single and direct electrolytic protocol. The method is thereby easy to conduct in an undivided cell with constant current conditions offering a versatile and short-cut alternative to conventional pathways. 相似文献
19.
Giuseppe Spedalotto Dr. Robert Gericke Marta Lovisari Dr. Erik R. Farquhar Dr. Brendan Twamley Dr. Aidan R. McDonald 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(51):11983-11990
Hydroxide-bridged high-valent oxidants have been implicated as the active oxidants in methane monooxygenases and other oxidases that employ bimetallic clusters in their active site. To understand the properties of such species, bis-μ-hydroxo-NiII2 complex ( 1 ) supported by a new dicarboxamidate ligand (N,N′-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide) was prepared. Complex 1 contained a diamond core made up of two NiII ions and two bridging hydroxide ligands. Titration of the 1 e− oxidant (NH4)2[CeIV(NO3)6] with 1 at −45 °C showed the formation of the high-valent species 2 and 3 , containing NiIINiIII and NiIII2 diamond cores, respectively, maintaining the bis-μ-hydroxide core. Both complexes were characterised using electron paramagnetic resonance, X-ray absorption, and electronic absorption spectroscopies. Density functional theory computations supported the spectroscopic assignments. Oxidation reactivity studies showed that bis-μ-hydroxide-NiIII2 3 was capable of oxidizing substrates at −45 °C at rates greater than that of the most reactive bis-μ-oxo-NiIII complexes reported to date. 相似文献
20.
Lulu Wang Jinmiao Wang Chuanbin Fan Caifeng Bi Xia Zhang Dongmei Zhang Mei Wang Yuhua Fan 《应用有机金属化学》2020,34(9):e5767
Two novel Co (II)- coordination polymers (CPs) based on 2,5-bis(4-carboxylpheny)-1,3,4-oxadiazole (bcpo), namely [Co/(bcpo)0.5(tib)(H2O)2]n (1) and [Co (bcpo)0.5(bidpe)(H2O)2]n (2) (tib = 1,3,5-tirs(1-imidazolyl)benzene, bidpe = 4,4′-bis (imidazolyl)diphenyl ether) have been synthesized under solvothermal conditions and characterized by powder X-ray diffraction (PXRD), single crystal X-ray diffraction, photochemistry as well as electrochemistry. The investigation of the photo-degradation methyl blue and methyl violet (MB, MV) properties of CPs 1–2 demonstrates that CP 1 shows great performance for the degradation of MB, and CP 2 could efficiently degrade MB/MV. Meanwhile, the possible photo-degradation mechanism has been proposed and explored. Simultaneously, electrochemistry studies show that both CPs 1 and 2 can catalyze water oxidation under an alkaline condition at the potential around 1.20 V vs. NHE with relatively low overpotential of 330–510 mV vs. NHE. 相似文献