APPLIED ORGANOMETALLIC CHEMISTRY
·
2021
·Vol. 35
·期 7
·e6245
·
IF 4.105
Ruonan Ma,Zhiyin Xiao,Wei Zhong,Chunxin Lu,Zhongquan Shen,Dan Zhao,Xiaoming Liu
Cuprous halides, best described as (CuX) n (X = Cl − , Br − , and I − ) in their solid state, catalyse selective aerobic oxidation of alcohols with the assistance of both NMI ( N -methylimidazole) and TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl), and the iodide generally demonstrates the highest activity, for example, in the oxidation of 1-octanol at ambient temperature under 24 h' reaction. However, in the aerobic oxidation of benzylic alcohols, the chloride showed superiority to the iodide in that the aerobic oxidation was quantitatively completed within 3 h at ambient temperature whereas the iodide showed only about half the activity of the chloride analogue. By probing the system using electrochemistry, electric conductivity, and 1 H NMR titration, it was revealed that the surprising anomaly was due to the difference in the rate of forming active species, [Cu (NMI) 2 X(MeCN)], from the polymeric solid in a two-stage process. Substrates expansion of 11 benzylic alcohols indicated that CuCl/NMI/TEMPO system demonstrated quantitative conversion of benzylic alcohols into corresponding aldehydes within 3 h and showed great tolerance to the substituents on the phenyl ring of the substrates. Furthermore, electron-withdrawing substituent was beneficial to the oxidation and could offset the steric effect at orthro -substituent. Such a behaviour suggested that in the catalysis, increasing the acidity of the hydroxyl group (OH) of the substrates could ease the oxidation, which implied that the deprotonation via an internal pathway might be one of the rate-determining steps. Our results also showed that the anion halide participated actively in the catalysis by coordinating to Cu(I) in the active species.
研究领域:
化学
·
催化反应
✓ 已验证
DOI
高影响因子
Energy Storage Materials
·
2019
·
IF 0
Yunjie Li,Xiucai Sun,Zhenjie Cheng,Xiao Xu,Jun Pan,Xianfeng Yang,Fang Tian,Yanlu Li,Jian Yang,Yitai Qian
Transitional metal chalcogenides , one important family of promising candidates as electrode materials for sodium-ion batteries, gradually convert to Cu 2 S or Cu 2 Se in the discharge/charge processes, due to electrochemically driven copper diffusion. Thus, their performances after the electrochemical activation, actually come from copper chalcogenides . In this regard, the thorough investigation on the electrochemical properties of copper chalcogenides is important and necessary for the rational design of transitional metal chalcogenides . Here, mesoporous Cu 2-x Se nanocrystals synthesized by a simple solvothermal reaction, are used as a model. They experience the complicated intercalation reaction and the conversion reaction upon cycling, as supported by in-situ / ex-situ techniques and first-principle calculations. All these reactions are highly reversible, leading to 96.1% of the theoretical capacity. These nanocrystals preserve 88% of the initial capacity after 3000 cycles at 5 A g −1 . Even at 10 A g −1 , the capacity is still kept as 92.1% of that at 0.1 A g −1 . In full cells, the nanocrystals without any pre-sodiation and pre-activation, present a lifespan up to 2000 cycles at 0.5 A g −1 and a capacity retention about 74.2%.
研究领域:
材料科学
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电化学
·
纳米科技
·
能源存储
·
无机化学
✓ 已验证
DOI
CHEMICAL PHYSICS
·
2024
·
IF 2
Chuang Li,Lidong Dai,Haiying Hu,Meiling Hong
High-pressure vibrational and electrical transport behaviors of cuprous oxide were systematically investigated in a diamond anvil cell through in-situ Raman spectroscopy and electrical conductivity measurements under different hydrostatic environments up to 25.3 GPa. Upon compression, Cu 2 O undergoes a series of structural transformations from Cu 2 O–I to Cu 2 O–Ia to Cu 2 O–Ib to Cu 2 O–II to Cu 2 O–III phases at the respective pressures of 1.7(2), 10.3(2), 12.9(3) and 21.0(2) GPa under non-hydrostatic condition. Meanwhile, the metallization of Cu 2 O at 19.5(3) GPa is well characterized by the variable-temperature electrical conductivity experiments. Under hydrostatic condition, the pressure delay of 0.6–1.6 GPa is detected in the phase transitions from Cu 2 O–Ia to Cu 2 O–Ib to Cu 2 O–II to Cu 2 O–III phases. Upon decompression, one huge discrepancy is observed in the Raman spectra and electrical conductivity before and after the metallization, which indicates the irreversibility of phase transitions under different hydrostatic environments.
研究领域:
材料科学
·
物理学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
You Xu,Kaili Ren,Tianlun Ren,Mingzhen Wang,Ziqiang Wang,Xiaonian Li,Liang Wang,Hongjing Wang
Electrochemical reduction of nitrate (NO 3 - ) to ammonia (NH 3 ) offers a sustainable avenue to close the NO 3 - cycle for NH 3 synthesis. Critical to the feasibility of electrochemical NO 3 - -to-NH 3 technology is the development of cost-effective, scalable and selective catalysts that can produce NH 3 with high yield. To this end, we design and constructure ultralow-content Pd (2.93 at%) in-situ incorporated Cu 2 O corner-etched octahedra (Pd-Cu 2 O CEO) with cavity and oxygen vacancy defects for selectively electrochemical NO 3 - -to-NH 3 transformation. The unique conner-etched cavity structure, rich surface oxygen vacancies, and Pd-Cu 2 O dual active sites, synergistically promote nitrate electroreduction undergo ammonia formation reaction pathway. Impressively, the as-made Pd-Cu 2 O CEO exhibited outstanding activity for electrocatalytic NO 3 - -to-NH 3 , with high ammonia selectivity (95.31%) and Faradaic efficiency (96.56%). The developed hierarchical-defect strategy may open a new avenue for reasonable design of defect electrocatalysts to contribute desirable properties and functionalities in specific applications.
研究领域:
电化学催化
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CRYSTENGCOMM
·
2023
·Vol. 25
·期 40
·5722-5729
·
IF 3.1
Abraham Mensah,Wei-Min Chen,Ennin Vendish Kweku,Peng-Lai Liu,Juan-Juan Shao,Fang-Ming Wang,Li-Zhuang Chen
Five novel ‘all-in-one’ (AIO) structured cuprous iodide coordination materials 1–5 are presented. With the introduction of planar aromatic groups on the ligand, 1,4-diazabicyclo[2.2.2]octane (DABCO), targeted at eliminating stronger π–π interactions through the twisted nature of the latter species, the complexes displayed good stability, solubility, and high quantum yields of emissions ranging from 70.3–95.3%. Further systematic studies were performed on the relationship between their luminescence and modification of the ligands with halogen atoms. This work provides a reasonable idea for designing luminescent cuprous iodide materials with high quantum yields of emission for use in solid-state lighting in the future.
研究领域:
无机化学
·
材料科学
·
光物理
✓ 已验证
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Weiqian Cai,Youqun Wang,Linshan Xiong,Yingjie Zheng,Zhibin Zhang,Xiaohong Cao,Yunhai Liu
Cuprous oxide (Cu 2 O), a promising semiconductor material, has been less employed in the photocatalytic removal of uranium. In this work, silver and gold nanoparticles were introduced on the surface of Cu 2 O. HR-TEM, XRD and XPS were applied in characterized the physic-chemical properties of composite. In comparison to Cu 2 O, Au modified Cu 2 O (Au/Cu 2 O-N) demonstrated a significantly enhanced uranium removal rate, reaching 100% within 120 minutes. This represents a 2-fold increase in the uranium removal rate compared to pure Cu 2 O-N. The reason con be interpreted including the red-shift of the absorption band from 600nm-800nm, the formation of Schottky junction between Au and Cu 2 O, the electron traps constructed by Au itself. Consequently, the rate of photogenerated electron-hole complexation is significantly diminished. Free trapping and EPR prove that reactive radicals are O 2 - . This has led to the development of a novel approach, namely the synergistic strategy of noble metal loading and nitrogen-doped cuprous oxide, which has the potential to facilitate the visible light removal of U(VI) from toxic wastewater.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Coatings
·
2022
·Vol. 12
·期 1
·68
·
IF 3.236
Xue Peng,Yanfei Lv,Shichao Zhao
Inorganic semiconductors usually show n-type characterization; the development of p-type inorganic semiconductor material will provide more opportunities for novel devices. In this paper, we investigated the chemical vapor deposition (CVD) of p-type cuprous phosphide (Cu3P) nanofilm and studied its thermal oxidation behavior. Cu3P film was characterized by optical microscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), laser Raman spectroscopy (Raman), and fluorescence spectroscopy (PL). We found that the thickness of film ranged from 4 to 10 nm, and the film is unstable at temperatures higher than room temperature in air. We provide a way to prepare inorganic phosphide nanofilms. In addition, the possible thermal oxidation should be taken into consideration for practical application.Keywords:cuprous phosphide;nanofilm;chemical vapor deposition;thermal oxidation
研究领域:
材料科学
·
半导体物理
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2022
·
IF 9.136
Zhiwei Wang,Zhi Li,Jiaojiao Bu,Juanjian Ru,Yixin Hua,Ding Wang
Cuprous sulfide (Cu 2 S) is the main composition of chalcocite and widely used in the catalyst. Deep eutectic solvents (DESs) are eco-friendly electrolytes for the separation and recycling of metals and their compounds in addition to environmental protection. In this work, choline chloride-ethylene glycol (ChCl-EG) DES is innovatively used towards one-step desulfurize cuprous sulfide to recycle copper for the first time. Cyclic voltammetry is employed to investigate the effect of initial potential, scan rate and temperature on the electrochemical behavior of Cu(I) in ChCl-EG DES. The effect of essential parameters (applied voltage, temperature and NH 4 HCO 3 ratio) on the chemical composition and microstructure of the product are discussed. Pure polycrystalline nano-Cu with an average size of ≈16.15 nm can be obtained with the current efficiency of 96.58% at the optimized parameters of 2.5 V, 353 K, 40% NH 4 HCO 3 and 10 h. The structure of Ch + is unbroken and the main existence form of Cu(I) is CuCl 2 − in the electrolyte. Mechanism analysis indicates the reduction of Cu 2 S to Cu is step-by-step with the feasible process of Cu 2 S→Cu 1.96 S→Cu 7.2 S 4 …→Cu. The S element is possibly converted and stabilized as the sulfate (SO 4 2− ) in the DES. All these findings are expected to provide new feasibility for the direct extraction and recycling of Cu from Cu 2 S with high current efficiency and less hazardous.
研究领域:
材料科学
·
环境科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
CRYSTENGCOMM
·
2017
·Vol. 19
·期 14
·1888-1895
·
IF 3.474
Chao Cai,Tang Zhu,Dongdong Li,Yun Ran,Haixia Dong,Ning Zhao,Jian Xu
In this paper, tannic acid (TA) was used to assist the fabrication of spherically aggregated Cu2O–TA hybrid sub-microparticles with good chemical stability and controllable sizes. TA exhibited multiple functions in the synthesis: the reductant for the formation of Cu2O crystal seeds, the stabilizer of the primary Cu2O crystals and the protector against the oxidation of Cu2O. A probable mechanism was presumed, including 1) seed formation and TA encapsulation, 2) primary crystal nucleation and growth, and 3) aggregation into spheres. We found that pH played a key role in determining the final morphology of the product while the precursor concentration strongly influenced the size of the particles. At a suitable pH, hierarchically structured Cu2O–TA sub-microspheres with nanocrystals as building blocks were produced. The size of the spheres can be tuned from 130 to 670 nm by adjusting the precursor concentration. Cu2O–TA hybrids exhibited excellent chemical stability against water and oxygen. The method reported here possessed many advantages like cost-effectiveness, facility of preparation, environmental friendliness, chemical stability and excellent adjustability. The properties of the prepared Cu2O particles might facilitate their applications in marine antifouling paints, adsorption materials and antibacterial agents.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2015
·
IF 4.504
Yanqing Cai,Hongxia Liu,Qian Xu,Qiushi Song,Liang Xu
The in-situ preparation of LiCl–KCl–ZrCl 4 melt was investigated by the replacement reaction between Zr and CuCl in LiCl–KCl melt at 500 °C, and the reaction progress was also investigated by a series of electrochemical techniques, such as cyclic voltammetry , square wave voltammetry and open circuit chronopotentiometry . The electrochemical signals show that the concentration of Zr(IV) ions increases gradually and then reaches to the maximum value with the reaction time increasing from 0 to 180 min, while the concentration of Cu(I) ions decreases rapidly and drops to below the detection limit of the electrochemical tests. Meanwhile, the concentrations of Cu and Zr ions in the melt were determined over time by chemical analysis in the course of reaction. The results are in good agreement with the electrochemical tests. Finally, LiCl–KCl melts with (0.837 wt.% ∼ 1.709 wt.%) ZrCl 4 are obtained, and the final concentration of Cu(I) in the melt has dropped to below 0.025 wt.% when the reaction lasted for 180 min.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2023
·
IF 7.7
Yanting Lv,Weiyong Shao,Yuling Kong,Nanhua Li,Xinrui Huang,Zhihao Tang,Murong Gong,Lizi Li,Weiqi Wei
Photocatalytic reforming of biomass has a broad prospects in the green and efficient production of high-value chemicals, which was in line with the sustainable development. Herein, we proposed a new photocatalytic system to produce lactic acid from xylose by using boron doping carbon nitride supported cuprous oxide (g-C 3 N 4 -B-Cu 2 O) under a weak alkaline system. The UV–vis and photoluminescence (PL) characterization showed that the introduction of boron and Cu 2 O into C 3 N 4 not only improved the catalyst UV–visible light absorption range, but promote the separation ability of photogenerated electron holes , which was beneficial for lactic acid forming. The poisoning experiments indicated that the free radicals such as 1 O 2 ,·OH,·O 2- and h + were the key active substances in the process of xylose photocatalytic reforming into lactic acid, and with the sacrificial agents such as benzoquinone (BQ), ethylene diamine tetraacetic acid (EDTA), isopropyl (IPA), and tryptophan (Trp) use, the yield of lactic acid significantly reduced. Remarkably, the maximum lactic acid yield of this work was 91.2 %, and it was obtained at 60 ℃ for 120 min with 99.3 % xylose conversion. More importantly, the g-C 3 N 4 -B-Cu 2 O photocatalyst exhibited the satisfied stability, and can be reused at least for nine times with the lactic acid yield loss less than 2.3 %. Finally, the plausible reaction pathway for xylose photocatalytic reforming to lactic acid over g-C 3 N 4 -B-Cu 2 O were also investigated in this work.
研究领域:
化学工程
·
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
·
2015
·
IF 4.097
Hongbo Li,Jing Li,Daye Chen,Yanxia Qiu,Wei Wang
A novel non-enzymatic and oxygen-sensitive photoelectrochemical (PEC) sensor for glucose was first constructed based on dual-functional cubic cuprous oxide. Herein, cuprous oxide acts both as an excellent catalyst for the preoxidation of glucose and as a photocathode for the PEC non-enzymatic glucose sensing. The fabricated cuprous oxide was characterized by scanning electron microscopy, X-ray diffractometry, X-ray photoelectron spectrometry, and UV–vis spectrophotometry. Under the optimized conditions, the PEC sensing was linear in its response to the logarithm of concentration of glucose in the range of 0.0005 to 6 mmol L −1 with a detection limit of 0.3 μmol L −1 . The same concentration of other common species did not interfere with the detection of glucose, and the results of the PEC sensor corresponded well with those obtained by the commercially available enzymatic glucose sensor. This novel non-enzymatic and oxygen-sensitive PEC sensor exhibited good performance with its high sensitivity, good selectivity, wide linear range, low cost, and portable features. Also it provides an alternative way for improving non-enzymatic PEC sensor of glucose.
研究领域:
生物传感器
·
材料科学
·
分析化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）