Chemistry-An Asian Journal
·
2020
·Vol. 15
·期 8
·1272-1276
·
IF 4.056
Yueming Cao,Peipei Li,Tengteng Wu,Meiling Liu,Youyu Zhang
Graphical HKUST-1 (Cu−BTC, BTC=benzene-1,3,5 tricarboxylate) was selected as an electrocatalyst for the reaction of conversion N 2 to NH 3 under ambient conditions. At −0.75 V vs. reversible hydrogen electrode, it achieves excellent performance with high NH 3 yield (46.63 μg h −1 mg −1 cat. or 4.66 μg h −1 cm −2 ) and Faraday efficiency (2.45%). Electrolytic ammonia synthesis from nitrogen at ambient conditions is appearing as a promising alternative to the Haber-Bosch process which is consuming high energy and emitting CO 2 . Here, a typical MOF material, HKUST-1 (Cu−BTC, BTC=benzene-1,3,5-tricarboxylate), was selected as an electrocatalyst for the reaction of converting N 2 to NH 3 under ambient conditions. At −0.75 V vs. reversible hydrogen electrode, it achieves excellent catalytic performance in the electrochemical synthesis of ammonia with high NH 3 yield (46.63 μg h −1 mg −1 cat. or 4.66 μg h −1 cm −2 ) and good Faraday efficiency (2.45%). It is indicated that the good performance of the HKUST-1 catalyst may originate from the formation of Cu(I). In addition, the catalyst also has good selectivity for N 2 to NH 3 .
研究领域:
材料科学
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电化学
·
催化反应
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Guangzhi Xu,Mingzhen Shi,Hailong Ning,Leizhi Zheng,Zhuoheng Tu,Xiaomin Zhang,Xingbang Hu,Youting Wu
The separation of C 3 H 6 and C 3 H 8 has been a technical challenge owing to their similar physical and chemical properties. The currently used separation technologies still suffer from the low efficiency, high operating cost and volatility of media, which urges researchers to develop greener and more efficient media. To achieve this, a series of protic cuprous-based ionic liquids (PCILs) combining both cuprous site and long alkyl chain were designed in this work for the absorption separation of C 3 H 6 and C 3 H 8 . Surprisingly, the solubility of C 3 H 6 in [TOAH][CuCl 2 ] is as high as 0.238 mol/kg at 313 K and 1.0 bar, which exceeds most of results reported so far. The experimental data and thermodynamic analysis showed that extending alkyl chain of ILs promoted the dissolution of C 3 H 6 and C 3 H 8 , while the introduction of Cu(I) improved the selectivity of C 3 H 6 /C 3 H 8 . In addition, the interaction mechanism of C 3 H 6 and C 3 H 8 with ILs was further clarified by quantum chemical calculations and FT-IR spectroscopy. Furthermore, regeneration of [TOAH][CuCl 2 ] can be easily realized under depressurizing condition without heating and loss in separation performance, and [TOAH][CuCl 2 ] was found very stable to both moisture and oxygen for at least fifteen days. The strategy of combining long-chain alkyl and Cu(I) site in this work may provide an important guideline for enhancing C 3 H 6 /C 3 H 8 selectivity, but more efforts on enhancing Cu(I) activity still need to be made for improving C 3 H 6 /C 3 H 8 selectivity.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COORDINATION CHEMISTRY
·
2018
·
IF 1.703
Kuan-Guan Liu,Ru Wang,Hong-Yan Han,Qi-De Shan,Jing Nie,Xiao-Wei Yan
Incorporating ferrocenecarboxylato(-1) into [CuI
2(μ-dppm)2]2+ (dppm = bis(diphenylphosphino)methane) led to the isolation of a heterometallic complex [Cu2(μ2-η1,η1dppm)2(μ2-η1, η1FcCOO)(CH3CN)]BF4·CH3CN (1). It was characterized by infrared spectroscopy (IR), elemental analysis (EA), powder X-ray diffraction analysis (PXRD), ultraviolet–visible spectrum (UV–Vis), nuclear magnetic resonance (NMR), and thermogravimetric analysis (TGA). Single-crystal X-ray structural analysis revealed that ferrocenecarboxylato(-1) coordinated to the [Cu2(μ2-η1,η1dppm)2]2+ unit via μ2-η1,η1 bridging mode in 1. The title complex shows good optical absorption and thermal stability, and reliable electrochemical stability. Moreover, this heterometallic copper(I) complex could be used as a promising electrochemical sensing material for the detection of H2O2.
研究领域:
化学
·
材料科学
·
分析化学
✓ 已验证
DOI
高影响因子
INORGANICA CHIMICA ACTA
·
2021
·
IF 2.545
Dan Zheng,Ting-Hong Huang,Cheng Luo,Jing Tang
Three dinuclear Cu(I) complexes, [Cu 2 (pnd)(PPh 3 ) 4 ](BF 4 ) 2 (1) , [Cu 2 (pnd)(dppp) 2 ] (BF 4 ) 2 (2) , and [Cu 2 (pnd)(DPEphos) 2 ](BF 4 ) 2 (3) (PPh 3 = triphenylphosphine , dppp = 1, 3-bis (diphenylphosphino)propane, DPEphos = bis(2-diphenylphosphinophenyl)ether, pnd = N , N ’-bis (pyridin-2-ylmethylene)naphthyl-1, 5-diimine), have been prepared and characterized by IR, 1 H NMR, 31 P NMR, 13 C NMR, XRD , elemental analysis and X-ray crystal structure analysis. The structural analysis reveals that the flexible pnd in 1 – 3 acts in a trans bridging coordination mode to connect two Cu + ions, forming a S-shape conformation, while each of Cu (I) ion is four-coordinate N2P2, adopting a distorted-tetrahedral geometry. DFT calculations show that the HOMOs of complexes 1 – 3 are primarily located on the copper d -orbital and the phosphine ligand, together with a specific contribution of pnd, while LUMOs are mostly composed of pnd with admixed Cu(I) d-orbital character. Corresponding calculations of atomic charges indicate that the charge of the copper atom in complexes 1 – 3 is below + 1, while the total charges of the coordinated atoms are 0.743–0.786. Moreover, the solid-state emission spectra of complexes 1 – 3 show the existence of broad emission bands at 350–550 nm.
研究领域:
无机化学
·
理论化学
·
材料科学
✓ 已验证
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2019
·
IF 4.914
Zhi-Hua Zhou,Xiao Zhang,Yong-Fu Huang,Kai-Hong Chen,Liang-Nian He
Inexpensive and efficient Cu(I) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO 2 , and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO 2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO 2 as a crucial cocatalyst under mild conditions.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2017
·
IF 2.843
Yongli Sun,Hanrong Bi,Haozhen Dou,Huawei Yang,Zhaohe Huang,Baoyu Wang,Rong Deng,Luhong Zhang
For the separation of an ethylene/ethane mixture, a novel copper(I)-based supported ionic liquid membrane (SILM) with high permeability has been fabricated. This SILM was prepared from a polyvinylidene fluoride microporous membrane impregnating the copper(I) based IL which formed by the cuprous chloride (CuCl) and 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]). Scanning electron microscopy, attenuated total reflection Fourier transform infrared spectroscopy, and time of flight mass spectroscopy were used to characterize the SILM. Pure and mixed gas permeation experiments were carried out to investigate the influences of ILs composition, trans-membrane pressure, temperature, and time upon the separation performance. This SILM showed comparable C2H4 permselectivity but outstanding permeability with a long-term stability beyond the reported polymeric membrane upper bound. At the CuCl/[Bmim][Cl] ratio of 2, the C2H4 permeability and permselectivity reached 2653 barrer and 11.8, respectively. Furthermore, the facilitated transport effect was studied by 1H NMR and quantum mechanical calculations. The anionic species formed by sp hybridization of Cu+ possesses unfilled attachment sites to selectively complex with C2H4 and weaken the interionic hydrogen bond of [Bmim][Cl], thus lowering the system’s viscosity.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2016
·
IF 5.267
Yuling Zhao,Jikuan Qiu,Li Tian,Zhiyong Li,Maohong Fan,Jianji Wang
Carbon dioxide (CO2) is an abundant and renewable feedstock for the production of high-value chemicals. Herein, CuI and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were employed as an efficient catalyst system to synthesize 2-oxazolidinones through the coupling reaction of CO2 and propargylic amines. It was found that this cost-competitive catalyst system could efficiently catalyze the reaction within only 4 h at atmospheric pressure CO2, and a wide range of substrates were suitable for this reaction. Various target products were obtained in excellent yields. Furthermore, the catalytic mechanism of the CuI/DBU system was investigated by using density functional theory. It was shown that copper(I) and DBU played synergistic roles in activating both the C≡C triple bond and the amino group of propargylic amines in the reaction.
研究领域:
有机化学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
INORGANICA CHIMICA ACTA
·
2021
·
IF 2.545
Tian-Cheng Wu,Qiao-Long Hu,Ting-Hong Huang,Yi-Shun Cui,Dan Zheng,Changyan Ji,Cheng Luo
A series of copper(I) - diimine complexes, [Cu(bdpp)(bpy)]BF 4 ( 1 ), [Cu(bdpp) (pen)]BF 4 ( 2 ), [Cu(bdpp)(damp)]BF 4 ( 3 ), [Cu(bdpp)(pen)]BF 4 ( 4 ) (bdpp = 4,6-bis-(biphenyl phosphino) phenoxazine, bpy = 2,2′-bipyridine, phen = 1,10-Phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, bphen = 4,7-diphenyl-1,10-phenanthroline), have been synthesized and characterized by IR, 1 H NMR, 31 P NMR, XRD and X-ray crystal structure analysis. Structural analysis reveals that each Cu + in 1 – 4 is four-coordinated by two N atoms and two P atoms and adopts a distorted tetrahedral geometry. DFT calculations show that the HOMOs in 1 – 4 are mainly comprised of bdpp and copper d–orbitals, while the LUMOs are mainly dominated by diimine ligands. Calculation of atomic charges indicates that the charges of the central Cu atoms in 1 – 4 are less than + 1, and the diimine ligands may be the key to the metal charge transfer to the coordinated atom. In 1 – 4 , the maximum phosphorescent lifetimes and quantum yields are up to 349 μs and 22%, respectively. Moreover, complex 3 is used for fabricating the LED device, showing a decent performance with the maximum EQE of 11%.
研究领域:
化学
·
材料科学
✓ 已验证
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-12
·
IF 14.7
He Xiaoyang,Lin Li,Li Xiangying,Zhu Minzhi,Zhang Qinghong,Xie Shunji,Mei Bingbao,Sun Fanfei,Jiang Zheng,Cheng Jun,Wang Ye
The membrane electrode assembly (MEA) is promising for practical applications of the electrocatalytic CO 2 reduction reaction (CO 2 RR) to multi-carbon (C 2+ ) compounds. Water management is crucial in the MEA electrolyser without catholyte, but few studies have clarified whether the co-feeding water in cathode can enhance C 2+ formation. Here, we report our discovery of pivotal roles of a suitable nanocomposite electrocatalyst with abundant Cu 2 O−Cu 0 interfaces in accomplishing water-promoting effect on C 2+ formation, achieving a current density of 1.0 A cm −2 and a 19% single-pass C 2+ yield at 80% C 2+ Faradaic efficiency in MEA. The operando characterizations confirm the co-existence of Cu + with Cu 0 during CO 2 RR at ampere-level current densities. Our studies reveal that Cu + works for water activation and aids C‒C coupling by enhancing formations of adsorbed CO and CHO species. This work offers a strategy to boost CO 2 RR to C 2+ compounds in industrial-relevant MEA by combining water management and electrocatalyst design.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ChemNanoMat
·
2021
·Vol. 7
·期 3
·277-283
·
IF 3.154
Jie Wang,Hongqin Ma,Jia Li,Xinyue Luo,Luqi Yu
Graphical Cu(I) decorated 2D black phosphorus nanosheets were synthesized by a ball-milling method . In the process of ball-milling, the bulk black phosphorus was exfoliated into nanosheets under the action of shearing force. Due to the reducibility of black phosphorus, it can react with CuCl 2 to form Cu(I)/BNPSs-n. As the active component of the adsorbent, Cu(I) species can interact with benzothiophene or dibenzothiophene in fuel to achieve the purpose of adsorption desulfurization. In this study, Cu(І) decorated two-dimensional black phosphorus nanosheets (BPNSs) adsorbents were prepared by a ball-milling method, and their adsorption-desorption performances were tested by batch adsorption experiments. The results showed that Cu(ІI) can be completely reduced to Cu(І) without adding any additional reducing agents during the ball-milling process, owing to the ability of black phosphorus to provide electrons to Cu(ІI). Moreover, the produced Cu(І) species were firmly anchored on BPNSs surface through chemical bonds formed between Cu and P atoms, effectively preventing them from aggregating. As the active sites on BPNSs surface, Cu(I) species can adsorb dibenzothiophene or benzothiophene from fuel by forming π-complexation bonds with them. The maximum adsorption capacity of the adsorbent for dibenzothiophene and benzothiophene were 13.16 and 18.02 mg S/g, respectively. Besides, the adsorption desulfurization activity can be recovered well by adopting simple thermal treatment.
研究领域:
材料科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
·
2013
·
IF 1.977
Tianzhi Yu,Haifang Chai,Yuling Zhao,Chengcheng Zhang,Peng Liu,Duowang Fan
Two new mononuclear Cu(I) complexes based on 2-(2′-pyridyl)benzimidazolyl derivative ligand containing hole-transporting carbazole ( L ), [Cu(L)(DPEphos)](BF 4 ) and [Cu(L)(PPh 3 ) 2 ](BF 4 ), where L = (4-(9 H -carbazol-9-yl)phenyl)methyl-2-(2′-pyridyl)benzimidazole; DPEphos = bis[2-(diphenylphosphino)phenyl]ether and PPh 3 = triphenylphosphine, have been synthesized and characterized on the basis of elemental analysis, 1 H NMR and FT-IR spectra. The structures of the ligand L and the Cu(I) complexes were characterized by single crystal X-ray diffraction. The results reveal that in the Cu(I) complexes the central Cu(I) ions assume the irregular distorted tetrahedral geometry and are tetra-coordinated by the two nitrogen atoms from L ligand and two phosphorus atoms from ancillary ligands. The photophysical properties of the complexes were examined by using UV–vis, photoluminescence spectroscopic analysis. The complexes exhibit weak MLCT absorption bands ranging from 360 to 480 nm, and display strong orange phosphorescence in the solid states at room temperature, which is completely quenched in solutions.
研究领域:
化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Materials Advances
·
2023
·Vol. 5
·期 3
·1234-1239
·
IF 5
Yi Lv,Jing Yang,Haibo Li,Wei Liu,Gangfeng Ouyang
In this paper, the structures and optical properties of copper(I) halide mononuclear hybrids have been studied. Three pairs of compounds with different organic ligands have been synthesized by a precursor approach, exhibiting significantly enhanced stability compared to typical copper halide monomers by the formation of stronger Cu–P bonds, proving that copper halide monomer-type hybrid compounds have the potential to be developed into high-performance light-emitting materials.
研究领域:
材料化学
·
光学材料
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）