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The efficiency of perovskite solar cells (PSCs) has undergone rapid advancement due to great progress in materials development over the past decade and is under extensive study. Despite the significant challenges (e.g., recombination and hysteresis), both the single-junction and tandem cells have gradually approached the theoretical efficiency limit. Herein, an overview is given of how passivation and crystallization reduce recombination and thus improve the device performance; how the materials of dominant layers (hole transporting layer (HTL), electron transporting layer (ETL), and absorber layer) affect the quality and optoelectronic properties of single-junction PSCs; and how the materials development contributes to rapid efficiency enhancement of perovskite/Si tandem devices with monolithic and mechanically stacked configurations. The interface optimization, novel materials development, mixture strategy, and bandgap tuning are reviewed and analyzed. This is a review of the major factors determining efficiency, and how further improvements can be made on the performance of PSCs.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Copper-mediated pentafluoroethylation of arenediazonium tetrafluoroborates with tetrafluoroethylene (TFE) on-site generated from TMSCF3 has been developed as a new method to prepare pentafluoroethyl arenes. The active pentafluoroethylation reagent ?CuC2F5? is pre-generated from CuSCN, TFE and CsF, and its generation and further reaction are strongly solvent-dependent. This pentafluoroethylation reaction represents the first example of Sandmeyer-type pentafluoroethylation, which exhibits good functional group tolerance and potential applications for the synthesis of complicated bioactive compounds.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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p-CuCNS coated with Rhodamine B and then photoplatinized is found to photogenerate oxygen from aqueous persulphate with the dye remaining photostable.The photochemical mechanisms involved are discussed.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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A process for preparing organic isocyanate compounds characterized by reacting a chloromethyl group-containing compound having the formula: wherein X, which can be the same or different, is chlorine, alkyl, cycloalkyl, alkenyl, phenyl, chloromethylphenyl or chloromethyl, n is 0 or an integer of 1 to 3, and R is an aromatic hydrocarbon radical or an olefin radical, With an alkali cyanate, in the presence of a catalyst composition comprising (a) a cuprous salt in an amount of 0.1 to 20% by weight, based on said chloromethyl group-containing compound, and (b) a tertiary amine compound or quaternary ammonium compound in an amount equivalent to 0.05 to 1.25 gram atoms of nitrogen per gram mole of said cuprous salt, in a high-boiling-point solvent having a dieelectric constant (epsilon) not higher than 20, at a reaction temperature of 150 to 250 C, for 0.1 to 10 hours.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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While the effects of structural disorder on the electronic properties of solids are poorly understood, it is widely accepted that spatially isotropic orbitals lead to robustness against disorder. In this paper, we use first-principles calculations to show that a cluster of occupied bands in the coordination polymer semiconductor beta-copper(I) thiocyanate undergo relatively little fluctuation in the presence of thermal disorder-a surprising finding given that these bands are composed of spatially anisotropic d-orbitals. Analysis with the tight-binding method and a stochastic network model suggests that the robustness of these bands to the thermal disorder can be traced to the way in which these orbitals are aligned with respect to each other. This special alignment causes strong inverse statistical correlations between orbital-orbital distances, making these bands robust to random fluctuations of these distances. As well as proving that disorder-robust electronic properties can be achieved even with anisotropic orbitals, our results provide a concrete example of when simple ‘averaging’ methods can be used to treat thermal disorder in electronic structure calculations.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Under different situations, solvothermal reactions of 3,5-diethyl-4-(4- pyridyl)-pyrazole (HL) with CuX or CuX2 (X = Cl, Br, I, and SCN) afforded five copper(I) coordination polymers, {CuX[CuL]3· solvent}n (X = Cl, 1; Br, 2; I, 3; X = SCN and solvent = MeCN, 4) and {Cu2I2[CuL]3}n (5). X-ray diffraction analyses show that all the complexes have trinuclear [CuL] 3 (referred as Cu3) secondary building units featuring planar nine-membered Cu3N6 metallocycles with three peripheral pyridyl groups as connectors, which are further linked by CuX or Cu2X2 motifs to generate single- or double-strand chains. Interestingly, the Cu(I) atoms within the Cu3 units in 1-5 behave as coordinatively unsaturated pi-acid centers to contact soft halide/pseudohalide X atoms of CuX and Cu2X2 motifs, which lead to novel sandwich substructures of [(Cu3)(Cu2X2)(Cu 3)] (X = Br, I, and SCN) in 2-4. In addition, both the pi-acid [Cu3]···X contacts and intertrimer Cu···Cu interactions contribute to the one-dimensional (1D) double-strand and 2D/3D supramolecular structures of 1-5. All of these complexes exhibit high thermostability and bright solid-state phosphorescence upon exposure to UV radiation at room temperature. The emissions arise from the mixtures of metal-centered charge transfer, metal to ligand charge transfer, and halide-to-ligand charge transfer excited states, and can be tuned by intermolecular pi-acid [Cu3]···halide/ pseudohalide contacts.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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The reaction of copper(I) salts CuX (X = Cl, Br, I, CN, SCN), [Cu(CH3CN)4]PF6 with 1-diphenylphosphino-1?-di-tert-butylphosphinoferrocene (dppdtbpf) in 1:1 M ratio in DCM-MeOH (50:50 V/V) at room temperature afforded mono and binuclear compounds having formula [Cu2(mu-Cl)2(kappa2-P,P-dppdtbpf)2] (1), [Cu2(mu-Br)2(kappa2-P,P-dppdtbpf)2] (2) [Cu2(mu-I)2(kappa2-P,P-dppdtbpf)2] (3), [Cu2(mu-CN)2(kappa2-P,P-dppdtbpf)2] (4), [Cu2(mu2-SCN)2(kappa2-P,P-dppdtbpf)2] (5), and [Cu(kappa2-P,P-dppdtbpf)(CH3CN)2]PF6 (6). Reacting palladium(II) complex [Pd(C6H5CN)2Cl2] with dppdtbpf gave mononuclear compound [Pd(kappa2-P,P-dppdtbpf)Cl2] (7). The reaction of dppdtbpf with sulfur powder under reflux in chloroform afforded a ferrocene diphosphine disulfide dppSdtbpSf (8). All of the synthesized compounds were characterized by elemental analyses, IR, 1H and 31P NMR, ESI-MS and electronic absorption spectroscopy. Molecular structures for the compounds 5, 6, 7 and 8 were determined crystallographically. Compound 5 exists as centrosymmetric dimer in which the two copper atoms are bonded to two dppdtbpf ligands and two bridging thiocyanate groups in mu2-manner. In cationic compound 6, the copper atom is coordinated to one dppdtbpf ligand in kappa2-manner and two acetonitrile molecules, whereas in 7, the palladium(II) adopted cis square-planar geometry by coordinating to one dppdtbpf ligand in kappa2-manner and two chlorine atoms. Compound 8 revealed a sandwiched structure with both phosphine groups sulfurized. The electrochemical properties of 1-6 were studied by cyclic voltammetry. Compounds 1-6 exhibited moderately weak to strong luminescence properties, however compounds 7 and 8 are non-emissive in the solution state.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Herein, a general procedure to access CF2PO(OEt)2-containing molecules is reported. The reagent CuCF2PO(OEt)2 is accessible by a simple protocol and a broad range of substrates can be functionalised. The procedure allows the conversion of aryl diazonium salts, as well as aryl, heteroaryl, vinyl and alkynyl iodonium salts, into the corresponding fluorinated molecules at room temperature. Mechanistic studies were performed to gain a better understanding of the reaction pathway. Under similar conditions, vinyl and aryl iodides, allyl halides, and benzyl bromides were also functionalised, and the scope and limitations of the reaction were studied. Finally, the procedure was extended to disulfides to offer new access to SCF2PO(OEt)2-containing molecules.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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This study focuses on employing cuprous iodide (CuI) as a hole-transporting material (HTM) in fabricating highly efficient perovskite solar cells (PSCs). The PSCs were made in air with either CuI or 2,2′,7,7′-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9′-spirobifluorene (spiro-OMeTAD) as HTMs. A simple and novel pressing method was employed for incorporating CuI powder layer between perovskite layer and Pt top-contact to fabricate devices with CuI, while spiro-OMeTAD was spin-coated between perovskite layer and thermally evaporated Au top-contact to fabricate devices with spiro-OMeTAD. Under illuminations of 100 mW/cm2 with an air mass (AM) 1.5 filter in air, the average short-circuit current density (JSC) of the CuI devices was over 24 mA/cm2, which is marginally higher than that of spiro-OMeTAD devices. Higher JSC of the CuI devices can be attributed to high hole-mobility of CuI that minimizes the electron-hole recombination. However, the average power conversion efficiency (PCE) of the CuI devices were lower than that of spiro-OMeTAD devices due to slightly lower open-circuit voltage (VOC) and fill factor (FF). This is probably due to surface roughness of CuI powder. However, optimized devices with solvent-free powder pressed CuI as HTM show a promising efficiency of over 8.0 % under illuminations of 1 sun (100 mW/cm2) with an air mass 1.5 filter in air, which is the highest among the reported efficiency values for PSCs fabricated in an open environment with CuI as HTM.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”

 

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Reaction of (4,4?-bis-tert-butyl-2,2?-dipyridyl) platinum bis-alkynyl [(tBu2bipy)Pt(C?CR)2] (R = C6H4Me 1a, SiMe3 1b) with Group 11 metal thiocyanate salts (M = Cu, Ag) affords 1:1 mixed-metal complexes [(tBu2bipy)Pt(C?CR)2M(SCN)] (M = Cu, R = C6H4Me 2a, SiMe3 2b; M = Ag, R = C6H4Me 3a, SiMe3 3b). X-ray analyses of the complexes 2a and 3b show that the group 11 metal is bonded in an eta2 fashion to two carbon-carbon triple bonds so that the co-ordination geometry is trigonal planar. The Pt atom geometry in both complexes is square planar. An electrochemical study of the copper complexes 2a and 2b reveals one fully reversible one electron reduction that is consistent with the first reduction of the co-ordinated bipyridyl ligand. There is also an irreversible one electron oxidation that corresponds to the CuI to CuII transition.

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Reference:
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”