Copper Hydroxyphosphate Research Articles

Morphology‐Controlled Synthesis of Hierarchical Copper Hydroxyphosphate Microcrystals in Alkaline Buffer Solution and their Optical Properties

AbstractA series of copper hydroxyphosphate (Cu2(OH)PO4) microcrystals with different shapes, including straw sheaf‐like microcrystals, microrods‐assembled microflowers, four‐edged arrow‐like microcrystals, and four‐pointed star‐like dendrites, are prepared by a hydrothermal method in Na2HPO4‐NaOH buffer solutions. The buffer solutions serve as both reactant and solvent. More importantly, the pH values of the alkaline buffer solutions significantly affect the morphologies of Cu2(OH)PO4 microcrystals. Four samples have absorption bands in the near‐ultraviolet, visible, and near‐infrared regions; furthermore, four Cu2(OH)PO4 microcrystals exhibit different band gap energies (3.06, 2.78, 2.68, and 2.39 eV) owing to their different structures. This strategy can be scaled up for the simple, green, and low‐cost production of Cu2(OH)PO4 microcrystals.

Direct reduction of diluted CO2 gas to C2 products by copper hydroxyphosphate microrods

AbstractElectrochemical reduction of CO2 is widely researched in recent years. However, direct electro‐reduction of diluted CO2 to C2 products is seldomly studied. In this work, electrocatalytic reduction of CO2 with different concentrations were conducted on Cu2(PO4)(OH) catalysts. The catalytic performance in diluted CO2 is comparable with that in pure CO2 by using Cu2(PO4)(OH) as catalyst. Besides, the selectivity of C2 product is still as high as 64.6% in 50%CO2 concentration. The normalized C2 current density of Cu2(PO4)(OH) was over 6.8 times higher than that of commonly used Cu2O–Cu catalyst with similar size. In situ Raman spectroscopy proved that Cu+ is the main active site at higher potentials. More importantly, a higher local pH is realized under diluted CO2 test conditions which is favorable for promoting C–C coupling. Finally, in situ ATR‐FTIR spectroscopy was performed to further monitor and identify the adsorbed intermediates and help reveal the mechanism for the catalysts.

H2S‐Activated Ion‐Interference Therapy: A Novel Tumor Targeted Therapy Based on Copper‐Overload‐Mediated Cuproptosis and Pyroptosis

AbstractCopper overload is a novel way to achieve copper‐ion‐interference therapy by disrupting copper homeostasis and treating diseases through multiple cell death pathways. However, it is difficult to reach copper overload since excess intracellular copper ions will be pumped out. Herein, copper overload is achieved by both raising cellular uptake and reducing the efflux of copper ions using hydrogen sulfide (H2S)‐responsive copper hydroxyphosphate nanoparticles (Cu2(PO4)(OH) NPs). After immersion in an H2S‐enriched colon cancer microenvironment, Cu2(PO4)(OH) NPs can transform into copper sulfide NPs with reduced size for higher cell entering, resulting in improved Fenton activity as well as copper ion dissociation. Reactive oxygen species generated by the Fenton reaction not only activate inflammasomes and Caspase‐1 proteins, cause the cleavage of gasdermin D to induce pyroptosis, but also affect mitochondrial function and down‐regulate copper exporter ATP7A to further reduce the copper excretion. The combination of higher endocytosis and lower exportation leads to maximized copper overload. Together with the efficient copper ions release, mitochondrial tricarboxylic acid cycle can be disrupted and iron‐sulfur cluster proteins are downregulated, ultimately triggering cuproptosis. As both pyroptosis and cuproptosis are efficient ways to induce cell death, this study provides a novel way to realize effective tumor‐targeted therapy based on H2S‐activated copper overload with simple Cu2(PO4)(OH) NPs.

Copper hydroxyphosphate Cu2(OH)PO4 as conversion-type anode material for lithium-ion batteries

Copper hydroxyphosphate Cu2(OH)PO4 as conversion-type anode material for lithium-ion batteries

Toward highly active electrochemical CO2 reduction to C2H4 by copper hydroxyphosphate

Toward highly active electrochemical CO2 reduction to C2H4 by copper hydroxyphosphate

Synthesis of copper hydroxyphosphate under the principles of green chemistry

This work aims to present two syntheses according to the green chemistry principles of Cu2(OH)PO4. The first one is a mechanochemical synthesis which was carried out with Cu3(PO4)2 and NaOH at room temperature and without solvent (principles five and six), the second one employed an aqueous suspension of copper phosphate (principle six). The products were characterized by X-ray diffraction, scanning electron microscopy, infrared spectroscopy and elemental analysis. Using an analysis and evaluation scale based on green principles, the synthesis method reported in this study was compared with the traditional hydrothermal synthesis method, which was found to be a polluting process, while the synthesis method reported in this study was a clean process. It was concluded that clean processes lead to time savings, low energy costs and environmental care.

Construction of poly-(γ-benzyl‐l‐glutamate) composite microcarriers with osteogenic and angiogenic properties for the restoration of alveolar bone defects

The repair of alveolar bone defects is one of the urgent clinical problems to be solved. Injectable microcarriers show great potential for bone repair due to their ability to fill irregular bone defects. In this study, the ICA@nCP/nHA-g-PBLG composite microcarriers with osteogenic and angiogenic properties were fabricated via double emulsion (W/O/W) method. Firstly, poly-(γ-benzyl‐l‐glutamate) (PBLG) was linkaged onto the surface of nano copper hydroxyphosphate (nCP) and nano hydroxyapatite (nHA) to construct nCP-g-PBLG and nHA-g-PBLG nanohybrids by chemical grafting, respectively. Then, nCP/nHA-g-PBLG porous microcarriers were fabricated via double emulsion (W/O/W) method and immersed in icariin (ICA) solution to obtain ICA@nCP/nHA-g-PBLG composite microcarriers. The composite microcarriers were more conducive to the proliferation of bone marrow mesenchymal stem cells (BMSCs) when the content of nCP and ICA in the composite microcarriers were 0.5 wt% and 0.1 wt%, respectively. The release of Cu2+ in nCP could promote angiogenesis, while the release of ICA could promote the osteogenic differentiation of BMSCs. The ability of ICA@nCP/nHA-g-PBLG microcarriers to restore alveolar bone defects was proved in a rabbit model. In conclusion, the ICA@nCP/nHA-g-PBLG microcarriers exhibited two functions: osteogenesis and angiogenesis, which could be served as a promising implant for alveolar bone defects repair.

RETENTION OF CU(II) IONS BY AMORPHOUS AND APATITIC TRICALCIUM PHOSPHATES: AN UNDEMANDING ROUTE TO PRODUCE LIBETHENITE

The retention of copper ions by amorphous and apatitic tricalcium phosphates was studied using X-ray photoelectron spectroscopy, X-ray diffraction, infrared spectroscopy, and induction-coupled plasma atomic emission spectroscopy. The experimental results of this study show that the amorphous tricalcium phosphate exposed for 48 hours to a 2.10-2 M copper ion solution with the initial molar ratio Cu(solution)/Ca(phosphate) = 1 retains 96% of the initial amount of copper. It also completely converts to copper hydroxyphosphate, the mineral known as libethenite. The research revealed that apatitic tricalcium phosphate subjected to a similar treatment removed only 38% of the initial amount of copper and was only partially transformed into libethenite. In this case, it turned out that by extending the exposure time of the phosphate or by increasing the initial molar ratio Cu(solution)/Ca(phosphate), the conversion of the apatitic phosphate becomes complete and leads to a retention capacity of 595 mg/g. X-ray photoelectron spectroscopy analysis of libethenite produced by the conversion of tricalcium phosphates confirms the chemical purity of this mineral. It reveals that the Cu2p core level exhibits a multiple structure that can be deconvoluted into five peaks at binding energies of 934.5 eV, 954.5 eV, 940.6 eV, 943.1, and 961.5 eV. The first two peaks were attributed to the Cu2p3/2 and Cu2p1/2 photoelectrons and are consistent with the divalent state of copper, while the other peaks, not all previously reported, were assigned to shake-up satellites arising from Cu+2 with d9 configuration in the ground state.

Copper hydroxyphosphate nanosheets-covered robust membranes with superhydrophilicity and underwater ultralow adhesive superoleophobicity for oil/water separation and visible light photodegradation

With the rapid increase of oil pollution accidents, the purification of oily water has become a serious global problem to be solved. Herein, the Cu2(OH)PO4 nanosheets-covered robust mesh membranes are fabricated by a facile green wet-chemical method at different pH conditions. By the combination of the superwetting ability with photocatalytic performance of Cu2(OH)PO4, the nanosheets-covered mesh membrane fabricated at pH 9.7 exhibits a superhydrophilicity and underwater ultralow oil adhesive superoleophobicity for efficient removal of various oils from water with an oil sliding angle about 1.4°. Simultaneously, the membrane presents a high photocatalytic activity for methylene blue under visible light irradiation. After 15 cycles of separation, the test demonstrates a superior separation stability of the membrane with high permeating flux of ∼94,801 Lm−2 h-1 and separation efficiency above 99.5%. In consideration of the excellent mechanical property, chemical stability, thermal resistance and high separation capacity, the as-prepared mesh membrane is promisingly applied in purifying oily wastewater.

Synthesis and applications of near-infrared absorbing additive copper hydroxyphosphate

Abstract

Photocatalytic and antibacterial properties of copper hydroxyphosphate with hierarchical superstructures synthesized by a hydrothermal method

Copper hydroxyphosphate, Cu2PO4OH, with various architectures was synthesized by adjusting pH values in a simple hydrothermal route. The photocatalytic activity of the Cu2PO4OH hierarchical superstructures was strongly related to their micro-morphology, as demonstrated by the degradation of eosin Y dye with a solar simulator. Excellent photocatalytic performance was achieved by Cu2PO4OH obtained under the pH values of 7 and 5. The antibacterial properties of the Cu2PO4OH complex superstructures were also explored by Escherichia coli (ATCC 8739) culturing. Cu2PO4OH showed apparent antibacterial properties but the samples obtained under the pH values of 5 and 7 exhibited better antibacterial properties than those of the Cu2PO4OH under the pH value of 2.5. Thus, Cu2PO4OH can be a promising photocatalyst with excellent antibacterial properties achieved by simply controlling its hierarchical superstructures by adjusting the pH values during feasible synthesis.

Self-Assembled 3D Hierarchical Copper Hydroxyphosphate Modified by the Oxidation of Copper Foil as a Recyclable, Wide Wavelength Photocatalyst.

In this work, three-dimensional flower-like and petal-like copper hydroxyphosphate Cu5(OH)4(PO4)2 (CHP) based on the self-assembly of numerous nanosheets has been successfully fabricated on a copper foil by a mild one-pot wet-chemical method without ligand assistance. This research contributes to the development of the method to change the morphology of the CHP active material by varying the degree of substrate oxidation. The two different CHP architectures were used to photocatalytically degrade rhodamine 6G (Rh 6G) under solar light, which can absorb wide-range light wavelength from the UV to the near-infrared region. They all exhibit high photocatalytic activity and good durability, which are potential candidates for high performance and recyclable wide wavelength photocatalysis.

Microwave-assisted Preparation of Copper Hydroxyphosphate and Characterization of Photocatalysis under Visible Light

Copper hydroxyphosphate (Cu2(OH)PO4) was quickly synthesized by microwave-assisted method at low temperature (< 100°C) and normal atmosphere pressure, then characterized by XRD, SEM and Raman spectra. The synthesis parameters were investigated by a series of controled experiments. It is found that molar ratio, initial concentration of CuCl2 and NaH2PO4, and surfactant species were crucial factors determining the formation and morphology of Cu2(OH)PO4. Cu2(OH)PO4 synthesized at different [PO4] (n(Cu)/n(P)=2) exhibited a various morphologies including grain-like, prism and long-prismatic. Addition of anionic surfactant and sodium dodecyl sulfate (SDS) greatly affects Cu2(OH)PO4 final morphology. The photocatalytic degradation of Cu2(OH)PO4 on methylene blue (MB) was evaluated with addition of H2O2 under visible light irradiation. The results showed that Cu2(OH)PO4 synthesized at conditions when n(Cu)/n(P)=2, [PO4]=0.0025 mol/L, 6.0 g urea and 0.10 g SDS, microwave heating at 80°C for 30 min exhibited best visible-light photo-degradation activity. The increase in HO· formation in the presence of Cu2(OH)PO4 and the inhibition of HO· generation by adding HO· scavengers (t-butanol) indicated that HO· generated 422 无 机 材 料 学 报 第 31 卷 in the reaction system was responsible for the enhanced MB decomposition. Cu2(OH)PO4 exhibited excellent stability and effectiveness after 5 consecutive runs in terms of photodegradation of MB.

Ionic liquid-assisted fabrication of copper hydroxyphosphate nanocrystals with exposed {100} facets for enhanced photocatalytic activity

Libethenite Cu2PO4OH nanocrystals with different morphologies were prepared by an ionic liquid-assisted hydrothermal route, and were further investigated as photocatalysts under visible-light irradiation. The Cu2PO4OH elongated truncated bipyramids exposing {100} facets exhibit superior photocatalytic activity compared to other particles, which can be attributed to the presence of 100% Cu5c atoms on {100} facets. It is highly expect this research can provide a useful fundamental understanding of shape-dependent photocatalytic performance of copper hydroxyphosphate.

Electrochemical and Photoelectrochemical Properties of the Copper Hydroxyphosphate Mineral Libethenite

not Available.

Electrochemical and Photoelectrochemical Properties of the Copper Hydroxyphosphate Mineral Libethenite

AbstractThere has been much interest recently in the discovery of new, non‐oxide materials for photoelectrochemical applications. The copper hydroxyphosphate mineral libethenite, Cu2(OH)PO4 (CHP), which has a Jahn–Teller distorted structure and d9 electron configuration, has recently been reported to display photocatalytic activity. To better understand the properties of this material, a detailed investigation of the relevant fundamental characteristics such as the flatband potential, conduction type, and band diagram was performed using electrochemical and photoelectrochemical methods on CHP thin films deposited onto fluorine‐doped tin oxide (FTO) substrates. Density functional theory was used to calculate the band structure, effective mass of electrons and holes, and vacancy formation energies in CHP. CHP was found to be active for electrochemical water oxidation, as confirmed by quantitative O2 measurements. Possible factors behind the low photocurrents observed in linear scanning voltammetry are discussed. Better understanding of this material may lead to the development of improved catalysts and photocatalysts from natural mineral sources.

Hydrothermal Synthesis of Copper Hydroxyphosphate Hierarchical Architectures

AbstractCopper hydroxyphosphate, Cu2(OH)PO4, with six hierarchical architectures was successfully synthesized through a hydrothermal route. The resulting hierarchical superstructures were characterized using powder X‐ray diffraction and scanning electron microscopy. In this hydrothermal process, the morphology of copper hydroxyphosphate changed drastically with the addition of different amounts of alcohol (ethanol, n‐propanol, or ethylene glycol) as solvent. A possible mechanism for the formation of these copper hydroxyphosphate hierarchical superstructures is proposed. This approach provides a facile strategy to synthesize copper hydroxyphosphate crystals with unique morphologies and complex architectures. This binary reaction medium (alcohol and water) could provide an alternative and versatile strategy for controlling inorganic microcrystals by manipulating the supersaturation of the growing solution.

Uniform copper hydroxyphosphate microstructures with tunable size: Synthesis by a facile surfactant-free hydrothermal route and photocatalytic properties

Uniform copper hydroxyphosphate quadrangle star-like microcrystals with tunable size and microprism bundles have been achieved through a simple hydrothermal method. Reactions are conducted in a water system using CuSO4, NH4H2PO4 and NaOH as reactants without adding any surfactants. Structures and morphologies of the products were characterized by powder X-ray diffraction, scanning electron microscopy, fourier transform infrared spectrometry, and UV–vis spectrometry. It was found that the size and morphology of the products depended strongly on the concentration and the molar ratio of the starting reagents. The possible mechanism of the products was discussed and the size dependent photocatalytic property of the products was investigated.

Hydrothermal Synthesis and Characterization of Copper Hydroxyphosphate Hierarchical Superstructures

The copper hydroxyphosphate nanostructured microspheres with uniform diameter have been achieved via a template-free hydrothermal synthetic route with ammonia as alkali and complexing agent. Powder x-ray diffraction, scanning electron microscopy, Fourier transform infrared spectrometry, and x-ray photoelectron spectroscopy were used to characterize the morphologies and structures of the products. It has been found that the morphology of the final product depends strongly on the concentrations, molar ratios of the starting reagents, and the kinds of alkali. The possible formation process of the microspheres is discussed.

Study of Photocatalytic Activities with Copper Hydroxyphosphate

Copper hydroxyphosphate,as self-assembled nanoparticles, was synthesized by using a hydrothermal method,with cupric acetate (Cu(CH3COO)2·H2O) and diammonium hydrogen phosphate ((NH4)2HPO4) as raw materials. Physical property of copper hydrophosphate was characterized by X-ray diffraction (XRD), Field-emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), and Ultraviolet obvious diffuse reflection(UV-vis DRS). No surfactants or templates were added in the procedure of preparation. By simply adjusting the pH from 3 to 9, the morphology of copper hydrophosphate varied from microrods to walnutshaped microspheres. Photocatalytic activity of the samples was also investigated. Photo decoloration of Rhodamine B in water under visible light irradiation shows that copper hydrophosphate (pH=7) have the best photocatalytic activity: Photodecoloration activity of 100 mL Rhodamine B (10 mg/L) was 98 % under illumination for 30 min.