Project description:The cobalt carbonate hydroxide Co2CO3(OH)2 is a technologically important solid which is used as a precursor for the synthesis of cobalt oxides in a wide range of applications. It also has relevance as a potential immobilizer of the toxic element cobalt in the natural environment, but its detailed crystal structure is so far unknown. The structure of Co2CO3(OH)2 has now been investigated using density functional theory (DFT) simulations and powder X-ray diffraction (PXRD) measurements on samples synthesized via deposition from aqueous solution. Two possible monoclinic phases are considered, with closely related but symmetrically different crystal structures, based on those of the minerals malachite [Cu2CO3(OH)2] and rosasite [Cu1.5Zn0.5CO3(OH)2], as well as an orthorhombic phase that can be seen as a common parent structure for the two monoclinic phases, and a triclinic phase with the structure of the mineral kolwezite [Cu1.34Co0.66CO3(OH)2]. The DFT simulations predict that the rosasite-like and malachite-like phases are two different local minima of the potential energy landscape for Co2CO3(OH)2 and are practically degenerate in energy, while the orthorhombic and triclinic structures are unstable and experience barrierless transformations to the malachite phase upon relaxation. The best fit to the PXRD data is obtained using a rosasite model [monoclinic with space group P1121/n and cell parameters a = 3.1408 (4) Å, b = 12.2914 (17) Å, c = 9.3311 (16) Å and γ = 82.299 (16)°]. However, some features of the PXRD pattern are still not well accounted for by this refinement and the residual parameters are relatively poor. The relationship between the rosasite and malachite phases of Co2CO3(OH)2 is discussed and it is shown that they can be seen as polytypes. Based on the similar calculated stabilities of these two polytypes, it is speculated that some level of stacking disorder could account for the poor fit of the PXRD data. The possibility that Co2CO3(OH)2 could crystallize, under different growth conditions, as either rosasite or malachite, or even as a stacking-disordered phase intermediate between the two, requires further investigation.
Project description:The catalytic activity of nanoparticles of cobalt hydroxide supported on reduced graphene oxide, Co(OH)2|rGO, was studied for the decomposition of ammonium perchlorate (AP), the principal ingredient of composite solid propellants. Co(OH)2|rGO was synthesized by an in situ reduction method, which avoided the application of extremely high temperatures and harsh processes. rGO stabilized the nanoparticles effectively and prevented their agglomeration. The performance of Co(OH)2|rGO as a catalyst was measured by differential scanning calorimetry. Co(OH)2|rGO affected the high-temperature decomposition (HTD) of AP positively, decreasing the decomposition temperature of AP to 292 °C, and increasing the energy release to 290 J g-1. The diminution of the HTD of AP by Co(OH)2|rGO is in between the best values reported to date, suggesting its potential application as a catalyst for AP decomposition.
Project description:We report a one-pot method for the preparation of graphene-cobalt hydroxide nanosheets (Co/G NSs) and their use as an effective elelctrocatalyst for water oxidation. Mechanical exfoliation of graphite via sonication produced graphene sheets, which were stabilized by the surface adsorption of a cationic surfactant (CTAB). In a subsequent step, varying amount of a cobalt complex [sodium hexanitrocobaltate(III)] was added which selectively bound with the positively charged head of surfactant. In the last step, cobalt complex was reduced with sodium borohydride to obtain Co/G NSs catalyst. The catalyst showed lower overpotential (280?mV) as compared to benchmark catalysts and decent stability and turnover frequency (TOF: 0.089?s-1) for oxygen evolution reaction (OER).
Project description:The therapeutic application of biofunctional proteins relies on their intracellular delivery, which is hindered by poor cellular uptake and transport from endosomes to cytoplasm. Herein, we constructed a two-dimensional (2D) ultrathin layered double hydroxide (LDH) nanosheet for the intracellular delivery of a cell-impermeable protein, gelonin, towards efficient and specific cancer treatment. The LDH nanosheet was synthesized via a facile method without using exfoliation agents and showed a high loading capacity of proteins (up to 182%). Using 2D and 3D 4T1 breast cancer cell models, LDH-gelonin demonstrated significantly higher cellular uptake efficiency, favorable endosome escape ability, and deep tumor penetration performance, leading to a higher anticancer efficiency, in comparison to free gelonin. This work provides a promising strategy and a generalized nanoplatform to efficiently deliver biofunctional proteins to unlock their therapeutic potential for cancer treatment.
Project description:The charge storage mechanism of mixed cobalt oxysulphide/hydroxide materials having electrochromic properties was investigated. The cobalt oxysulphide/hydroxide materials exhibit a dual reversible redox reaction and electrochromic properties in 1 M KOH during charging and discharging.
Project description:The reaction of a strongly basic phosphazene (Schwesinger base) with water afforded the corresponding metastable hydroxide trihydrate [OH(OH2 )3 ]- salt. This is the first hydroxide solvate that is not in contact with a cation and furthermore one of rare known water-stabilized hydroxide anions. Thermolysis in vacuum results in the decomposition of the hydroxide salt and quantitative liberation of the free phosphazene base. This approach was used to synthesize the Schwesinger base from its hydrochloride salt after anion exchange in excellent yields of over 97 %. This deprotonation method can also be used for the phosphazene-base-catalyzed preparation of the Ruppert-Prakash reagent Me3 SiCF3 using fluoroform (HCF3 ) as the trifluoromethyl building block and sodium hydroxide as the formal deprotonation agent.
Project description:Constructing noble metal-free electrocatalytically active sites for the simultaneous hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline solution is key to realizing electricity-driven water splitting in practical applications. Here, we rationally designed Co(OH)2@CoSe nanorods (NRs) as an excellent bifunctional electrocatalyst by an in situ electrochemical transformation strategy, where the Co-based nanorod template was converted into Co(OH)2@CoSe at the cathode. The obtained electrode exhibits superior electrocatalytic activity for both the HER (overpotential of 208 mV at 20 mA cm-2) and the OER (268 mV at 20 mA cm-2) at high current density in a 1 M KOH solution. The theoretical calculations and experimental evidence indicate that the chemical coupling Co-OH active site between Co(OH)2 and CoSe regulates the hydrogen adsorption and desorption energy and fast electron transfer capability, which is responsible for the improved HER. Moreover, the Co(OH)2@CoSe NRs can be further converted into CoOOH nanosheets which serve as OER active sites. Toward practical electrolytic cell applications, the Co(OH)2@CoSe nanorods as both the cathode and anode achieved a current density of 100 mA cm-2 at 1.94 V for overall water splitting, better than that of noble metal-based electrocatalysts.
Project description:Macrophages play a vital role for guiding the fate of osteogenesis- related cells. It is well known that nano-topography and bioactive ions can directly enhance osteogenic behavior. However, the effects of nano-structure combined with bioactive ions release on macrophage polarization and the following osteogenesis and angiogenesis are rarely reported. Herein, Mg(OH)2 films with nano-sheet structures were constructed on the surface of Ti using hydrothermal treatment. The film presented nano-sheet topography and sustained release of Mg ions. The results of in vitro culture of bone marrow-derived macrophages (BMDMs), including PCR, western blot and flow cytometry suggested that the nano-Mg(OH)2 films were more favorable for macrophages polarizing to tissue healing M2 phenotype. Moreover, air-pouch model confirmed that the nano-Mg(OH)2 film coated Ti would induce milder inflammation and thinner fibrous layer in vivo, compared with untreated Ti. Furthermore, macrophages-conditioned culture mediums were collected from nano-Mg(OH)2 coated Ti group was superior for the osteogenic behaviors of mice bone marrow stem cells and the angiogenic behaviors of human umbilical vein endothelial cells. With harmonious early inflammatory response and subsequently improved osteogenesis and angiogenesis, the nano-Mg(OH)2 coated Ti is promising for orthopedic applications.
Project description:Hierarchical Ni-Co double transition metal hydroxide nanosheets have been explored as an effective strategy for the design of nonenzymatic glucose sensors. Ni-Co hydroxide nanosheets constructed hollow cubes were successfully synthesized by using Cu2O cubes as templates and subsequently etched by Na2S2O3 to achieve a hollow cubic structure. The molar ratio between Ni and Co was tuned by varying the precursor ratio of NiCl2 and CoCl2. It was observed by transmission electron microscopy (TEM) that the increasing Ni precursor resulted in particle morphology, and the increasing ratio of the Co precursor resulted in more lamellar morphology. The sample with the composition of Ni0.7Co0.3(OH)2 displayed the best performance for glucose sensing with high selectivity (1541 μA mM-1 cm-2), low detection limit (3.42 µM with S/N = 3), and reasonable selectivity. Similar strategies could be applied for the design of other electrode materials with high efficiency for nonenzymatic glucose determination.
Project description:Faradaic electrode materials have significantly improved the performance of membrane capacitive deionization, which offers an opportunity to produce freshwater from seawater or brackish water in an energy-efficient way. However, Faradaic materials hold the drawbacks of slow desalination rate due to the intrinsic low ion diffusion kinetics and inferior stability arising from the volume expansion during ion intercalation, impeding the engineering application of capacitive deionization. Herein, a pseudocapacitive material with hollow architecture was prepared via template-etching method, namely, cuboid cobalt hydroxide, with fast desalination rate (3.3 mg (NaCl)·g-1 (h-Co(OH)2)·min-1 at 100 mA·g-1) and outstanding stability (90% capacity retention after 100 cycles). The hollow structure enables swift ion transport inside the material and keeps the electrode intact by alleviating the stress induced from volume expansion during the ion capture process, which is corroborated well by in situ electrochemical dilatometry and finite element simulation. Additionally, benefiting from the elimination of unreacted bulk material and vertical cobalt hydroxide nanosheets on the exterior surface, the synthesized material provides a high desalination capacity (117 ± 6 mg (NaCl)·g-1 (h-Co(OH)2) at 30 mA·g-1). This work provides a new strategy, constructing microscale hollow faradic configuration, to further boost the desalination performance of Faradaic materials.