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 ? = 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: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 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: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.
Project description:Copper electrodes are especially effective in catalysis of C2 and further multi-carbon products in the CO2 reduction reaction (CO2 RR) and therefore of major technological interest. The reasons for the unparalleled Cu performance in CO2 RR are insufficiently understood. Here, the electrode-electrolyte interface was highlighted as a dynamic physical-chemical system and determinant of catalytic events. Exploiting the intrinsic surface-enhanced Raman effect of previously characterized Cu foam electrodes, operando Raman experiments were used to interrogate structures and molecular interactions at the electrode-electrolyte interface at subcatalytic and catalytic potentials. Formation of a copper carbonate hydroxide (CuCarHyd) was detected, which resembles the mineral malachite. Its carbonate ions could be directly converted to CO at low overpotential. These and further experiments suggested a basic mode of CO2 /carbonate reduction at Cu electrodes interfaces that contrasted previous mechanistic models: the starting point in carbon reduction was not CO2 but carbonate ions bound to the metallic Cu electrode in form of CuCarHyd structures. It was hypothesized that Cu oxides residues could enhance CO2 RR indirectly by supporting formation of CuCarHyd motifs. The presence of CuCarHyd patches at catalytic potentials might result from alkalization in conjunction with local electrical potential gradients, enabling the formation of metastable CuCarHyd motifs over a large range of potentials.
Project description:Emulsification of elemental mercury in aqueous solution in the form of grey particles occurs upon exposure to intense sound fields. We show the concomitant formation of molecular Hg(OH)2 in the solution phase reaching a saturation limit of 0.24 mM at 25 °C. The formation of Hg(OH)2 is consistent with the 'hot spot' model which suggests the formation of OH˙ as a result of acoustic cavitation; such radicals are proposed to combine with Hg to form the Hg(OH)2 species here characterised using voltammetry.
Project description:Consecutive layers of Ni(OH)2 and Co(OH)2 were electrodeposited on stainless steel current collectors for preparing charge storage electrodes of high specific capacity with potential application in hybrid supercapacitors. Different electrodes were prepared consisting on films of Ni(OH)2, Co(OH)2, Ni1/2Co1/2(OH)2 and layered films of Ni(OH)2 on Co(OH)2 and Co(OH)2 on Ni(OH)2 to highlight the advantages of the new architecture. The microscopy studies revealed the formation of nanosheets in the Co(OH)2 films and of particles agglomerates in the Ni(OH)2 films. Important morphological changes were observed in the double hydroxides films and layered films. Film growth by electrodeposition was governed by instantaneous nucleation mechanism. The new architecture composed of Ni(OH)2 on Co(OH)2 displayed a redox response characterized by the presence of two peaks in the cyclic voltammograms, arising from redox reactions of the metallic species present in the layered film. These electrodes revealed a specific capacity of 762?C?g-1 at the specific current of 1?A?g-1. The hybrid cell using Ni(OH)2 on Co(OH)2 as positive electrode and carbon nanofoam paper as negative electrode display specific energies of 101.3?W?h g-1 and 37.8?W?h g-1 at specific powers of 0.2?W?g-1 and 2.45?W?g-1, respectively.
Project description:The development of technologies that allow us to reduce CO2 emissions is mandatory in today's society. In this regard, we present herein a comparative study of CO2 adsorption over three types of materials: zeolites, layered double hydroxides (LDH), and zeolites coated LDH composites. The influence of the zeolite Si/Al ratio on zeolites sorption capacity along with the presence of mesopores was investigated. By comparing these results with the well-known performance of LDHs, we aim to provide insights on the factors that may influence the CO2 capture capacity over zeolites, thus providing useful tools for tuning their properties upon post-treatments.
Project description:Two-dimensional (2D) materials are of considerable interest for catalyzing the heterogeneous conversion of CO2 to synthetic fuels. In this regard, 2D siloxene nanosheets, have escaped thorough exploration, despite being composed of earth-abundant elements. Herein we demonstrate the remarkable catalytic activity, selectivity, and stability of a nickel@siloxene nanocomposite; it is found that this promising catalytic performance is highly sensitive to the location of the nickel component, being on either the interior or the exterior of adjacent siloxene nanosheets. Control over the location of nickel is achieved by employing the terminal groups of siloxene and varying the solvent used during its nucleation and growth, which ultimately determines the distinct reaction intermediates and pathways for the catalytic CO2 methanation. Significantly, a CO2 methanation rate of 100?mmol?gNi-1?h-1 is achieved with over 90% selectivity when nickel resides specifically between the sheets of siloxene.