Cobalt Silicate Research Articles

Full-component recovery of cobalt-rich waste by sodium carbonate roasting combined with cascade leaching

The rapid development of the battery industry, which relies heavily on cobalt, has significantly increased focus on the cobalt industry chain. In this context, the extraction and recovery of cobalt from secondary resources, which are often considered waste products or byproducts of other industrial processes, have emerged as an important source of the cobalt industry chain. This study developed an environmentally friendly sodium carbonate roasting process combined with cascade leaching process to realize the full-component recovery of a complex cobalt-rich waste containing valuable elements, including cobalt, tungsten, chromium, tantalum, and niobium. Sodium carbonate roasting was used for pre-treatment to decompose the composite metal oxides and convert dicobalt orthosilicate to sodium cobalt silicate. Water leaching after sodium carbonate roasting can selectively separate W and Cr with leaching efficiencies exceeding 99%. Subsequently, the leaching efficiency of cobalt reached 99.9% via sulfuric acid leaching with sodium sulfite as the reducing agent. A method for precipitating tungsten and chromium was proposed, achieving precipitation efficiencies of 97.1% for tungsten and 99.9% for chromium, respectively. The results of this study provide a resource guarantee for the sustainable development of the cobalt industry.

A pyroxene-based quantum magnet with multiple magnetization plateaus.

Pyroxenes (AMX2O6) consisting of infinite one-dimensional edge-sharing MO6 chains and bridging XO4 tetrahedra are fertile ground for finding quantum materials. Thus, here, we have studied calcium cobalt germanate (CaCoGe2O6) and calcium cobalt silicate (CaCoSi2O6) crystals in depth. Heat capacity data show that the spins in both compounds are dominantly Ising-like, even after being manipulated by high magnetic fields. On cooling below the Néel temperatures, a sharp field-induced transition in magnetization is observed for CaCoGe2O6, while multiple magnetization plateaus beneath the full saturation moment are spotted for CaCoSi2O6. Our analysis shows that these contrasting behaviors potentially arise from the different electron configurations of germanium and silicon, in which the 3d orbitals are filled in the former but empty in the latter, enabling electron hopping. Thus, silicate tetrahedra can aid the interchain superexchange pathway between cobalt(II) ion centers, while germanate ones tend to block it during magnetization.

Dual modification of cobalt silicate nanobelts by Co3O4 nanoparticles and phosphorization boosting oxygen evolution reaction properties

Oxygen evolution reaction (OER) process is the “bottleneck” of water splitting, and the low-cost and high-efficient OER catalysts are of great importance and attractive but they are still challenging. Herein, a dual modification strategy is developed to tune and enrich the structure of cobalt silicate (Co2SiO4) showing boosted OER properties. Cobalt oxide (Co3O4) decorated Co2SiO4 nanobelts, denoted as CS, is firstly prepared using a Co-based precursor by a facile hydrothermal reaction. Then, cobalt phosphide (CoP) nanoparticles are in-situ grown on CS (denoted as CS-P) by the phosphorization process, which provide many active sites and boost the surface reactivity. The experimental results and density function theory (DFT) calculations both reveal that the CoP on CS can improve the conductivity and ensure fast kinetics, thus leading to boost the OER properties of Co2SiO4. When the phosphorization temperature is at 400 °C (CS-P400), it gains the lowest overpotential of 297 mV, which is much lower than CS (340 mV) and Co2SiO4 (409 mV) at 10 mA·cm−2, and even superior to the state-of-the-art transition metal silicates. CS-P400 also achieves high electrochemical active surface area (ECSA) and small Tafel slope owing to its porous structures with large specific surface area and nanosheet-like structures which are good for exposing many active sites and favorable to the fast kinetics. This work not only provides a dual modification route to boost catalytic activity of Co2SiO4 (CS-P400), but also sheds light on a new avenue for developing highly dispersed CoP on silicates to boost OER performances.

Halloysite-derived hierarchical cobalt silicate hydroxide hollow nanorods assembled by nanosheets for highly efficient electrocatalytic oxygen evolution reaction

The oxygen evolution reaction (OER) is regarded as the bottleneck of electrolytic water splitting. Thus, developing robust earth-abundant electrocatalysts for efficient OER has received a great deal of attention and it is an ongoing scientific challenge. Herein, hierarchical hollow nanorods assembled with ultrathin mesoporous cobalt silicate hydroxide nanosheets (denoted as CoSi) were successfully fabricated, using the silica nanotube derived from halloysite as a sacrificial template, via a simple hydrothermal method. The resulting cobalt silicate hydroxide nanosheets stack with thicknesses ∼10 nm, as confirmed by transmission electron microscopy. The elaborated nanoarchitecture possesses a high specific surface area (SSA) allowing good exposure to the cobalt active centers exhibiting superior catalytic activity vs analogs synthesized using sodium silicate. Among all as-prepared CoSi samples, those synthesized at 150 °C (CoSi-150) exhibited the minimum overpotential of ∼347 mV at a current density of 10 mA cm–2. In addition, CoSi-150 also exhibited superior performance against typical cobalt-based catalysts, and its surface hydroxyl groups were beneficial for the enhancement of OER performance. Furthermore, the CoSi-150 showed excellent durability and stability after the 105 s chronopotentiometry test in 1 M KOH. This design concept provides a new strategy for the low-cost preparation of high-quality cobalt water splitting electrocatalysts.

Tree-inspired semiconductor-on-ceramic 2D/1D heterostructure for efficient CO2 photoreduction

Two-dimension nanosheets are ideal photocatalysts for CO2 reduction due to their high exposure of active sites and short charge transfer pathway. However, 2D photocatalysts have a tendency to agglomeration, thus compromising the performance of photocatalytic CO2 reduction. Trees, one of the most important plants for photosynthesis, have a unique “leaf-on-branch” structure. This unique two-dimension/one-dimension (2D/1D) configuration maximizes the adsorption of CO2 molecules and light harvesting. Herein, a tree-inspired semiconductor-on-ceramic 2D/1D heterostructure for efficient photocatalytic CO2 reduction is reported. The cobalt silicate (CoSi) nanosheets (∼0.68 nm) are in situ grown on the surfaces of hydroxyapatite (HAP) nanowires, creating a well-defined 2D/1D hierarchical structure. The vertical alignment of ultrathin CoSi nanosheets on the HAP nanowires effectively suppresses their agglomeration, leading to a large BET surface area (106.45 m2/g) and excellent CO2 adsorption (8.00 cm3 g−1). The results of photoelectrochemical characterization demonstrate that the 2D/1D hierarchical structure is powerful to expedite charge transfer. As a result, the gas generation rate of CO is as high as 28780 μmol g−1 h−1 over the CoSi-on-HAP 2D/1D heterostructure. In addition, the electron transfer mechanism and reaction pathways of CO2 reduction are revealed by in situ irradiated XPS and in situ DRIFT spectra.

Anion Structure Regulation of Cobalt Silicate Hydroxide Endowing Boosted Oxygen Evolution Reaction.

Transition metal silicates (TMSs) are attempted for the electrocatalyst of oxygen evolution reaction (OER) due to their special layered structure in recent years. However, defects such as low theoretical activity and conductivity limit their application. Researchers always prefer to composite TMSs with other functional materials to make up for their deficiency, but rarely focus on the effect of intrinsic structure adjustment on their catalytic activity, especially anion structure regulation. Herein, applying the method of interference hydrolysis and vacancy reserve, new silicate vacancies (anionic regulation) are introduced in cobalt silicate hydroxide (CoSi), named SV-CoSi, to enlarge the number and enhance the activity of catalytic sites. The overpotential of SV-CoSi declines to 301mV at 10mA cm-2 compared to 438mV of CoSi. Source of such improvement is verified to be not only the increase of active sites, but also the positive effect on the intrinsic activity due to the enhancement of cobalt-oxygen covalence with the variation of anion structure by density functional theory (DFT) method. This work demonstrates that the feasible intrinsic anion structure regulation can improve OER performance of TMSs and provides an effective idea for the development of non-noble metal catalyst for OER.

Clean-up of divalent cobalt ions by massive sequestration in a low-cost calcium silicate hydrate material

Cobalt is a critical resource in industrial economies for the manufacture of electric-vehicle batteries, alloys, magnets, and catalysts, but has acute supply-chain risks and poses a threat to the environment. Large-scale sequestration of cobalt in low-cost materials under mild conditions opens a path to cobalt recycling, recovery and environmental clean-up. We describe such sequestration of cobalt by a widely available commercial calcium silicate material containing the mineral xonotlite. Xonotlite rapidly and spontaneously takes up 40 percent of its weight of cobalt under ambient conditions of temperature and pressure and reduces dissolved cobalt concentrations to low parts per million. A new Sharp Front experimental design is used to obtain kinetic and chemical information. Sequestration occurs by a coupled dissolution-precipitation replacement mechanism. The cobalt silicate reaction product is largely amorphous but has phyllosilicate features.

Cobalt-based hybrid nanoparticles loaded with curcumin for ligand-enhanced synergistic nanocatalytic therapy/chemotherapy combined with calcium overload.

The therapeutic efficacy of Fenton or Fenton-like nanocatalysts is usually restricted by the inappropriate pH value and limited concentration of hydrogen peroxide (H2O2) at the tumor site. Herein, calcium carbonate (CaCO3)-mineralized cobalt silicate hydroxide hollow nanocatalysts (CSO@CaCO3, CC) were synthesized and loaded with curcumin (CCC). This hybrid system can simultaneously realize nanocatalytic therapy, chemotherapy and calcium overload. With the stabilization of liposomes, CCC is able to reach the tumor site smoothly. The CaCO3 shell first degrades in an acidic tumor environment, releasing Cur and Ca2+, and the pH value of the tumor is increased simultaneously. Then the exposed CSO catalyzes the Fenton-like reaction to convert H2O2 into ˙OH and enhances the cytotoxicity of curcumin (Cur) by catalytically oxidizing it to a ˙Cur radical. Curcumin not only induces the chemotherapy effect but also serves as a nucleophilic ligand and an electron donor in the catalytic system, enhancing the Fenton-like activity of CCC by electron transfer. In addition, calcium overload also amplifies the efficacy of ROS-based therapy. In vitro and in vivo results show that CCC exhibited an excellent synergistic tumor inhibition effect without any clear side effect. This work proposes a novel concept of nanocatalytic therapy/chemotherapy synergistic mechanism by the ligand-induced enhancement of Fenton-like catalytic activity, and inspires the construction of combined therapeutic nanoplatforms and multifunctional nanocarriers for drug and ion delivery in the future.

Fully utilizing the organic and inorganic fractions in rice husk for electrode materials towards an excellent asymmetric solid-state supercapacitor

Rice husk is selected as the feedstock for the production of activated carbons (RHAC). The desilication process is performed to enhance its potential application in supercapacitors, meanwhile, cobalt silicates (Co/Si-x) are synthesized from recycled waste silica. To explain the effect of desilication processes on the characteristics of derived activated carbons, the desilication steps are carried out after carbonization and activation to produce two different types of desilicated RHAC (CD-RHAC and AD-RHAC). Results show that the specific surface area of CD-RHAC and AD-RHAC are 3404.5 and 3451.3 m2 g−1, which are both higher than that of untreated RHAC (2075.1 m2 g−1). Furthermore, Co/Si-x samples exhibit significantly different properties due to the various Co/Si ratios. In a three-electrode system, the capacitance of CD-RHAC and Co/Si-3 can achieve the capacitances of 264.5 and 400.3 F g−1 at the current density of 0.5 A g−1. The CD-RHAC//Co/Si-3 asymmetric solid-state supercapacitor shows an excellent capacitance retention of about 100 % after 6000 cycles and a high energy density of 19.0 Wh kg−1 at a power density of 176.8 W kg−1. Overall, the work offers a feasible pathway to fully utilize the organic and inorganic fractions of lignocellulosic biomass in the field of energy storage.

Mn‐doping ensuring cobalt silicate hollow spheres with boosted electrochemical property for hybrid supercapacitors

AbstractRecently, transition metal silicates (TMSs) have garnered significant attention as promising candidates for electrode materials in supercapacitors (SCs), especially cobalt silicate (Co2SiO4, CoSi) related materials. However, due to the poor conductivity and narrow potential range of CoSi, its electrochemical properties are not fully developed and far from desirable. Herein, to enhance the electrochemical properties of CoSi, hollow spheres of Mn‐doped CoSi (CoMnSi) were fabricated through a hydrothermal method. The dopant Mn facilitates the formation of CoMnSi hollow spheres assembled by nanosheets and these nanosheets connect with each other to form the core‐shell hollow architecture. The effect of the Mn/Co ratio on the electrochemical properties of CoSi has been investigated. CoMnSi‐2 (Mn/Co = 1/9) displays the specific capacitance of 495 F g−1 at 0.5 A g−1, surpassing to that of CoSi (279 F g−1 at 0.5 A g−1) and manganese silicate (denoted as MnSi, 38 F g−1 at 0.5 A g−1). The CoMnSi‐2//active carbon hybrid supercapacitor (CoMnSi‐2//AC HSC) achieves the specific capacitance with 181 mF cm−2 (151 F g−1) at 1 mA cm−2 and energy density with 0.644 Wh m−2 at 2 W m−2. The device displays a practical application by powering the LED lamp circuit bulb working for more than 25 min repeatedly. The performance achieved by CoMnSi is superior to some state‐of‐the‐art electrode materials of TMSs. Density functional theory calculations have provided evidence that Mn‐doping enhances the electronic conductivity and reduces the electron transport barrier of CoSi, boosting its electrochemical properties. This work supplies a strategy for tailoring structures of TMSs to enhance their electrochemical performance.

Manganese as a structural promoter in silica-supported cobalt Fischer-Tropsch catalysts under simulated high conversion conditions

Understanding the deactivation mechanism of cobalt-based Fischer-Tropsch catalysts is of significant practical importance. Herein, we explored the role of manganese as a structural promoter on silica-supported cobalt nanoparticles under simulated high CO conversion conditions, i.e., high relative humidity. The structural changes in cobalt dispersion and oxidation state were followed by in situ Mössbauer emission spectroscopy. Adding manganese oxide to silica-supported cobalt enhanced the dispersion of metallic cobalt in the reduced catalysts. This higher cobalt dispersion, however, led to a stronger tendency of cobalt silicate formation under humid conditions. Without manganese, the cobalt particles sintered, and the larger ones were prone to transformation into cobalt carbide under high conversion conditions. As such, silica is not preferred as a support for practical FTS.

Bi-functional two-dimensional cobalt silicate catalyst for selective catalytic oxidation of ammonia

We have newly synthesized the zeolitic cobalt silicate catalysts via a simple hydrothermal treatment of borosilicate MWW precursor with Co precursor solution. As the hydrothermal temperature increased, a structural transformation occurred, shifting from three-dimensional (3D) to two-dimensional (2D) delaminated MWW layers (DML), and further to 2D amorphous phyllosilicate, accompanied by a continuous increase in Co content. The synthesized bi-functional 2D cobalt silicate facilitates the selective catalytic oxidation of NH3 (NH3-SCO), a process that requires both surface acidity and redox characteristics. In particular, Co-DML-160 prepared by hydrothermal treatment at 160 °C exhibited the coexistence of Co3O4 and framework Co species resulting in a strong redox ability and high Lewis acidity, respectively, due to their synergetic effect.

Enhanced photo-Fenton-like performance of biotemplated manganese-doped cobalt silicate catalysts

Cobalt-based catalysts are one of the preferred materials for effective activation of hydrogen peroxide, and metal element doping and active site dispersion are effective methods to enhance their catalytic activity. In this work, manganese-doped cobalt silicate@diatomite composites with enhanced photo-Fenton-like oxidation performance were prepared and used for degradation of methyl orange (MO) dyes. Experiments showed that manganese doping increased the specific surface area of the samples and decreased the band gap energy of the materials. Moreover, the samples doped with manganese elements had better photo-Fenton-like properties. The degradation of methyl orange by Co0.25MnSi@DE/H2O2-UV reached more than 95%. In addition, density-functional theory (DFT) calculations showed that the Mn-doped samples were more prone to activate H2O2 than non-manganese-doped samples, and the synergistic effect from using a bimetallic catalyst increased the photo-Fenton oxidation activity in the system. ESR spectroscopy and bursting tests indicated that the possible degradation mechanism consisted of hydroxyl radicals and superoxide radicals generated by the synergistic effect of cobalt ions and manganese under UV radiation. This study thus presents a feasible idea for the preparation of cobalt-based photo-Fenton catalysts that also provides a basis for understanding the catalytic mechanism analysis of other types of bimetallic catalysts.

Superelastic Cobalt Silicate@Resorcinol Formaldehyde Resin Core-Shell Nanobelt Aerogel Monoliths with Outstanding Fire Retardant and Thermal Insulating Capability.

The practical applications of resorcinol formaldehyde resin (RFR) aerogels are prevented by their poor mechanical properties. Herein, a facile template-directed method is reported to produce macroscopic free-standing cobalt silicate (CS)@RFR core-shell nanobelt aerogels that display superelastic behavior and outstanding thermal insulating and fire-resistant capability. The synthesis relies on the polymerization of RFR on pre-formed CS nanobelts which leads to in situ formation of hydrogel monoliths that can be transformed to corresponding aerogels by a freeze-drying method. The composite nanobelt aerogel can withstand a compressive load of more than 4000 times of its own weight and fully recover after the removal of the weight. It can also sustain 1000 compressive cycles with 6.9% plastic deformation and 91.8% of the maximum stress remaining, with a constant energy loss coefficient as low as 0.16, at the set strain of 30%. The extraordinary mechanical properties are believed to be associated with the structural flexibility of the nanobelts and the RFR-reinforced joints between the crosslinked nanobelts. These inorganic-organic composite aerogels also show good thermal insulation and excellent fire-proof capability. This work provides an effective strategy for fabricating superelastic RFR-based aerogels which show promising applications in fields such as thermal insulation, energy storage, and catalyst support.

Modulating Co reduction degree and Fischer-Tropsch synthesis performance by reducing cobalt silicate at different conditions

It is always hard to reduce Co2SiO4 to active Co0 on supported Co-based catalyst for Fischer-Tropsch synthesis (FTS). Here, amorphous Co2SiO4 material was prepared by in-situ doping TMOS during synthesis of ZIF-67, which was then reduced at different temperature and time to obtain ReX-2h (X = 400, 450, 500, 550, 600) and Re500-Yh (Y = 2, 4, 8) catalysts. The effects of reduction temperature and time on Co reduction degree and FTS performance were investigated. Results indicated that the ReX-2h and Re500-Yh catalysts exhibited low CH4 selectivity due to no obvious Co microcrystal found. The reduction degree of ReX-2h increased with reduction temperature, which led to enhanced FTS activity. However, both Re550-2h and Re600-2h exhibited poorer stability than Re500-2h, so the effects of reduction time on Re500-Yh were done. The reduction degree and FTS activity of Re500-Yh were also promoted with extending reduction time. The Re500-8h exhibited higher FTS activity with good stability.

One-pot Mild Hydrothermal Synthesis of the Nanosheets Constructed Cobalt Silicate Hydroxide Hierarchical Porous Hollow Submicron Spheres as Efficient Adsorbents for Organic Dyes Removal

One-pot Mild Hydrothermal Synthesis of the Nanosheets Constructed Cobalt Silicate Hydroxide Hierarchical Porous Hollow Submicron Spheres as Efficient Adsorbents for Organic Dyes Removal

Phosphate-modified cobalt silicate hydroxide with improved oxygen evolution reaction

Oxygen Evolution Reaction (OER) has gained significant attention due to its crucial role in renewable energy systems. The quest for efficient and low-cost OER catalysts remains a challenge of significant interest and importance. In this work, phosphate-incorporated cobalt silicate hydroxide (denoted as CoSi-P) is reported as a potential electrocatalyst for OER. The researchers first synthesized hollow spheres of cobalt silicate hydroxide Co3(Si2O5)2(OH)2 (denoted as CoSi) using SiO2 spheres as a template through a facile hydrothermal method. Phosphate (PO43−) was then introduced to layered CoSi, leading to the reconstruction of the hollow spheres into sheet-like architectures. As expected, the resulting CoSi-P electrocatalyst demonstrated low overpotential (309 mV at 10 mA·cm−2), large electrochemical active surface area (ECSA), and low Tafel slope. These parameters outperform CoSi hollow spheres and cobaltous phosphate (denoted as CoPO). Moreover, the catalytic performance achieved at 10 mA cm−2 is comparable or even better than that of most transition metal silicates/oxides/hydroxides. The findings indicate that the incorporation of phosphate into the structure of CoSi can enhance its OER performance. This study not only provides a non-noble metal catalyst CoSi-P but also demonstrates that the incorporation of phosphates into transition metal silicates (TMSs) offers a promising strategy for the design of robust, high-efficiency, and low-cost OER catalysts.

Sulfide-modified cobalt silicate activated periodate for nitenpyram degradation: Enhanced radical and non-radical pathway

Periodate-based advanced oxidation processes (PI-AOPs) exhibited a promising future for the reduction of emerging refractory organic pollutants. However, the underlying mechanism and the sulfuretted effect of sulfide-modified metal silicate materials for PI activation were still unclear. In this study, sulfide-modified metal silicates (S-CoSi) were first synthesized and applied in the PI-AOPs system. Different from traditional metal silicate materials, sulfurization improved the catalytic performance. The enhanced degradation performance was from the increase in specific surface area and charge transfer efficiency, which derived from the sulfurization in metal silicate. DFT calculations revealed that the enhanced charge densities of Co-S bonds promoted the existence of Co (Ⅱ), which was more conducive to PI activation. Experimental and calculation results further demonstrated that Co was the active site in S-CoSi, and sulfur species strengthened the radical pathway by assisting Co (Ⅱ) regeneration (electron transfer from S to Co) rather than participating in the PI activation. Moreover, sulfurization promoted the generation of 1O2 (non-radical pathway) by increasing oxygen vacancy in the metal silicate. This study provided new insights into the effect of sulfurization on the radical and non-radical pathways in the metal silicates PI system.

Catalytic Oxidation of VOC over Cobalt-Loaded Hierarchical MFI Zeolite

The zeolites ZSM-5 with different Si/Al ratios were modified with a buffer solution of HF and NH4F. This acidic treatment led to the obtaining of a material with secondary mesoporosity. The deposition of cobalt from an aqueous solution of cobalt acetate on the surface of treated samples generates the formation of different cobalt oxide species: bulk-like Co3O4 phases strongly interacting with the support, Co2+ in ion exchange positions (γ and β sites) and silicate-like phases. The mechanism of cobalt silicate phase formation is proposed here and includes a replacement of silanol groups and the bridging hydrogens by Co and the inclusion of the Co atoms in tetrahedral framework positions. The catalysts, obtained through use of the treated ZSM-5, exhibit higher activity in the reactions of propane, and n-hexane completes oxidation compared with the catalyst samples containing un-treated zeolite. Both the finer dispersion of metal oxide particles on the hierarchical sample and the presence of secondary mesoporosity improve the effectiveness of the active phase utilization via access to larger number of active sites.

Uniformly stable hydroxylated cobalt(II) silicate species embedded within silicalite-1 zeolite for boosting propane dehydrogenation

Co-based catalysts are promising alternatives to replace expensive Pt- and toxic Cr-based catalysts for propane dehydrogenation (PDH), while the catalytic stability and propylene selectivity have been subjected to the diversity of Co speciations. Given the situation, uniformly stable hydroxylated Co2+ silicate sites (depicted as {OH–Si–(OH)–Co–O–Si-(OH)3}) are successfully embedded into the silicalite-1 zeolite framework located in the straight and intersection channels (Co@S-1) with the assistance of Co precursors and geminal silanols via a facile hydrothermal synthesis, as revealed by detail characterizations. Under comparable conditions, a superior catalytic PDH performance with attractive propylene formation rate of 14.6 mmol·gcat−1·h−1, propylene selectivity higher than 93% and very low deactivation rate of 0.0206 h−1 after 7 h is achieved over the Co@S-1(EDA) catalyst. Furthermore, the catalytic performance can be restored to the same as that of the fresh catalyst after 3 successive regenerations. In situ FTIR spectra analysis further reveals the dynamic changes in the characteristic absorption bands associated with the hydroxylated Co2+ silicate sites and the intermediate product (2-propyl) during the PDH reaction and a reaction mechanism is proposed accordingly. This work provides a new insight for designing high-efficiency nonprecious metal PDH catalysts.