Cobalt-phosphate Catalyst Research Articles

Simultaneous Solar-Thermal Desalination and Catalytic Degradation of Wastewater Containing Both Salt Ions and Organic Contaminants.

Although solar steam generation is promising in generating clean water by desalinating seawater, it is powerless to totally degrade organic contaminants in the seawater. Herein, solar steam generation and catalytic degradation are integrated to generate clean water by simultaneous solar-driven desalination and catalytic degradation of wastewater containing both salt ions and organic contaminants. Stepwise decoration of three-dimensional nickel foam with polypyrrole, reduced graphene oxide (RGO), and cobalt phosphate is realized to obtain polypyrrole/RGO/cobalt phosphate/nickel foam (PGCN) hybrids for solar-driven desalination and catalytic degradation of wastewater containing antibiotics and salt ions. The oxygen-containing groups of the RGO integrated with the porous nickel foam make the porous PGCN hybrid hydrophilic and ensure the upward transport of water to the evaporation surface, and the oxygen vacancies of the cobalt phosphate allow the PGCN to generate abundant highly active singlet oxygen that could still exhibit excellent catalytic degradation performances in the high salinity and highly alkaline environment of seawater. In addition to the high solar light absorbance and satisfactory solar-thermal conversion efficiency of polypyrrole and RGO, the thermally conductive nickel foam skeleton can effectively transfer the heat generated by the solar-thermal energy conversion to the adjacent cobalt phosphate catalyst and nearby wastewater, achieving a solar-thermal-promoted catalytic degradation of organic contaminants. Therefore, a high pure water evaporation rate of 2.08 kg m-2 h-1 under 1 sun irradiation and 100% catalytic degradation of Norfloxacin and dyes are achieved. The PGCN hybrid is highly efficient in purifying seawater containing 10 ppm Norfloxacin and simultaneously achieves a high purification efficiency of 100 kg m-2 h-1.

Surface reconfiguration of silver nanoparticle doped cobalt phosphate for enhancing overall water electrocatalysis in alkali

The exploitation of bifunctional catalysts with low energy consumption and high energy efficiency is vital for water splitting under alkaline conditions. Cobalt-based phosphate is regarded to be highly promising for water electrolysis. However, its poor electrical conductivity and low number of exposed active sites on the surface hinder the further improvement of electrocatalytic performance. In-situ reconstitution of the surface is an effective strategy to enhance the catalytic activity of transition metal-based materials. Herein, AgCoPi-OH-6h was obtained by etching Ag-doped cobalt-based phosphates (AgCoPi) with strong alkaline solutions. The doping of Ag increases the intrinsic activity of cobalt-based phosphates, and the etching process enlarges the specific surface area which provides more active sites. As a result, AgCoPi-OH-6h shows excellent OER and HER performance, which affords a current density of 10 mA cm-2 at low overpotentials of 259 mV and 56 mV, respectively. Moreover, the catalyst exhibits great electrocatalytic stability for over 50 h under industrial current (1500 mA cm-2) in 6 M KOH solution. This work provides a new strategy for enhancing the alkaline electrocatalytic behavior of cobalt phosphate catalysts for water splitting under industrial conditions.

Phosphate Coordination in a Water-Oxidizing Cobalt Oxide Electrocatalyst Revealed by X-ray Absorption Spectroscopy at the Phosphorus K-Edge

In the research on water splitting at neutral pH, phosphorus-containing transition metal oxyhydroxides are often employed for catalyzing the oxygen evolution reaction (OER). We investigated a cobalt–phosphate catalyst (CoCat) representing this material class. We found that CoCat films prepared with potassium phosphate release phosphorus in phosphate-free electrolytes within hours, contrasting orders of magnitude’s faster K+ release. For P speciation and binding mode characterization, we performed technically challenging X-ray absorption spectroscopy experiments at the P K-edge and analyzed the resulting XANES and EXAFS spectra. The CoCat-internal phosphorus is present in the form of phosphate ions. Most phosphate species are likely linked to cobalt ions in Co–O–PO3 motifs, where the connecting oxygen could be a terminal or bridging ligand in Co-oxide fragments (P–Co distance, ~3.1 Å), with additional ionic bonds to K+ ions (P–K distance, ~3.3 Å). The phosphate coordination bond is stronger than the ionic K+-binding, explaining the strongly diverging ion release rates of phosphate and K+. Our results support a structural role of phosphate in the CoCat, with these ions binding at the margins of Co-oxide fragments, thereby limiting the long-range material ordering. The relations of catalyst-internal phosphate ions to cobalt’s redox-state changes, proton transfer, and catalytic activity are discussed.

Integration of cobalt-phosphate catalyst and titanium dioxide interlayer in the hematite photoanodes to improve photoelectrochemical water splitting for hydrogen production

Integration of cobalt-phosphate catalyst and titanium dioxide interlayer in the hematite photoanodes to improve photoelectrochemical water splitting for hydrogen production

Improving the anode performance of microbial fuel cell with carbon nanotubes supported cobalt phosphate catalyst

Microbial fuel cell (MFC) is a sustainable technology that can convert waste to energy by harnessing the power of exoelectrogenic bacteria. However, the poor biocompatibility and low electrocatalytic activities of surface usually cause weak bacterial adhesion and low electron transfer efficiency, which seriously hampers the development of MFCs. Herein, a novel carbon nanotube supported cobalt phosphate (CNT/Co-Pi) electrode is fabricated by assembling CNTs on carbon cloth, followed by the electrodeposition of Co-Pi catalyst. The deposited amorphous Co-Pi thin film contains phosphate and the cobalt ions of multiple oxidation states. The hydrophilic phosphate can promote the adhesion of microorganisms on electrode. The strong conversion ability of multiple states of cobalt offers excellent electrocatalytic activity for the electron transfer across biotic/abiotic interface. Therefore, the highly conductive CNTs substrate, along with the Co-Pi catalyst, provide an effective electron transfer between the electrogenic bacteria and the electrode, which endows MFC high power densities up to 1200 mW m−2. Our work has demonstrated for the first time that CNT/Co-Pi catalyst can promote the interfacial electron transfer between electrogenic bacteria and electrode, and highlighted the application potentials of Co-Pi as an anode catalyst for the fabrication of high performance MFC anodes.

Insight into the improvement mechanism of Co−Pi-modified hematite nanowire photoanodes for solar water oxidation

The composite photoanodes composed by cobalt phosphate catalyst (Co−Pi) modified semiconductor have been widely used for solar water splitting, but the improvement mechanism has not been experimentally confirmed. Here we use transient photoelectrochemical measurements and impedance spectroscopy to investigate the effect of Co−Pi catalyst on hematite nanowire photoanode. It is found that under illumination the Co−Pi catalyst can efficiently promote the transfer of photo-generated holes to the Co−Pi layer by increasing the electrical conductivity of the composite structure under a low potential. The Co−Pi catalyst can recombine with photo-generated electrons to reduce the surface recombination efficiency of photo-generated holes and electrons under a high potential. These results provide important new understanding of the performance improvement mechanism for the Co−Pi-modified semiconductor nanowire composite photoanodes.

Observation of a potential-dependent switch of water-oxidation mechanism on Co-oxide-based catalysts

Summary O–O bond formation is a key elementary step of the water-oxidation reaction. However, it is still unclear how the mechanism of O–O coupling depends on the applied electrode potential. Herein, using water-in-salt electrolytes, we systematically altered the water activity, which enabled us to probe the O–O bond-forming mechanism on heterogeneous Co-based catalysts as a function of applied potential. We discovered that the water-oxidation mechanism is sensitive to the applied potential: At relatively low driving force, the reaction proceeds through an intramolecular oxygen coupling mechanism, whereas the water nucleophilic attack mechanism prevails at high driving force. The observed mechanistic switch has major implications for the understanding and control of the water-oxidation reaction on heterogeneous catalysts.

Correction to “Iron-Tuned 3D Cobalt–Phosphate Catalysts for Efficient Hydrogen and Oxygen Evolution Reactions Over a Wide pH Range”

Correction to “Iron-Tuned 3D Cobalt–Phosphate Catalysts for Efficient Hydrogen and Oxygen Evolution Reactions Over a Wide pH Range”

Iron-Tuned 3D Cobalt–Phosphate Catalysts for Efficient Hydrogen and Oxygen Evolution Reactions Over a Wide pH Range

The design and synthesis of highly efficient and low-cost bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are crucial for electrochemical wat...

Cobalt-Phosphate Catalysts with Reduced Bivalent Co-Ion States and Doped Nitrogen Atoms Playing as Active Sites for Facile Adsorption, Fast Charge Transfer, and Robust Stability in Photoelectrochemical Water Oxidation.

A cobalt-phosphate (Co-Pi) catalyst having octahedral CoO6 molecular units as reaction sites is a key component in photoelectrochemical (PEC) water oxidation systems, but its limited adsorption sites for oxygen-evolving intermediates (*OH, *OOH), slow charge transfer rates, and fast degradation of reaction sites are yet to be overcome. Here, we report that Co-Pi nanoparticles with low-coordinate Co ions and doped nitrogen atoms could be decorated on hematite nanorod arrays to form N-CoPi/hematite composites. Moreover, the local atomic configuration and bond distance studies show that trivalent Co3+ states are partially reduced through nitrogen radicals in the plasma to low-coordinate bivalent Co2+ states playing as the facile adsorption sites of oxygen-evolving intermediates due to the decreased activation barrier for water oxidation. Electron transport is also reinforced by nitrogen species due to the formation of hybridizing N 2p orbitals that give the acceptor levels in the bandgap. As a result, both the incident photon-to-electron conversion efficiency and the charge transfer resistance on N-CoPi/hematite outperform those on a bare hematite by about 3 fold. Furthermore, N-CoPi/hematite gives high activity retention over 90% after the long operation of water oxidation, in support of the reaction sites on N-CoPi not degrading during the successive water oxidation.

TiO2/Fe2O3 photoanodes for solar water oxidation prepared via electrodeposition of amorphous precursors

Hematite-titania thin films with various ratios of Ti/Fe have been prepared on FTO substrate via cathodic and anodic deposition of amorphous Ti oxyhydroxide gel (TiOx) and iron oxyhydroxide (FeOOH) films, respectively followed by annealing processes. TiOx underlayer behaved as a template for FeOOH electrodeposition. The photocatalytic behavior of the photoanodes based on the prepared structures was studied. An increased photocurrent density was obtained without anodic shifting of the photocurrent onset potential. Mott-Schottky studies showed that Ti contributes little to donor density in hematite-titania photoanodes prepared by this technique. The impedance measurements suggest that both separation and transfer of charge carriers are promoted in these hematite-titania photoanodes. For comparative studies, hematite-titania photoanodes have been prepared from TiOx and FeOOH precursors formed by spin-coating technique and anodic deposition method, respectively. The photoelectrochemical performance of these photoanodes in the presence of cobalt-phosphate catalyst was also evaluated.

Co3+ -Rich Na1.95 CoP2 O7 Phosphates as Efficient Bifunctional Catalysts for Oxygen Evolution and Reduction Reactions in Alkaline Solution.

Implementing sustainable energy conversion and storage technologies is highly reliant on crucial oxygen electrocatalysis, such as the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). However, the pursuit of low cost, energetic efficient and robust bifunctional catalysts for OER and ORR remains a great challenge. Herein, the novel Na-ion-deficient Na2-x CoP2 O7 catalysts are proposed to efficiently electrocatalyze OER and ORR in alkaline solution. The engineering of Na-ion deficiency can tune the electronic structure of Co, and thus tailor the intrinsically electrocatalytic performance. Among the sodium cobalt phosphate catalysts, the Na1.95 CoP2 O7 (NCPO5) catalyst exhibits the lowest ΔE (EJ10,OER -EJ-1,ORR ) of only 0.86 V, which favorably outperforms most of the reported non-noble metal catalysts. Moreover, the Na-ion deficiency can stabilize the phase structure and morphology of NCPO5 during the OER and ORR processes. This study highlights the Na-ion deficient Na2-x CoP2 O7 as a promising class of low-cost, highly active and robust bifunctional catalysts for OER and ORR.

Electrodeposition of Cobalt-Phosphate Oxygen Evolution Catalyst on Inert Electrode for Electrolysis.

This study describes the electrodepositon of potentially competent oxygen evolution catalyst on inert anode using phosphate buffered solution containing cobalt ions. The thickness of deposited amorphous cobalt-phosphate catalyst thin film varies depending on the deposition potential and deposition time. The electrodeposited catalyst can actively be used to improve water oxidation reaction under neutral condition.

Powerful amorphous mixed metal catalyst for efficient water-oxidation

One of the greatest challenges of our era is the splitting of water in a cheap and effective way to produce an abundance of clean hydrogen fuel in order to sustain current levels of energy consumption. Today, Oxygen Evolution Reaction (OER) electrode materials are largely based on rare earth elements RuO2 and IrO2, which are increasingly scarce. Here, we report the discovery of an inexpensive new material based on oxides of cobalt and vanadium that exhibits excellent stability under alkaline water electrolysis conditions and one of the lowest overpotentials reported to date for OER in both neutral and alkaline conditions. This material outperforms IrO2 and a recently discovered cobalt phosphate catalyst in terms of both OER catalytic activity and long-term materials stability, associated with a low overpotential.

Oxidative Degradation of Multi-Carbon Substrates by an Oxidic Cobalt Phosphate Catalyst

The development of heterogeneous catalysts to affect the activation of recalcitrant biomolecules has applications for biomass processing, biomass fuel cells, and wastewater remediation. We demonstrate that a cobalt oxygen evolution catalyst (Co-OEC) can catalyze the oxidation of carbon feedstocks completely to CO2. A quantitative analysis of the product distribution from the oxidative degradation of the C2 compound, ethylene glycol, is elaborated and a reaction sequence is proposed. The Co-OEC is also found to be competent for oxidatively degrading C2+ compounds, including glucose and lignin, to carbon dioxide at consequential Faradaic efficiencies.

Photoelectrochemical behaviour of WO3 and Se-WO3 films modified with cobalt-based oxygen evolving catalyst

Thin films of bare and Se-containing tungsten trioxide (WO3) on AISI304 stainless steel were prepared by electrochemical deposition using peroxy-tungstate solutions. Cobalt-phosphate catalyst was photochemically deposited onto the surface of semiconductor particles in order to enhance their activity towards the oxygen evolution reaction. The photoelectrochemical properties of as-prepared electrodes were investigated in neutral 0.1 M phosphate buffer solutions. The voltammetric characteristics revealed that the presence of cobalt-based catalyst effectively changes the photoelectrocatalytic activity of WO3 and Se-WO3 particles.

Photoelectrochemical Properties of GaN Photoanodes with Cobalt Phosphate Catalyst for Solar Water Splitting in Neutral Electrolyte

Cyclic voltammetry measurements are carried out in neutral phosphate-buffered electrolyte using n-type Ga-polar GaN thin-film photoelectrodes with and without cobalt phosphate (Co-Pi) modification. Without Co-Pi, the variation of the photocurrent with the bias potential exhibits a two-step behavior and under chopped illumination spikes occur at low bias potential. Thus in this regime surface recombination is dominant. Co-Pi modification suppresses surface recombination and significantly increases the photocurrent, especially for low bias potentials. At the same time, stability tests reveal that Co-Pi does not protect GaN against photocorrosion. Experiments using H2O2 imply that this photocorrosion is a reductive process and probably related to the presence of charged surface defects.

Photocurrent of BiVO4 is limited by surface recombination, not surface catalysis.

Bismuth vanadate is one of the most promising photoanode materials for photoelectrochemical water splitting. In order to achieve high photocurrents the surface of BiVO4 always has to be modified with water oxidation catalysts, such as cobalt phosphate (CoPi), FeOOH, or NiFeO x . While this has generally been attributed to the poor intrinsic catalytic activity of BiVO4, detailed insight into the fate of the photogenerated charge carriers at the surface is still lacking. We used intensity modulated photocurrent spectroscopy (IMPS) to investigate the surface carrier dynamics of bare and CoPi-modified spray-deposited BiVO4 films. Using a model developed by Peter et al., it was possible to distinguish the reaction rate constants for surface recombination and charge transfer to the electrolyte. We found that modification with CoPi reduced the surface recombination of BiVO4 with a factor of 10-20, without significantly influencing the charge transfer kinetics. Control experiments with RuO x , one of the best known OER electrocatalysts, did not affect surface recombination and led to an actual decrease of the photocurrent. These results show that the main role of the CoPi is to passivate the surface of BiVO4 and that, contrary to earlier assumptions, the photocurrent of BiVO4 is limited by surface recombination instead of charge transfer. The importance of surface recombination is well recognized for conventional semiconductors in the field of photovoltaics; these findings show that it may also play a crucial role in oxide-based semiconductors for photoelectrochemical energy conversion.

Suppression of Photoanodic Surface Oxidation of n-Type 6H-SiC Electrodes in Aqueous Electrolytes.

The photoelectrochemical characterization of silicon carbide (SiC) electrodes is important for enabling a wide range of potential applications for this semiconductor. However, photocorrosion of the SiC surface remains a key challenge, because this process considerably hinders the deployment of this material into functional devices. In this report, we use cyclic voltammetry to investigate the stability of n-type 6H-SiC photoelectrodes in buffered aqueous electrolytes. For measurements in pure Tris buffer, photogenerated holes accumulate at the interface under anodic polarization, resulting in the formation of a porous surface oxide layer. Two possibilities are presented to significantly enhance the stability of the SiC photoelectrodes. In the first approach, redox molecules are added to the buffer solution to kinetically facilitate hole transfer to these molecules, and in the second approach, water oxidation in the electrolyte is induced by depositing a cobalt phosphate catalyst onto the semiconductor surface. Both methods are found to effectively suppress photocorrosion of the SiC electrodes, as confirmed by atomic force microscopy and X-ray photoelectron spectroscopy measurements. The presented study provides straightforward routes to stabilize n-type SiC photoelectrodes in aqueous electrolytes, which is essential for a possible utilization of this material in the fields of photocatalysis and multimodal biosensing.

Heterogeneous Water Oxidation: Surface Activity versus Amorphization Activation in Cobalt Phosphate Catalysts

AbstractIs water oxidation catalyzed at the surface or within the bulk volume of solid oxide materials? This question is addressed for cobalt phosphate catalysts deposited on inert electrodes, namely crystallites of pakhomovskyite (Co3(PO4)2⋅8 H2O, Pak) and phosphate‐containing Co oxide (CoCat). X‐ray spectroscopy reveals that oxidizing potentials transform the crystalline Pak slowly (5–8 h) but completely into the amorphous CoCat. Electrochemical analysis supports high‐TOF surface activity in Pak, whereas its amorphization results in dominating volume activity of the thereby formed CoCat material. In the directly electrodeposited CoCat, volume catalysis prevails, but not at very low levels of the amorphous material, implying high‐TOF catalysis at surface sites. A complete picture of heterogeneous water oxidation requires insight in catalysis at the electrolyte‐exposed “outer surface”, within a hydrated, amorphous volume phase, and modes and kinetics of restructuring upon operation.