Search

Amorphous Co–Ni–B nanocatalyst with high electrocatalytic activity toward hydrogen evolution reaction (HER) in wide pH range was successfully synthesized. The content of Ni was varied by adjusting the molar ratio Ni/(Ni + Co) in Co–Ni–B from 10% to 50% to identify the most suitable composition for HER. Co-30Ni–B (with 30% Ni/(Ni + Co)) showed the highest catalytic activity and could reach a current density of 10 mA/cm 2 at just 170 mV in pH 7 and 133 mV in pH 14. It also exhibited a Tafel slope value of 51 mV/dec in pH 7 suggesting Volmer-Heyrovsky reaction mechanism for HER. The role of each element in improving the activity was justified with results from XPS, XAS and DFT calculations. It was observed that the presence of Ni promotes higher electron density at Co active sites of Co–Ni–B which in turn facilitates efficient reduction reaction to enhance HER rate. Co-30Ni–B could sustain 1000 cycles and prolonged hours of operation for about 40 h without losing activity making it an excellent low-cost electrocatalyst material. [ABSTRACT FROM AUTHOR]

Lattice location of B in TiO 2 is tuned to determine its effect on the photocatalytic activity of Co-B codoped TiO 2 . Sol–gel method was used to synthesize the samples. The concentrations of Co and B were first optimized by maximizing the photocatalytic activity for the monodoped (Co or B)-TiO 2 . In addition to the DFT calculations for discovering new energetic levels introduced in TiO 2 by codoping, various characterization techniques were used to determine the dopant lattice sites in TiO 2 and interactions between them; and also determining their consequences on electronic, morphological, structural, and optical properties. At low concentration of B-doping (1 at.%), B occupies the interstitial site (B int ), but as the concentration increases (2 at.% and 3 at.%) B also occupies substitutional O position (B sub ) in addition to B int to form TiO 2 containing B int+sub . Both these B-doped TiO 2 showed improved photocatalytic activity attributed to effective charge separation obtained for TiO 2 –B int due to the formation of shallow energy level while higher visible light absorption is achieved with TiO 2 –B int+sub owing to the presence of two deep energy levels in the band gap as confirmed by DFT calculations. In the case of Co doping, the band gap of TiO 2 is reduced but the recombination rates are always high and are caused by the formation of Co states in the band gap. For Co monodoped TiO 2 , the photocatalytic activity is low for all the concentrations considered, except for very low concentration of Co (0.1 at.%). Two opposite effects were observed when small amount of Co (0.1 at.%) was codoped with B int or B int+sub . In particular, the photocatalytic degradation rate of organic aqueous pollutants ( p -nitrophenol and rhodamine B dye) reduces for TiO 2 –Co–B int whereas it is enhanced remarkably for TiO 2 –Co–B int+sub as compared to (Co or B) monodoped (∼2.1 times) and undoped (∼7.8 times) TiO 2 . Higher photocatalytic activity observed in Co-doped TiO 2 –B int+sub is discussed in terms of the interactions of Co with B at two different lattice positions in TiO 2 and the synergistic effect created by higher visible light absorption and the improved charge separation. [ABSTRACT FROM AUTHOR]

A porous coating assembled with hierarchical 3D Co 3 O 4 urchin-like particles was synthesized by Pulsed Laser Deposition (PLD) and thermal oxidation. Laser ablation of Co B powder, used as the target material, in oxygen atmosphere formed core–shell particles on the coating surface with mainly a metallic Co core and a mixture of Co, B and O accommodating the shell. The thermal oxidation of these core–shell particles in air at 600 °C induces the morphological transformation to urchin-like particles consisting of nanowires (NWs) (diameter: 30–60 nm and length 1–3 μm) grown radially from the core surface. The extrusion marks on the surface of NWs indicate that the stress induced growth process is caused by difference in the thermal expansion coefficient. XRD, Raman, EXAFS and HRTEM analysis confirmed that the NWs are polycrystalline consisting of pure Co 3 O 4 phase. A wet-chemistry hydrothermal procedure was also employed to synthesize nanostructured urchin-like particles which are hollow and the structure is held together by the radially oriented nanorods (diameter: 40–150 nm). During photocatalysis, urchin-like particles synthesized by PLD displayed significantly higher (∼5 times) degradation rates when compared to chemical urchins for degradation of methylene blue dye via a photo-Fenton reaction in presence of H 2 O 2 and visible light. This is mainly attributed to poor stability of the nanorods in the chemical urchin structure. Features such as high surface area, enhanced stability against agglomeration, polycrystalline nature of the NWs, porous surface and superior adhesion, are responsible for the enhanced photocatalytic activity of Co 3 O 4 urchin-like particles assembled in a porous coating synthesized by PLD and thermal oxidation. Reusability tests also demonstrate the robust nature of the catalyst coating. [ABSTRACT FROM AUTHOR]

Highlights: [•] V–N-codoped TiO2 thin films have been prepared using RF-magnetron sputtering. [•] The band gap was narrowed up to 2.5eV when V and N were codoped in TiO2. [•] V–N-codoped TiO2 thin film was able to degrade organic water pollutants much faster than mono-doped and undoped TiO2. [•] Increased visible light absorption and charge separation are mainly responsible for enhanced photocatalytic activity for codoped-TiO2. [ABSTRACT FROM AUTHOR]

Highlights: [•] Co-B catalyst particles were supported over three type of mesoporous silica of different pore sizes. [•] Co-B supported over SBA-15 showed highest H2 generation rate for hydrolysis of AB. [•] Confinement of Co-B within the pores creates smaller NPs (6nm) with uniform size distribution. [•] Thicker pore walls of SBA-15 avoid agglomeration of Co-B NPs at elevated temperature (873K). [Copyright &y& Elsevier]

Abstract: Co3O4 nanoparticles assembled coatings have been synthesized by physical (pulsed laser deposition (PLD) and electron beam deposition) and chemical (sol–gel and electroless) techniques. The morphological, structural, and optical properties of all the coatings were analyzed by SEM, XRD, Raman spectroscopy, XPS, and UV–vis spectroscopy. The catalytic activities of the several Co3O4 heterogeneous catalyst coatings have been compared by looking at their efficiency on degradation of methylene blue dye that occurs via photo Fenton reaction in presence of H2O2 or oxone oxidants. The coating synthesized by PLD exhibits the best photo-degradation rate of dye in presence of H2O2 (4h) or oxone (8min). The NPs produced by PLD process exhibit smaller average size (18nm), narrow size distribution (σ =3nm), perfect spherical shape, low degree of agglomeration, and mixed amorphous-nanocrystalline phase. These special features of NPs, along with better visible light absorption, are the main factors responsible for the enhanced photocatalytic activity of the PLD Co3O4 NPs assembled coating. It is also observed that although the concentration of oxone (0.5mM) was very small as compared to H2O2 (100mM) the photo-degradation of MB dye solution is much faster for oxone. [Copyright &y& Elsevier]

Abstract: V- and N-codoped TiO2 photo-catalyst is synthesized by sol–gel method to sensitize TiO2 to visible light. The concentrations of V and N were varied and optimized to enhance photo-catalytic activity. In order to increase the active surface area, the crystalline powder was ball milled to obtain nanosized particles. The photo-catalysts were characterized by Micro-Raman, TEM, XPS and UV–vis (in diffused reflectance mode) techniques. The co-doped TiO2 photocatalyst displayed narrower band gap (2.3eV) compared to singly doped TiO2 catalyst, namely V (2at.%)-doped (2.42eV), N (4at.%)-doped (2.95eV), and undoped TiO2 (3.13eV). The photocatalytic activity for the degradation of Rhodamine B (an organic dye) under visible light irradiation obtained with co-doped TiO2 photo-catalyst is significantly better as compared to the undoped, V-doped, and N-doped TiO2. The incorporation of V and N in TiO2 lattice induces isolated energy levels near the conduction and valence bands, respectively, causing an effective narrowing of the band gap. In addition, due to the low dopants concentrations, these energy levels can also act as traps for photoexcited holes or electrons thus reducing the recombination between photo-generated charges. Both these effects, namely band narrowing and enhanced charge separation produce synergistic effects to increase the photocatalytic activity of V-N-codoped TiO2. [Copyright &y& Elsevier]

Abstract: Co-P-B catalyst coatings have been synthesized on Ni-foam by using electroless deposition (ED) and their catalytic activity was investigated by catalytic dehydrogenation of ammonia borane (AB, NH3BH3) for H2 generation. Co-P-B catalyst (both in form of powder and coating) showed superior catalytic activity in hydrolysis reaction of AB than that of Co-B powder, with complete evolution of H2 (97%) at very high rate (2l/min/gcatalyst). This was mainly attributed to synergic effect caused by B and P over Co active sites to lower the activation energy of the process. For thermolysis reaction, it was observed that AB loaded on Co-P-B/Ni catalyst releases first mole of H2 at considerably low temperature starting at 50°C and with desorption peak centered at 80°C. To our knowledge this value is the lowest reported for solid state catalyst. Moreover, the catalytic thermolysis did not present any induction time and minimizes the formation of undesirable byproduct like borazine and ammonia. The present result suggests that Co-P-B coated on Ni is a highly efficient and low cost catalyst and can be used for both hydrolysis as well as thermolysis reaction of NH3BH3 with the important advantage that it can be easily recovered and repeatedly reused. [Copyright &y& Elsevier]

Abstract: Nanoparticle-assembled Co-B thin films were synthesized by Pulsed Laser Deposition (PLD) and used as catalysts for the hydrolysis of NH3BH3 (ammonia borane, AB) to produce molecular hydrogen. Amorphous Co-B-based catalyst powders, produced by chemical reduction of cobalt salts, were used as target material for Co-B thin film catalysts preparation through PLD. Surface morphology of Co-B powder and film catalyst was studied using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Compositional and structural characterizations were carried out using X-photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) techniques, respectively. The efficiency of both powder and film catalysts was tested by comparative kinetic analysis of the AB hydrolysis for hydrogen production. It was observed that nanoparticles produced during the laser ablation process act as active catalytic centers to produce significantly higher rate (about 6 times) of H2 than the same amount of the corresponding Co-B powders. Almost complete conversion (95%) of AB was obtained, as confirmed by 11B NMR, by using Co-B films at room temperature. Active Co-B nanoparticles on the surface of the PLD-deposited films is able to decrease the activation energy, for hydrolysis of AB, to the very low value of 34kJmol−1. We also found that by adding small amount of NaBH4 to the NH3BH3 solution increases the efficiency of the Co-B catalyst films, thus generating H2 with higher rate. Maximum H2 generation rate of about ∼8.2LH2 min−1 (g of Co)−1 and ∼13LH2 min−1 (g of Co)−1 was measured by hydrolysis of AB and mixture of (AB+NaBH4) solutions, respectively. [Copyright &y& Elsevier]

Abstract: Cr-modified Co–B (Co–Cr–B) catalyst alloy powders have been synthesized by chemical reduction of cobalt and chromium salt at room temperature to study the hydrogen production by catalytic hydrolysis of NaBH4. The Cr/Co molar ratio was varied in the catalyst in order to study the effect of Cr doping on surface modification and catalytic efficiency of Co–B catalyst. The resulting catalyst powders were characterized by scanning electron microscopy, X-ray diffraction, X-photoelectron spectroscopy, and BET surface area measurement. When the molar ratio χ Cr =Cr/(Cr+Co) exceeds 9% the BET surface area of the Co–Cr–B catalyst increases by one order of magnitude as compared to that of Co–B catalyst. The catalytic activity of the Co–Cr–B for hydrogen production depends on Cr concentration: specifically, the activity increases by increasing χ Cr up to about 4% and then it gradually decreases by further increasing χ Cr. We established that the increased catalytic activity is related to the formation of chromium oxide on the catalyst surface, with the oxide favoring the dispersion of Co–B particles resulting in high catalyst surface area. However as χ Cr exceeds 4%, Cr starts to cover the Co active sites and the corresponding catalytic activity decreases. The highest catalytic activity was obtained at the optimum Cr-content, χ Cr =4%, in Co–Cr–B catalyst, showing nearly 4 times higher H2 generation rate than that of pure Co–B catalyst. Kinetic studies on the hydrolysis reaction of NaBH4 with Co–Cr–B catalyst reveal that the concentrations of both NaBH4 and NaOH have essentially no effects on hydrogen generation rate. The promoting effect of Cr in Co–Cr–B catalyst results in lower activation energy for hydrogen production, which is 37kJmol−1 as compared to 45kJmol−1 obtained with pure Co–B powder. Finally, the possible role of Cr3+ species in the electron exchange mechanisms involved in NaBH4 hydrolysis with the Co–Cr–B catalyst has been discussed. [Copyright &y& Elsevier]

Cu–N-codoped TiO 2 photocatalyst is synthesized by sol–gel method to obtain enhanced optical absorption in the visible region. Optimum concentrations of Cu and N were obtained by maximizing the photocatalytic activity for the monodoped (Cu or N) TiO 2 . These optimized concentrations were used for synthesizing (Cu, N)–codoped TiO 2 . The photocatalysts were characterized using XRD, micro-Raman, SEM, XPS, BET surface area analyzer, UV–vis diffuse reflectance spectroscopy and photoluminescence. XPS study suggests the incorporation of Cu 2+ into TiO 2 lattice, which assists N to substitutionally replace oxygen in codoped TiO 2 , while maintaining the anatase phase even after doping. N-doping creates minor variation in the energy band gap of TiO 2 reducing it upto 3.0 eV, while Cu doping was able to narrow the band gap to 2.2 eV mainly due to the localized levels of Cu-3d states and shifting of Ti-3d states to lower energy (due to oxygen vacancies) in the band-gap as deduced from XPS data and confirmed by the DFT calculation. In (Cu, N)–codoped TiO 2 , visible light absorption is higher than the other TiO 2 samples, a feature that is mainly attributed to the formation of an isolated intermediate band (IB) occurring due to the strong hybridization between Cu 3d and N 2p orbitals. This IB contributes to visible light absorption by two step optical transition with the first transition from valence band (VB) to IB and the second from IB to conduction band (CB). The dopant species may also act to reduce the charge carrier recombination by acting as the trapping sites for photogenerated charges. (Cu, N)–codoped TiO 2 was able to degrade Methylene Blue dye and p -Nitrophenol solution under light irradiation with significantly better rate in comparison to monodoped and undoped TiO 2 . High photocatalytic activity is attributed to the presence of IB in the energy band gap of TiO 2 , which creates the synergic effect by higher visible light absorption and lower recombination of photogenerated charges. [ABSTRACT FROM AUTHOR]

• Amorphous Co-P-B electrocatalyst synthesized by facile non-toxic reduction method. • Co-P-B shows excellent bifunctional behaviour in alkaline medium. • Co-P-B inherits electron transfer properties from both Co-B and Co-P. • DFT studies identified Co sites in Co-P-B more favourable for H-adsorption. • Wide-pH suitability and stability was established for Co-P-B catalyst. A unique cobalt-phosphide-boride (Co-P-B) catalyst was synthesized via simple chemical-reduction route. The obtained catalyst was amorphous in nature, resembling the spherical morphology of Co-B nanoparticles. X-ray photoelectron spectroscopy revealed that B loses electrons to Co while P gains electrons from Co. This unique electron transfer mechanism in Co-P-B is a combination of the characteristics showcased by Co-B and Co-P catalysts individually. The optimized catalyst (Co-P-B-5) showed overpotentials of 145 mV and 290 mV to achieve the benchmark current density of 10 mA/cm2 for HER and OER, respectively, in 1 M NaOH. From theoretical calculations, it was observed that addition of P modulates the electron density at Co sites, thereby optimizing the H-adsorption capability, leading to higher HER rate. During anodic polarization, Co-P-B-5 shows formation of large number of CoOOH species on its surface, facilitating OER. Finally, stability, recyclability and wide-pH suitability of Co-P-B-5 was established to demonstrate its industrial viability. [ABSTRACT FROM AUTHOR]