A novel method for preparing BiOI nanoplates and their use as precursors to synthesize porous BiVO4 water oxidation photocatalysts.

In this work, we report an innovative method for synthesizing BiOI nanoplate powder by a slow basification of an aqueous solution constituted of Bi(NO3)3 and KI. The basification was done with NH3 vapor which was naturally generated on top of an NH4OH solution kept in a closed space. The impact of the basification rate on the morphology and crystallinity of the BiOI product was investigated. Herein, we also report on the use of newly produced BiOI nanoplate powder together with the VO(acac)2 precursor for fabricating BiVO4 photoanodes for solar driven water splitting applications. We also discuss how the morphology of BiOI nanoplates and their orientation on a fluorine doped tin oxide substrate will affect the morphology, topology and photocatalytic performance of the electrode. The BiVO4 photoanode showed a photocatalytic current density of 0.55 mA cm-2 at 1.23 V vs. the Reversible Hydrogen Electrode (RHE) when assayed in a pH 7 phosphate buffer electrolyte and under 1 sun illumination.

Fabrication of inverse opal molybdenum sulfide and its use as a catalyst for H2 evolution.

Amorphous molybdenum sulfide (MoSx) and crystalline molybdenum disulfide (MoS2) are attractive noble-metal-free electrocatalysts for the H2 evolution reaction from water. Their actual activities depend on the quantity of active sites which are exposed to the electrolyte, which in turn, is influenced by their specific electrochemical surface area. Herein we report on the fabrication of regular inverse opal MoSx and MoS2 films by employing polystyrene nanoparticles with diameters in the range of 30-90 nm as hard templates. The use of these catalysts for the H2 evolution reaction in an acidic electrolyte solution is also presented. Impacts of the regular porous structure, the film thickness as well as the chemical nature of the catalyst (MoS2versus MoSx) are discussed. It shows a catalytically-effective-thickness of ca. 300 nm where the electrolyte can fully penetrate the catalyst macropores, thus all the catalytic active sites can be exposed to the electrolyte to achieve the maximal catalytic operation.

[Mo2 S12 ]2- Complex as a Precursor for In-situ Generation of Molybdenum Sulfide Catalyst During the H2 Evolution.

For decades, the sulfido molybdenum complexes like [MoS4 ]2- , [Mo2 S12 ]2- , [Mo3 S13 ]2- have gained great attention because of their chemical versatility as well as their structural similarity to the edge-plan of the molybdenum disulfide (MoS2 ) which shows promising catalytic ability for the H2 generation. In this work, we report on the investigation of the dinuclear complex [Mo2 S12 ]2- in both organic and aqueous solution. We demonstrate that [Mo2 S12 ]2- is not intact during the H2 evolution catalysis when it is assayed as a homogeneous catalyst in an electrolyte solution (e. g. in DMF or water solvent) nor when it is immobilized on an electrode surface (e. g. mesoporous carbon black). It transforms into the polymeric amorphous molybdenum sulfide [MoS] which subsequently acts as an actual catalyst. We discuss on the possible [Mo2 S12 ]2- to [MoS] transformation mechanism by employing an arsenal of electrochemical analysis, spectroscopic analyses and microscopic analyses. Effects of the electrochemical operating conditions to the [Mo2 S12 ]2- to [MoS] transformation as well as to the chemical nature and the catalytic performance of the [MoS] product are also emphasized.

Exploring the Sub-nanoscale Structure of Cobalt Molybdenum Sulfide and the Role of a Cobalt Promoter in Catalytic Hydrogen Evolution.

Cobalt-promoted molybdenum sulfide (CoMoS) is known as a promising catalyst for H2 evolution reaction and hydrogen desulfurization reaction. This material exhibits superior catalytic activity as compared to its pristine molybdenum sulfide counterpart. However, revealing the actual structure of cobalt-promoted molybdenum sulfide as well as the plausible contribution of a cobalt promoter is still challenging, especially when the material has an amorphous nature. Herein, we report, for the first time, on the use of positron annihilation spectroscopy (PAS), being a nondestructive nuclear radiation-based method, to visualize the position of a Co promoter within the structure of MoS at the atomic scale, which is inaccessible by conventional characterization tools. It is found that at low concentrations, a Co atom occupies preferably the Mo-vacancies, thus generating the ternary phase CoMoS whose structure is composed of a Co-S-Mo building block. Increasing the Co concentration, e.g., a Co/Mo molar ratio of higher than 1.12/1, leads to the occupation of both Mo-vacancies and S-vacancies by Co. In this case, secondary phases such as MoS and CoS are also produced together with the CoMoS one. Combining the PAS and electrochemical analyses, we highlight the important contribution of a Co promoter to enhancing the catalytic H2 evolution activity. Having more Co promoter in the Mo-vacancies promotes the H2 evolution rate, whereas having Co in the S-vacancies causes a drop in H2 evolution ability. Furthermore, the occupation of Co to the S-vacancies leads also to the destabilization of the CoMoS catalyst, resulting in a rapid degradation of catalytic activity.

Crystallization Pathways and Evolution of Morphologies and Structural Defects of α-MnO2 under Air Annealing.

Manganese dioxide nanomaterials have wide applications in many areas from catalysis and Li-ion batteries to gas sensing. Understanding the crystallization pathways, morphologies, and formation of defects in their structure is particularly important but still a challenging issue. Herein, we employed an arsenal of X-ray diffraction (XRD), scanning electron microscopy (SEM), neutron diffraction, positron annihilation spectroscopies, and ab initio calculations to investigate the evolution of the morphology and structure of α-MnO2 nanomaterials prepared via reduction of KMnO4 solution with C2H5OH prior to being annealed in air at 200-600 °C. We explored a novel evolution that α-MnO2 nucleation can be formed even at room temperature and gradually developed to α-MnO2 nanorods at above 500 °C. We also found the existence of H+ or K+ ions in the [1 × 1] tunnels of α-MnO2 and observed the simultaneous presence of Mn and O vacancies in α-MnO2 crystals at low temperatures. Increasing the temperature removed these O vacancies, leaving only the Mn vacancies in the samples.

Electrocatalytic H2 evolution using binuclear cobalt complexes as catalysts.

We report herein on the use of two binuclear cobalt complexes with the N,N'-bis(salicylidene)-phenylmethanediamine ligand as catalysts for the H2 evolution in DMF solution with acetic acid as proton source. Both experimental analyses (electrochemical analysis, spectroscopy analysis) and theoretical analysis (foot-of-the wave analysis) were employed. These catalysts required an overpotential of ca. 470 mV to catalyze the H2 evolution and generated H2 gas with a faradaic efficiency of 85-95% as calculated on the basis of after 5 hour bulk electrolysis. The kinetic investigation showed the maximal TOF value of 50 s-1 on the basis of an ECEC mechanism. Two cobalt centers, standing at a long distance of 4.175 Å, operated independently during catalysis without a synergetic effect or cooperation capability.

Synthesis of NiFeOx nanocatalysts from metal-organic precursors for the oxygen evolution reaction.

Production of hydrogen from a renewable source that is water requires the development of sustainable catalytic processes. This implies, among others, developing efficient catalytic materials from abundant and low-cost resources and investigating their performance, especially in the oxidation of water as this half-reaction is the bottleneck of the water splitting process. For this purpose, NiFe-based nanoparticles with sizes ca. 3-4 nm have been synthesized by an organometallic approach and characterized by complementary techniques (WAXS, TEM, STEM-HAADF, EDX, XPS, and ATR-FTIR). They display a Ni core and a mixed Ni-Fe oxide shell. Once deposited onto FTO electrodes, they have been assessed in the electrocatalytic oxygen evolution reaction under alkaline conditions. Three different Ni/Fe ratios (2/1, 1/1 and 1/9) have been studied in comparison with their monometallic counterparts. The Ni2Fe1 nanocatalyst displayed the lowest overpotential (320 mV at j = 10 mA cm-2) as well as excellent stability over 16 h.

Water-Splitting Artificial Leaf Based on a Triple-Junction Silicon Solar Cell: One-Step Fabrication through Photoinduced Deposition of Catalysts and Electrochemical Operando Monitoring.

Solar hydrogen generation via water splitting using a monolithic photoelectrochemical cell, also called artificial leaf, could be a powerful technology to accelerate the transition from fossil to sustainable energy sources. Identification of scalable methods for the fabrication of monolithic devices and gaining insights into their operating mode to identify solutions to improve performance and stability represent great challenges. Herein, we report on the one-step fabrication of a CoWO|ITO|3jn-a-Si|Steel|CoWS monolithic device via the simple photoinduced deposition of CoWO and CoWS as oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalyst layers, respectively, onto an illuminated ITO|3jn-a-Si|Steel solar cell using a single-deposition bath containing the [Co(WS4)2]2- complex. In a pH 7 phosphate buffer solution, the best device achieved a solar-to-hydrogen conversion yield of 1.9%. Evolution of the catalyst layers and that of the 3jn-a-Si light-harvesting core during the operation of the monolithic device are examined by conventional tools such as scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and inductively coupled plasma optical emission spectroscopy (ICP-OES) together with a bipotentiostat measurement. We demonstrate that the device performance degrades due to the partial dissolution of the catalyst. Still, this degradation is healable by simply adding [Co(WS4)2]2- to the operating solution. However, modifications on the protecting indium-doped tin oxide (ITO) layer are shown to initiate irreversible degradation of the 3jn-a-Si light-harvesting core, resulting in a 10-fold decrease of the performances of the monolithic device.

Covalent Grafting of Ruthenium Complexes on Iron Oxide Nanoparticles: Hybrid Materials for Photocatalytic Water Oxidation.

The present environmental crisis prompts the search for renewable energy sources such as solar-driven production of hydrogen from water. Herein, we report an efficient hybrid photocatalyst for water oxidation, consisting of a ruthenium polypyridyl complex covalently grafted on core/shell Fe@FeOx nanoparticles via a phosphonic acid group. The photoelectrochemical measurements were performed under 1 sun illumination in 1 M KOH. The photocurrent density of this hybrid photoanode reached 20 µA/cm2 (applied potential of +1.0 V vs reversible hydrogen electrode), corresponding to a turnover frequency of 0.02 s-1. This performance represents a 9-fold enhancement of that achieved with a mixture of Fe@FeOx nanoparticles and a linker-free ruthenium polypyridyl photosensitizer. This increase in performance could be attributed to a more efficient electron transfer between the ruthenium photosensitizer and the Fe@FeOx catalyst as a consequence of the covalent link between these two species through the phosphonate pendant group.

Highly porous Co-doped NiO nanorods: facile hydrothermal synthesis and electrocatalytic oxygen evolution properties.

Highly porous 3d transition metal oxide nanostructures are opening up the exciting area of oxygen evolution reaction (OER) catalysts in alkaline medium thanks to their good thermal and chemical stability, excellent physiochemical properties, high specific surface area and abundant nanopores. In this paper, highly porous Co-doped NiO nanorods were successfully synthesized by a simple hydrothermal method. The porous rod-like nanostructures were preserved with the added cobalt dopant ranging from 1 to 5 at% but were broken into aggregated nanoparticles at higher concentrations of additional cobalt. The catalytic activity of Co-doped NiO nanostructures for OER in an alkaline medium was assayed. The 5%Co-NiO sample showed a drastically enhanced activity. This result could originate from the combination of advantageous characteristics of highly porous NiO nanorods such as large surface area and high porosity as well as the important role of Co dopant that could provide more catalytic active sites, leading to an enhanced catalytic activity of the nanocatalyst.

Effects of CO2 and temperature on phytolith dissolution.

Phytoliths, silica structures derived from plant residues in silicon (Si)-accumulating plant species, have recently been recognized as a sink and source of nutrients and a hosting phase for carbon sequestration in soil. While the solubility of phytoliths in relation to their respective nature and solution chemistry has been intensively studied, the combined effects of CO2 and temperature, two highly variable parameters in soil, have not been fully understood. We hypothesized that changes in CO2 and temperature may affect the dissolution rate, thereby resizing the soil phytolith pool. Rice straw phytoliths were obtained from either open burning or controlled heating of straw from 300 to 900 °C and used to determine their batch incubation kinetics in a closed chamber at CO2 concentrations of 0 to 15% vol. and a temperature range of 20 to 50 °C for six days. The results revealed a contrasting effect in which temperature and CO2 were correspondingly found to accelerate or decelerate the dissolution rate of phytoliths. Under the most dissimilar conditions, i.e., 0% vol. CO2 and 50 °C and 15% vol. CO2 and 20 °C, the discrepancy in solubility was approximately six-fold, indicating a high vulnerability of phytoliths to CO2 and temperature changes. This finding also suggests that the soil phytolith pool can be diminished in the case of either increasing soil temperature or decreasing CO2 flux. Calculations based on these data revealed that the dissolution rate of phytoliths could be increased by an average of 4.5 to 7.3% for each 1 °C increase in temperature. This finding suggests a possible impact of current global warming on the global biogenic silica pool, and more insight into the relationship between this pool and climate change is, therefore, necessary to maintain the function of the phytolith phase in soil.

Embedding Amorphous Molybdenum Sulfide within a Porous Poly(3,4-ethylenedioxythiophene) Matrix to Enhance its H2 -evolving Catalytic Activity and Robustness.

Amorphous molybdenum sulfide (MoSx ) is a promising alternative to Pt catalyst for the H2 evolution in water. However, it is suffered of an electrochemical corrosion. In this report, we present a strategy to tack this issue by embedding the MoSx catalyst within a porous poly(3,4-ethylenedioxythiophene) (PEDOT) matrix. The PEDOT host is firstly grown onto a fluorine-doped tin oxide (FTO) electrode by electrochemical polymerization of EDOT monomer in an acetonitrile solution to perform a porous structure. The MoSx catalyst is subsequently deposited onto the PEDOT by an electrochemical oxidation of [MoS4 ]2- monomer. In a 0.5 M H2 SO4 electrolyte solution, the MoSx /PEDOT shows higher H2 -evolving catalytic activities (current density of 34.2 mA/cm2 at -0.4 V vs RHE) in comparison to a pristine MoSx grown on a planar FTO electrode having similar catalyst loading (24.2 mA/cm2 ). The PEDOT matrix contributes to enhance the stability of MoSx catalyst by a significant manner. As such, the MoSx /PEDOT retains 81 % of its best catalytic activity after 1000 potential scans from 0 to -0.4 V vs. RHE, whereas a planar MoSx catalyst is completely degraded after about 240 potential scans, due to its complete corrosion.

Investigation on the Growth Mechanism of Cu2 MoS4 Nanotube, Nanoplate and its use as a Catalyst for Hydrogen Evolution in Water.

Cu2 MoS4 is a ternary transition-metal sulfide that shows great potential in the field of energy conversion and storage, namely catalytic H2 evolution in water and Li-, Na- or Mg-ion battery. In this work, we report on a growth mechanism of the single-crystalline Cu2 MoS4 nanotube from (NH4 )2 MoS4 salt and Cu2 O nanoparticle. By probing the nature and morphology of solid products generated in function of reaction conditions we find that the crystalline Cu(NH4 )MoS4 nanorod is first generated at ambient conditions. The nanorod is then converted into Cu2 MoS4 nanotube under hydrothermal treatment due to the Kirkendall effect or a selective etching of the Cu2 MoS4 core. Extending the hydrothermal treatment causes a collapse of nanotube generating Cu2 MoS4 nanoplate. The catalytic activities of these sulfides are investigated. The Cu2 MoS4 shows superior catalytic activity to that of Cu(NH4 )MoS4 . Catalytic performance of the former largely depends on its morphology. The nanoplate shows superior catalytic activity to the nanotube, thanks to its higher specific electrochemical surface area.

Gold nanorod/molybdenum sulfide core-shell nanostructures synthesized by a photo-induced reduction process.

Coupling of plasmonic nanostructures and semiconductors gives promising hybrid nanostructures that can be used in different applications such as photosensing and energy conversion. In this report, we describe an approach for fabricating a new hybrid material by coupling a gold nanorod (Au NR) core and amorphous molybdenum sulfide (MoSx) shell. The Au NR/MoSx core-shell structure is achieved by exploiting the hot electrons generated in the plasmonic excitation of Au NRs to drive the reduction of [MoS4]2-, which is pre-adsorbed on the Au NR surface, producing a thin MoSx layer. This approach allows us to control the thickness of the MoSx coating layer on the Au NR surface. The resultant Au NR/MoSx hybrid is characterized by absorption spectroscopy, scanning electron microscopy, transmission electron microscopy, energy-dispersive x-ray spectroscopy elemental mapping, x-ray diffraction and x-ray photoelectron spectroscopy.

Insights into the Electrochemical Polymerization of [Mo3 S13 ]2- Generating Amorphous Molybdenum Sulfide.

Amorphous molybdenum sulfide is an attractive electrode material for Li/Mg batteries and an efficient Pt-free catalyst for the hydrogen evolution reaction in water. By using the electrochemical quartz crystal microbalance (EQCM) analysis, new insights were gained into the electrochemical polymerization of the [Mo3 S13 ]2- cluster, which generates amorphous molybdenum sulfide thin films. In this work, it is shown that, at the anodic potential, a two-electron oxidative elimination of the terminal disulfide ligand within the [Mo3 S13 ]2- cluster induces the polymerization. A reductive elimination of the terminal disulfide ligand also occurs at the cathodic potential, inducing the polymerization. However, in sharp contrast to the anodic polymerization, according to which the film growth is rapid, the cathodic polymerization competes with the electrochemical reductive corrosion of the readily grown film, therefore occurring at a significant lower growth rate.

Electrodeposited Amorphous Tungsten-doped Cobalt Oxide as an Efficient Catalyst for the Oxygen Evolution Reaction.

Thin film of amorphous tungsten-doped cobalt oxide (W:CoO) was successfully grown on a conducting electrode via an electrochemical oxidation process employing a [Co(WS4 )2 ]2- deposition bath. The W:CoO catalyst displays an attractive performance for the oxygen evolution reaction in an alkaline solution. In an NaOH solution of pH 13, W:CoO operates with a moderate onset overpotential of 230 mV and requires 320 mV overpotential to generate a catalytic current density of 10 mA cm-2 . A low Tafel slope of 45 mV decade-1 was determined, indicating a rapid O2 -evolving kinetics. The as-prepared W:CoO belongs to the best cobalt oxide-based catalysts ever reported for the oxygen evolution (OER) reaction.

Gold nanoparticles as an outstanding catalyst for the hydrogen evolution reaction.

An electrode made of Au nanoparticles, ca. 13 nm in diameter, displays outstanding catalytic activity for the hydrogen evolution reaction in water. At an overpotential of 200 mV it operates with a catalytic rate TOF of 0.3 s-1, which is among the best performances ever achieved for a Pt-free H2-evolving catalyst.

Novel Amorphous Molybdenum Selenide as an Efficient Catalyst for Hydrogen Evolution Reaction.

Amorphous molybdenum selenide nanopowder, obtained by refluxing Mo(CO)6 and Se precursors in dichlorobenzene, shows several structural and electrochemical similarities to the amorphous molybdenum sulfide analogue. The molybdenum selenide displays attractive catalytic properties for the hydrogen evolution reaction in water over a wide range of pH. In a pH 0 solution, it operates with a small onset overpotential of 125 mV and requires an overpotential of 270 mV for generating a catalytic current of 10 mA/cm2. Compared with molybdenum sulfide, the selenide analogue is more robust in a basic electrolyte. Therefore, molybdenum selenide is a potential candidate for incorporating within an electrolyzer or a photoelectrochemical cell for water electrolysis in acidic, neutral, or alkaline medium.

Molecular Cobalt Complexes with Pendant Amines for Selective Electrocatalytic Reduction of Carbon Dioxide to Formic Acid.

We report here on a new series of CO2-reducing molecular catalysts based on Earth-abundant elements that are very selective for the production of formic acid in dimethylformamide (DMF)/water mixtures (Faradaic efficiency of 90 ± 10%) at moderate overpotentials (500-700 mV in DMF measured at the middle of the catalytic wave). The [CpCo(PR2NR'2)I]+ compounds contain diphosphine ligands, PR2NR'2, with two pendant amine residues that act as proton relays during CO2-reduction catalysis and tune their activity. Four different PR2NR'2 ligands with cyclohexyl or phenyl substituents on phosphorus and benzyl or phenyl substituents on nitrogen were employed, and the compound with the most electron-donating phosphine ligand and the most basic amine functions performs best among the series, with turnover frequency >1000 s-1. State-of-the-art benchmarking of catalytic performances ranks this new class of cobalt-based complexes among the most promising CO2-to-formic acid reducing catalysts developed to date; addressing the stability issues would allow further improvement. Mechanistic studies and density functional theory simulations confirmed the role of amine groups for stabilizing key intermediates through hydrogen bonding with water molecules during hydride transfer from the Co center to the CO2 molecule.