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Few-layer two-dimensional (2D) molybdenum disulfide (MoS2) has great potential in designing high-performance supercapacitors due to its high theoretical specific capacity, tunable bandgap, and fascinating 2D layered structure. However, the lack of efficient synthesis methods, cost-effectiveness, and mass production of few-layered MoS2 hindered its practical applications. Moreover, a large gap between theoretical specific capacitance and the experiment comes from the traditional manufacturing approaches involving polymer binders to prepare the electrode for electrochemical testing. We report an accessible and efficient approach to liquid-phase exfoliation of bulk MoS2 into high-quality, few-layered MoS2 using the green method. We have constructed few layered MoS2 on a Ni-foam as an electrode for electrochemical analysis without any polymer binder or black carbon, which exhibits significant improvements in supercapacitor performance compared to the bulk. The highest specific capacitance achieved is 985 F g−1 at 8 A g−1. The 2D layered structure provides stable channels that facilitate K+ intercalation/desorption during charging and discharging processes, helping to prevent the deposition and accumulation of ions. Finally, theoretical calculations were performed to calculate the electronic structure, adsorption energy, diffusion barrier, and charge transfer of K intercalated and adsorbed bulk and monolayer 2H-MoS2, respectively. The calculated migration energy of the K atom diffusion on monolayer MoS2 (0.05 eV) is considerably lower than that of the bulk (0.8 eV), demonstrating a significant enhancement in electrochemical performance with reducing layer thickness. [ABSTRACT FROM AUTHOR]

Blade-coating is a roll-to-roll (R2R) compatible processing technique and has the potential to address the industry's needs for scalable manufacturing of future organic electronics. Here we investigate the applicability of blade-coating for the fabrication of organic thin-film transistors (OTFTs) based on best-in-class organic semiconducting blends comprised of the conjugated small-molecule 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT), and the conjugated polymer poly(indacenodithiophene-co-benzothiadiazole) (C16IDT-BT). We show that the operating characteristics of blade-coated transistors consistently outperform devices prepared via spin-coating, showcasing the compatibility of the technique. Introducing the molecular p-dopant C60F48 into the binary C8-BTBT:C16IDT-BT blend formulation, in combination with carefully optimized blade-coating conditions, helps to enhance the performance of the ensuing transistors further resulting in a maximum hole mobility of ≈14 cm2 V−1 s−1, and an all-around improvement of the device operating characteristics. Our results show that p-doped blend OTFTs can be manufactured using industry relevant processing techniques without sacrificing their state-of-the-art performance. [ABSTRACT FROM AUTHOR]

Simple, scalable and cost-effective synthesis of quality two-dimensional (2D) transition metal dichalcogenides (TMDs) is critical for fundamental investigations but also for the widespread adoption of these low-dimensional materials in an expanding range of device applications. Here, we report on the liquid-phase exfoliation (LPE) of molybdenum disulfide (MoS2) and tungsten disulfide (WS2) in aqueous ammonia (NH3(aq.)) as a greener alternative to commonly used but less environmentally friendly solvents. The synthesized nanosheets can be prepared in high concentrations (0.5–1 mg mL−1) and exhibit excellent stoichiometric and structural quality with a semiconducting character. These characteristics make them ideal for application in organic optoelectronics, where optical transparency and suitable energetics are two important prerequisites. When MoS2 and WS2 are used as the hole transport layer materials in organic photovoltaics, cells with a power conversion efficiency of 14.9 and 15.6%, respectively, are obtained, highlighting the potential of the aqueous ammonia-based LPE method for the preparation of high quality TMDs. The method could potentially be extended to other TMDs. [ABSTRACT FROM AUTHOR]

A platinum complex, (CH3)2Pt(COD), is grafted via surface organometallic chemistry (SOMC) on morphology-controlled anatase TiO2 to generate single, isolated Pt atoms on TiO2 nano-platelets. The resulting material is characterized by FT-IR, high resolution scanning transmission electron microscopy (HRSTEM), NMR, and XAS, and then used to perform photocatalytic water splitting. The photocatalyst with SOMC-grafted Pt shows superior performance in photocatalytic hydrogen evolution and strongly suppresses the backwards reaction of H2 and O2 forming H2O under dark conditions, compared to the photocatalyst prepared by impregnation at the same Pt loading. However, single Pt atoms on this surface also rapidly coalesce into nanoparticles under photocatalytic conditions. It is also found that adsorption of CO gas at room temperature also triggers the aggregation of Pt single atoms into nanoparticles. A detailed mechanism is investigated for the mobility of Pt in the formation of its carbonyls using density functional theory (DFT) calculations. [ABSTRACT FROM AUTHOR]

SiOx is a promising anode material for lithium-ion batteries (LIBs) due to its relatively high capacity. Nevertheless, the poor conductivity and large volume expansion of SiOx upon Li+ insertion/extraction limit its application. Herein, a novel strategy for preparing ternary Ni/SiOx/nitrogen-doped carbon (NSC) composites has been developed through in situ transformation of a Ni3Si2O5(OH)4/nitrogen-doped carbon precursor derived from dried bamboo leaves. The 3D interconnected SiOx/nitrogen-doped carbon (SC) framework provides sufficient void spaces for relieving the volume change during the lithiation process while facilitating electrolyte infiltration and lithium ion diffusion processes. The growth of uniform Ni nanoparticles (NPs) on the surface of the SC matrix restricts the formation of cracks, reduces volume expansion during the lithiation process, and effectively improves the electrical conductivity of SiOx. The optimized sample delivers a high discharge capacity of 864.6 mA h g−1 after 70 cycles at 200 mA g−1 and a superior rate capability of 289.8 mA h g−1 at 10 A g−1. The electrode delivers a capacity of 427.6 mA h g−1 even at 5 A g−1 after 1000 cycles along with outstanding capacity retention (∼100%). Our method provides insight into the utilization of biomass towards high performance energy storage through simple and low-cost procedures. [ABSTRACT FROM AUTHOR]

The direct conversion of propane into aromatics (BTX) using modified ZSM-5 was achieved with a strategy of “catalysis by design”. In contrast to the classical mode of action of classical aromatization catalysts which are purely based on acidity, we have designed the catalyst associating two functions: One function (Ti-hydride) was selected to activate the C–H bond of propane by σ-bond metathesis to further obtain olefin by β-H elimination and the other function (Brønsted acid) being responsible for the oligomerization, cyclization, and aromatization. This bifunctional catalyst was obtained by selectively grafting a bulky organometallic complex of tetrakis(neopentyl)titanium (TiNp4) at the external surface (external silanol (≡Si–OH) group) of [H-ZSM-5300] to obtain [Ti/ZSM-5] catalyst 1. This metal was chosen to activate the C–H bond of paraffin at the periphery of the ZSM-5 while maintaining the Brønsted acid properties of the internal [H-ZSM-5] for oligomerization, cyclization, and aromatization. Catalyst 2 [Ti–H/ZSM-5] was obtained after treatment under H2 at 550 °C of freshly prepared catalyst 1 ([Ti/ZSM-5]) and catalyst 1 was thoroughly characterized by ICP analysis, DRIFT, XRD, N2-physisorption, multinuclear solid-state NMR, XPS and HR-TEM analysis including STEM imaging. The conversion of propane to aromatics was studied in a dynamic flow reactor. With the pristine [H-ZSM-5300] catalyst, the conversion of propane is very low. However, with [Ti–H/ZSM-5] catalyst 2 under the same reaction conditions, the conversion of propane remains significant during 60 h of the reaction (ca. 22%). Furthermore, the [Ti–H/ZSM-5] catalyst shows a good and stable selectivity (55%) for aromatics (BTX) of time on stream. With 2, it was found that the Ti remains at the periphery of the [H-ZSM-5] even after reaction time. [ABSTRACT FROM AUTHOR]

A specific allotrope of titanium dioxide (anatase) was synthesized both with a standard thermodynamic morphology ({101}-anatase) and with a highly anisotropic morphology ({001}-anatase) dominated by the {001} facet (81%). The surface chemistry of both samples after dehydroxylation was studied by 1H NMR and FT-IR. The influence of surface fluorides on the surface chemistry was also studied by 1H NMR, FT-IR and DFT. Full attribution of the IR spectra of anatase with dominant {001} facets could be provided based on experimental data and further confirmed by DFT. Our results showed that chemisorbed H2O molecules are still present on anatase after dehydroxylation at 350 °C, and that the type of surface hydroxyls present on the {001} facet is dependent on the presence of fluorides. They also provided general insight into the nature of the surface species on both fluorinated and fluorine-free anatase. The use of vanadium oxychloride (VOCl3) allowed the determination of the accessibility of the various OH groups spectroscopically observed. [ABSTRACT FROM AUTHOR]

Tin oxide has been demonstrated to possess outstanding optoelectronic properties such as optical transparency and high electron mobility; therefore, it was successfully utilized as an electron transporting layer in various kinds of solar cells. In this study, for the first time, highly dispersible SnO2 nanoparticles were synthesized by a microwave-assisted non-aqueous sol–gel route in an organic medium. Ethanol dispersion of the as-prepared nanoparticles was used to cast a uniform thin layer of SnO2 without the aid of an aggregating agent and at low temperatures. Organohalide perovskite solar cells were fabricated using SnO2 as the electron transporting layer. Morphological and spectroscopic investigations, in addition to the good photoconversion efficiency obtained, evidenced that the nanoparticles synthesized by this route have optimal properties such as small size and crystallinity to form a continuous film. Furthermore, this method allows high reproducibility and scalability of the film deposition process. [ABSTRACT FROM AUTHOR]

Continuous flow chemistry is used to trap the nucleation and growth stages of platinum–nickel nano-octahedra with second time resolution and high throughputs to probe their properties ex situ. The growth starts from poorly crystalline particles (nucleation) at 5 seconds, to crystalline 1.5 nm particles bounded by the {111}-facets at 7.5 seconds, followed by truncation and further growth to octahedral nanoparticles at 20 seconds. [ABSTRACT FROM AUTHOR]

The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum–ruthenium core–shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core–shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ∼2–3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity. [ABSTRACT FROM AUTHOR]

Inorganic nanocrystals composed of earth-abundant and non-toxic elements are crucial to fabricate sustainable photovoltaic devices on a large scale. In this study, various shapes and different phases of antimony sulfide nanocrystals, which are composed of non-scarce and non-toxic elements, are synthesized using a colloidal hot-injection method. The effect of various synthetic parameters on the final morphology is explored. Also, foreign ion (chlorine) effects on the morphology of Sb2S3 nanocrystals have been observed. Structural, optical and morphological properties of the nanocrystals were investigated, and Sb2S3 nanocrystal-based solid-state semiconductor-sensitized solar cells were fabricated using the as-prepared nanocrystals. We achieved a promising power conversion efficiency of 1.48%. [ABSTRACT FROM AUTHOR]

Stoichiometric and gallium-rich wurtzite Cu–Ga–S ternary nanocrystals were synthesized via a facile solution-based hot injection method using 1-dodecanethiol as a sulfur source. The use of 1-dodecanethiol was found to be essential not only as a sulfur source but also as a structure-directing reagent to form a metastable wurtzite structure. In addition, the substitution of zinc in the wurtzite gallium-rich Cu–Ga–S nanocrystals was also investigated. The obtained nanocrystals were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), photoluminescence (PL), and inductively coupled plasma atomic emission spectroscopy (ICP-OES). Electronic structures of pristine and the Zn-substituted Cu–Ga–S system were investigated using density functional theory (DFT) with HSE06 exchange-correlation functional. The calculated bandgaps accurately reflect the measured ones. The allowed electronic transitions occur upon the photon absorption from the (Cu + S) band towards the (Ga + S) one. The Zn substitution was found not to contribute to the band edge structure and hence altered the bandgaps only slightly, the direct transition nature remaining unchanged with the Zn substitution. The photocatalytic activities of H2 evolution from an aqueous Na2S/Na2SO3 solution under visible-light illumination on the synthesized nanocrystals were investigated. While the stoichiometric CuGaS2 exhibited negligible activity, the gallium-rich Cu–Ga–S ternary nanocrystals displayed reasonable activity. The optimum Zn substitution in the gallium-rich Cu–Ga–S ternary nanocrystals enhanced the H2 evolution rate, achieving an apparent quantum efficiency of ＞6% at 400 nm. [ABSTRACT FROM AUTHOR]

A dramatic improvement in electrical conductivity is necessary to make conductive polymer fibers viable candidates in applications such as flexible electrodes, conductive textiles, and fast-response sensors and actuators. In this study, high-performance poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) conjugated polymer microfibers were fabricated via wet-spinning followed by hot-drawing. Due to the combined effects of the vertical hot-drawing process and doping/de-doping the microfibers with ethylene glycol (EG), we achieved a record electrical conductivity of 2804 S cm−1. This is, to the best of our knowledge, a six-fold improvement over the best previously reported value for PEDOT/PSS fibers (467 S cm−1) and a two-fold improvement over the best values for conductive polymer films treated by EG de-doping (1418 S cm−1). Moreover, we found that these highly conductive fibers experience a semiconductor–metal transition at 313 K. They also have superior mechanical properties with a Young's modulus up to 8.3 GPa, a tensile strength reaching 409.8 MPa and a large elongation before failure (21%). The most conductive fiber also demonstrates an extraordinary electrical performance during stretching/unstretching: the conductivity increased by 25% before the fiber rupture point with a maximum strain up to 21%. Simple fabrication of the semi-metallic, strong and stretchable wet-spun PEDOT/PSS microfibers described here could make them available for conductive smart electronics. [ABSTRACT FROM AUTHOR]

Efficient photocatalytic hydrogen generation in a suspension system requires a sophisticated nano-device that combines a photon absorber with effective redox catalysts. This study demonstrates an innovative molecular linking strategy for fabricating photocatalytic materials that allow effective charge separation of excited carriers, followed by efficient hydrogen evolution. The method for the sequential replacement of ligands with appropriate molecules developed in this study tethers both quantum dots (QDs), as photosensitizers, and metal nanoparticles, as hydrogen evolution catalysts, to TiO2 surfaces in a controlled manner at the nano-level. Combining hydrophobic and hydrophilic interactions on the surface, CdSe-ZnS core-shell QDs and an Au-Pt alloy were attached to TiO2 without overlapping during the synthesis. The resultant nano-photocatalysts achieved substantially high-performance visible-light-driven photocatalysis for hydrogen evolution. All syntheses were conducted at room temperature and in ambient air, providing a promising route for fabricating visible-light-responsive photocatalysts. [ABSTRACT FROM AUTHOR]

Poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) is a widely used conductive polymer in the field of flexible electronics. The ways its microstructure changes over a broad range of temperatures remain unclear. This paper describes microstructure changes at different temperatures and correlates the microstructure with its physical properties (mechanical and electrical). We used High-Angle Annular Dark-Field Scanning Electron Microscopy (HAADF-STEM) combined with electron energy loss spectroscopy (EELS) to determine the morphology and elemental atomic ratio of the film at different temperatures. These results together with the Atomic Force Microscopy (AFM) analysis provide the foundation for a model of how the temperature affects the microstructure of PEDOT/PSS. Moreover, dynamic mechanical analysis (DMA) and electrical characterization were performed to analyze the microstructure and physical property correlations. [ABSTRACT FROM AUTHOR]

In this report, we demonstrate that solution-processed amorphous zinc oxide (a-ZnO) interlayers prepared at low temperatures (~100 °C) can yield inverted bulk-heterojunction (BHJ) solar cells that are as efficient as nanoparticle-based ZnO requiring comparably more complex synthesis or polycrystalline ZnO films prepared at substantially higher temperatures (150-400 °C). Low-temperature, facile solution-processing approaches are required in the fabrication of BHJ solar cells on flexible plastic substrates, such as PET. Here, we achieve efficient inverted solar cells with a-ZnO buffer layers by carefully examining the correlations between the thin film morphology and the figures of merit of optimized BHJ devices with various polymer donors and PCBM as the fullerene acceptor. We find that the most effective a-ZnO morphology consists of a compact, thin layer with continuous substrate coverage. In parallel, we emphasize the detrimental effect of forming rippled surface morphologies of a-ZnO, an observation which contrasts with results obtained in polycrystalline ZnO thin films, where rippled morphologies have been reported to improve efficiency. After optimizing the a-ZnO morphology at low processing temperature for inverted P3HT:PCBM devices, achieving a power conversion efficiency (PCE) of ca. 4.1%, we demonstrate inverted solar cells with low bandgap polymer donors on glass/flexible PET substrates: PTB7:PC71BM (PCE: 6.5% (glass)/5.6% (PET)) and PBDTTPD:PC71BM (PCE: 6.7% (glass)/5.9% (PET)). Finally, we show that a-ZnO based inverted P3HT:PCBM BHJ solar cells maintain ca. 90-95% of their initial PCE even after a full year without encapsulation in a nitrogen dry box, thus demonstrating excellent shelf stability. The insight we have gained into the importance of surface morphology in amorphous zinc oxide buffer layers should help in the development of other low-temperature solution-processed metal oxide interlayers for efficient flexible solar cells. [ABSTRACT FROM AUTHOR]

Preparing evenly-dispersed small size nickel nanoparticles over inert oxides remains a challenge today. In this context, a versatile method to prepare supported small size nickel nanoparticles (ca. 1 -3 nm) with narrow size distribution via a surface organometallic chemistry (SOMC) route is described. The grafted mono(η3-allyl)nickel complex ≡ MONi(η³-C3H5) as precursors are synthesized and fully characterized by elemental analysis, FTIR spectroscopy and paramagnetic solid-state NMR. [ABSTRACT FROM AUTHOR]

Molybdenum carbide nanocrystals (Mo2C) with sizes ranging from 3 to 20 nm were synthesized within a carbon matrix starting from a mesoporous graphitic carbon nitride (mpg-C3N4) template with confined pores. A molybdenum carbide phase (Mo2C) with a hexagonal structure was formed using a novel synthetic method involving the reaction of a molybdenum precursor with the carbon residue originating from C3N4 under nitrogen at various temperatures. The synthesized nanocomposites were characterized using powder X-ray diffraction (XRD), temperature-programmed reaction with mass spectroscopy (MS), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results indicated that the synthesized samples have different surface structures and compositions, which are accordingly expected to exhibit different electrocatalytic activities toward the hydrogen evolution reaction (HER). Electrochemical measurements demonstrated that the sample synthesized at 1323 K exhibited the highest and most stable HER current in acidic media, with an onset potential of -100 mV vs. RHE, among the samples prepared in this study. This result is attributed to the sufficiently small particle size (~8 nm on average) and accordingly high surface area (308 m2 g-1), with less oxidized surface entrapped within the graphitized carbon matrix. [ABSTRACT FROM AUTHOR]

A flux-assisted method was used to synthesize SnNb2O6 as a visible-light-responsive metal oxide photocatalyst. The role of flux was investigated in detail using different flux to reactant molar ratios (1 : 1, 3 : 1, 6 : 1, 10 : 1, and 14 : 1) and different reaction temperatures (300, 500, and 600 °C). The obtained products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), the Brunauer–Emmett–Teller method (BET), and high resolution scanning transmission electron microscopy (HRTEM). Flux-assisted synthesis led to tin niobate particles of platelet morphology with smooth surfaces. The synthesized crystal showed a 2D anisotropic growth along the (600) plane as the flux ratio increased. The particles synthesized with a high reactant to flux ratio (1 : 10 or higher) exhibited slightly improved photocatalytic activity for hydrogen evolution from an aqueous methanol solution under visible radiation (λ ＞ 420 nm). The photo-deposition of platinum and PbO2 was examined to gain a better understanding of electrons and hole migration pathways in these layered materials. The HR-STEM observation revealed that no preferential deposition of these nanoparticles was observed depending on the surface facets of SnNb2O6. [ABSTRACT FROM AUTHOR]

Tantalum carbide and nitride nanocrystals were prepared through the reaction of a tantalum precursor with mesoporous graphitic (mpg)-C3N4. The effects of the reaction temperature, the ratio of the Ta precursor to the reactive template (mpg-C3N4), and the selection of the carrier gas (Ar, N2 and NH3) on the resultant crystal phases and structures were investigated. The produced samples were characterized using powder X-ray diffraction (XRD), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, a temperature-programmed reaction with mass spectroscopy (MS), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results indicate that the different tantalum phases with cubic structure, TaN, Ta2CN, and TaC, can be formed under a flow of nitrogen when formed at different temperatures. The Ta3N5 phase with a Ta5+ oxidation state was solely obtained at 1023 K under a flow of ammonia, which gasified the C3N4 template and was confirmed by detecting the decomposed gaseous products via MS. Significantly, the formation of TaC, Ta2CN, and TaN can be controlled by altering the weight ratio of the C3N4 template relative to the Ta precursor at 1573 K under a flow of nitrogen. The high C3N4/Ta precursor ratio generally resulted in high carbide content rather than a nitride one, consistent with the role of mpg-C3N4 as a carbon source. Electrochemical measurements revealed that the synthesized nanomaterials were consistently able to produce hydrogen under acidic conditions (pH 1). The obtained Tafel slope indicates that the rate-determining step is the Volmer discharge step, which is consistent with adsorbed hydrogen being weakly bound to the surface during electrocatalysis. [ABSTRACT FROM AUTHOR]

We report the synthesis of atomically monodisperse thiol-protected silver nanoclusters [Ag44(SR)30 ]m, (SR = 5-mercapto-2-nitrobenzoic acid) in which the product nanocluster is highly stable in contrast to previous preparation methods. The method is one-pot, scalable, and produces nanoclusters that are stable in aqueous solution for at least 9 months at room temperature under ambient conditions, with very little degradation to their unique UV-Vis optical absorption spectrum. The composition, size, and monodispersity were determined by electrospray ionization mass spectrometry and analytical ultracentrifugation. The produced nanoclusters are likely to be in a superatom charge-state of m = 4−, due to the fact that their optical absorption spectrum shares most of the unique features of the intense and broadly absorbing nanoparticles identified as [Ag44(SR)30]4− by Harkness et al. (Nanoscale, 2012, 4, 4269). A protocol to transfer the nanoclusters to organic solvents is also described. Using the disperse nanoclusters in organic media, we fabricated solid-state films of [Ag44(SR)30]m that retained all the distinct features of the optical absorption spectrum of the nanoclusters in solution. The films were studied by X-ray diffraction and photoelectron spectroscopy in order to investigate their crystallinity, atomic composition and valence band structure. The stability, scalability, and the film fabrication method demonstrated in this work pave the way towards the crystallization of [Ag44(SR)30]m and its full structural determination by single crystal X-ray diffraction. Moreover, due to their unique and attractive optical properties with multiple optical transitions, we anticipate these clusters to find practical applications in light-harvesting, such as photovoltaics and photocatalysis, which have been hindered so far by the instability of previous generations of the cluster. [ABSTRACT FROM AUTHOR]

A platinum complex, (CH 3 ) 2 Pt(COD), is grafted via surface organometallic chemistry (SOMC) on morphology-controlled anatase TiO 2 to generate single, isolated Pt atoms on TiO 2 nano-platelets. The resulting material is characterized by FT-IR, high resolution scanning transmission electron microscopy (HRSTEM), NMR, and XAS, and then used to perform photocatalytic water splitting. The photocatalyst with SOMC-grafted Pt shows superior performance in photocatalytic hydrogen evolution and strongly suppresses the backwards reaction of H 2 and O 2 forming H 2 O under dark conditions, compared to the photocatalyst prepared by impregnation at the same Pt loading. However, single Pt atoms on this surface also rapidly coalesce into nanoparticles under photocatalytic conditions. It is also found that adsorption of CO gas at room temperature also triggers the aggregation of Pt single atoms into nanoparticles. A detailed mechanism is investigated for the mobility of Pt in the formation of its carbonyls using density functional theory (DFT) calculations.

The direct conversion of propane into aromatics (BTX) using modified ZSM-5 was achieved with a strategy of "catalysis by design". In contrast to the classical mode of action of classical aromatization catalysts which are purely based on acidity, we have designed the catalyst associating two functions: One function (Ti-hydride) was selected to activate the C-H bond of propane by σ-bond metathesis to further obtain olefin by β-H elimination and the other function (Brønsted acid) being responsible for the oligomerization, cyclization, and aromatization. This bifunctional catalyst was obtained by selectively grafting a bulky organometallic complex of tetrakis(neopentyl)titanium (TiNp4) at the external surface (external silanol ([triple bond, length as m-dash]Si-OH) group) of [H-ZSM-5300] to obtain [Ti/ZSM-5] catalyst 1. This metal was chosen to activate the C-H bond of paraffin at the periphery of the ZSM-5 while maintaining the Brønsted acid properties of the internal [H-ZSM-5] for oligomerization, cyclization, and aromatization. Catalyst 2 [Ti-H/ZSM-5] was obtained after treatment under H2 at 550 °C of freshly prepared catalyst 1 ([Ti/ZSM-5]) and catalyst 1 was thoroughly characterized by ICP analysis, DRIFT, XRD, N2-physisorption, multinuclear solid-state NMR, XPS and HR-TEM analysis including STEM imaging. The conversion of propane to aromatics was studied in a dynamic flow reactor. With the pristine [H-ZSM-5300] catalyst, the conversion of propane is very low. However, with [Ti-H/ZSM-5] catalyst 2 under the same reaction conditions, the conversion of propane remains significant during 60 h of the reaction (ca. 22%). Furthermore, the [Ti-H/ZSM-5] catalyst shows a good and stable selectivity (55%) for aromatics (BTX) of time on stream. With 2, it was found that the Ti remains at the periphery of the [H-ZSM-5] even after reaction time.

A specific allotrope of titanium dioxide (anatase) was synthesized both with a standard thermodynamic morphology ({101}-anatase) and with a highly anisotropic morphology ({001}-anatase) dominated by the {001} facet (81%). The surface chemistry of both samples after dehydroxylation was studied by 1H NMR and FT-IR. The influence of surface fluorides on the surface chemistry was also studied by 1H NMR, FT-IR and DFT. Full attribution of the IR spectra of anatase with dominant {001} facets could be provided based on experimental data and further confirmed by DFT. Our results showed that chemisorbed H2O molecules are still present on anatase after dehydroxylation at 350 °C, and that the type of surface hydroxyls present on the {001} facet is dependent on the presence of fluorides. They also provided general insight into the nature of the surface species on both fluorinated and fluorine-free anatase. The use of vanadium oxychloride (VOCl3) allowed the determination of the accessibility of the various OH groups spectroscopically observed.

Efficient photocatalytic hydrogen generation in a suspension system requires a sophisticated nano-device that combines a photon absorber with effective redox catalysts. This study demonstrates an innovative molecular linking strategy for fabricating photocatalytic materials that allow effective charge separation of excited carriers, followed by efficient hydrogen evolution. The method for the sequential replacement of ligands with appropriate molecules developed in this study tethers both quantum dots (QDs), as photosensitizers, and metal nanoparticles, as hydrogen evolution catalysts, to TiO2 surfaces in a controlled manner at the nano-level. Combining hydrophobic and hydrophilic interactions on the surface, CdSe-ZnS core-shell QDs and an Au-Pt alloy were attached to TiO2 without overlapping during the synthesis. The resultant nano-photocatalysts achieved substantially high-performance visible-light-driven photocatalysis for hydrogen evolution. All syntheses were conducted at room temperature and in ambient air, providing a promising route for fabricating visible-light-responsive photocatalysts.

Preparing evenly-dispersed small size nickel nanoparticles over inert oxides remains a challenge today. In this context, a versatile method to prepare supported small size nickel nanoparticles (ca. 1-3 nm) with narrow size distribution via a surface organometallic chemistry (SOMC) route is described. The grafted mono(η(3)-allyl)nickel complexes ≡MONi(η(3)-C3H5) (M = Si or Al) as precursors are synthesized and fully characterized by elemental analysis, FTIR spectroscopy and paramagnetic solid-state NMR.

A flux-assisted method was used to synthesize SnNb2O6 as a visible-light-responsive metal oxide photocatalyst. The role of flux was investigated in detail using different flux to reactant molar ratios (1 : 1, 3 : 1, 6 : 1, 10 : 1, and 14 : 1) and different reaction temperatures (300, 500, and 600 °C). The obtained products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), the Brunauer-Emmett-Teller method (BET), and high resolution scanning transmission electron microscopy (HRTEM). Flux-assisted synthesis led to tin niobate particles of platelet morphology with smooth surfaces. The synthesized crystal showed a 2D anisotropic growth along the (600) plane as the flux ratio increased. The particles synthesized with a high reactant to flux ratio (1 : 10 or higher) exhibited slightly improved photocatalytic activity for hydrogen evolution from an aqueous methanol solution under visible radiation (λ > 420 nm). The photo-deposition of platinum and PbO2 was examined to gain a better understanding of electrons and hole migration pathways in these layered materials. The HR-STEM observation revealed that no preferential deposition of these nanoparticles was observed depending on the surface facets of SnNb2O6.