Observation of inherited plasmonic properties of TiN in titanium oxynitride (TiOxNy) for solar-drive photocatalytic applications.

This study demonstrates the synthesis of titanium oxynitride (TiOxNy) via a controlled step-annealing of commercial titanium nitride (TiN) powders under normal ambience. The structure of the formed TiOxNy system is confirmed via XRD, Rietveld refinements, XPS, Raman, and HRTEM analysis. A distinct plasmonic band corresponding to TiN is observed in the absorption spectrum of TiOxNy, indicating that the surface plasmonic resonance (SPR) property of TiN is being inherited in the resulting TiOxNy system. The prerequisites such as reduced band gap energy, suitable band edge positions, reduced recombination, and enhanced carrier-lifetime manifested by the TiOxNy system are investigated using Mott-Schottky, XPS, time-resolved and steady-state PL spectroscopy techniques. The obtained TiOxNy photocatalyst is found to degrade around 98% of 10 ppm rhodamine B dye in 120 min and produce H2 at a rate of ∼1546 µmolg-1h-1 under solar light irradiation along with consistent recycle abilities. The results of cyclic voltammetry, linear sweep voltammetry, electrochemical impedance and photocurrent studies suggest that this evolved TiOxNy system could be functioning via plasmonic Ohmic interface rather than the typical plasmonic Schottky interface due to their amalgamated band structures in the oxynitride phase.

Mechanochemical bottom-up synthesis of phosphorus-linked, heptazine-based carbon nitrides using sodium phosphide.

Herein, we present the bottom-up, mechanochemical synthesis of phosphorus-bridged heptazine-based carbon nitrides (g-h-PCN). The structure of these materials was determined through a combination of powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), 31P magic angle spinning nuclear magnetic resonance (MAS NMR), density functional theory (DFT) and electron energy loss spectroscopy (EELS). Compared to traditional furnace-based techniques, the presented method utilizes milder conditions, as well as shorter reaction times. Both samples of g-h-PCN directly after milling and aging and after an hour of annealing at 300 °C (g-h-PCN300) show a reduction in photoluminescent recombination, as well as a nearly two-time increase in photocurrent under broad spectrum irradiation, which are appealing properties for photocatalysis.

Chemically Bonded Plasmonic Triazole-Functionalized Au/Zeolitic Imidazole Framework (ZIF-67) for Enhanced CO2 Photoreduction.

The design of functionalized metallic nanoparticles is considered an emerging technique to ensure the interaction between metal and semiconductor material. In the literature, this interface interaction is mainly governed by electrostatic or van der Waals forces, limiting the injection of electrons under light irradiation. To enhance the transfer of electrons between two compounds, close contact or chemical bonding at the interface is required. Herein, a new approach was reported for the synthesis of chemically bonded plasmonic Au NPs/ZIF-67 nanocomposites. The structure of ZIF-67 was grown on the surface of functionalized plasmonic Au NPs using 1H-1,2,4-triazole-3-thiol as the capping agent, which acted as both stabilizer of Au nanoparticles and a molecular linker for ZIF-67 formation. As a result, the synthesized material exhibited outstanding photocatalytic CO2 reduction with a methanol production rate of 2.70 mmol h-1 g-1 cat under sunlight irradiation. This work emphasizes that the diligent use of capping agents, with suitable functional groups, could facilitate the formation of intimate heterostructure for enhanced photocatalytic CO2 reduction.

Direct Z-scheme mediated SmVO4/UiO-66-NH2 heterojunction nanocomposite for the degradation of antibiotic tetracycline hydrochloride molecules under sunlight.

The use of tetracycline hydrochloride (TCH) for veterinary, human therapy, and agriculture has risen in the past few decades, making it to become one of the most exploited antibiotics. However, TCH residue in the environment is causing issues related to the evolution of antibiotic-resistant bacteria. To address such a problem, photodegradation offers a potential solution to decompose these pollutants in wastewater and thereby mitigates negative environmental impacts. In this context, the research focuses on the use of the rare-earth metal oxide samarium orthovanadate (SmVO4) with nanorod structure, coupled with UiO-66-NH2 for the photocatalytic degradation. Their photocatalytic activity to degrade antibiotic TCH molecules is explored under simulated solar light irradiation. The integration of UiO-66-NH2 with SmVO4 enhanced the light absorption, recombination resistance, carrier lifetime (from 0.382 to 0.411 ns) and specific surface area (from 67.17 to 246 m2/g) of the composite system as confirmed from multiple analyses. The obtained results further indicated that SmVO4/UiO-66-NH2 nanocomposites could form a direct Z-scheme based heterojunction. Such mechanism of charge transfer leads to the effective degradation of TCH molecules up to 50% in 90 min under solar light, while it is degraded only 30% in the case of bare-SmVO4 nanorods. In this work, the incorporation of UiO-66-NH2 positively influences photoelectrochemical properties and improves the overall photoredox properties of SmVO4 for the degradation of complex compounds like antibiotic TCH molecules. Therefore, UiO-66-NH2 can be proposed as an effective material to sensitize the rare-earth based photocatalytic material.

Emerging Hybrid Nanocomposite Photocatalysts for the Degradation of Antibiotics: Insights into Their Designs and Mechanisms.

The raising occurrence of antibiotics in the global water bodies has received the emerging concern due to their potential threats of generating the antibiotic-resistive and genotoxic effects into humans and aquatic species. In this direction, the solar energy assisted photocatalytic technique offers a promising solution to address such emerging concern and paves ways for the complete degradation of antibiotics with the generation of less or non-toxic by-products. Particularly, the designing of hybrid photocatalyticcomposite materials has been found to show higher antibiotics degradation efficiencies. As the hybrid photocatalysts are found as the systems with ideal characteristic properties such as superior structural, surface and interfacial properties, they offer enhanced photoabsorbance, charge-separation, -transfer, redox properties, photostability and easy recovery. In this context, this review study presents an overview on the recent developments in the designing of various hybrid photocatalytic systems and their efficiency towards the degradation of various emerging antibiotic pharmaceutical contaminants in water environments.

Synergistic Effect of Fe Doping and Plasmonic Au Nanoparticles on W18O49 Nanorods for Enhancing Photoelectrochemical Nitrogen Reduction.

Photoelectrochemical (PEC) nitrogen fixation has opened up new possibilities for the production of ammonia from water and air under mild conditions, but this process is confronted by the inherent challenges associated with theoretical and experimental works, limiting the efficiency of the nitrogen reduction reaction. Herein, we report for the first time a novel and efficient photoelectrocatalytic system, which has been prepared by assembling plasmonic Au nanoparticles with Fe-doped W18O49 nanorods (denoted as WOF-Au). (i) The introduction of exotic Fe atoms into nonstoichiometric W18O49 can eliminate bulk defects of the W18O49 host, which resulted in narrowing bandgap energy and facilitating electron-hole separation and transportation. (ii) Meanwhile, Au nanoparticles combined with a semiconductor induce the localized surface plasmon resonance and generate energetic (hot) electrons, increasing electron density on W18O49 nanorods. Consequently, this plasmonic WOF-Au system shows an NH3 production yield of 9.82 µg h-1 cm-2 at -0.65 V versus Ag/AgCl, which is ∼2.5-folds higher than that of the WOF (without Au loading), as well as very high stability, and no NH3 formation was found for the bare W18O49 (WO). This high activity can be associated with the synergistic effects between the Fe dopant and plasmonic Au NPs on the host semiconductor W18O49. This work can bring some insights into the target-directed design of efficient plasmonic hybrid systems for N2 fixation and artificial photocatalysis.

Plasmonic Photocatalysts for Sunlight-Driven Reduction of CO2 : Details, Developments, and Perspectives.

Plasmonic photocatalysis is among the most efficient processes for the photoreduction of CO2 into valuable fuels. The formation of localized surface plasmon resonance (LSPR), energy transfer, and surface reaction are the significant steps in this process. LSPR plays an essential role in the performance of plasmonic photocatalysts as it promotes an excellent, light absorption over a broad wavelength range while simultaneously facilitating an efficient energy transfer to semiconductors. The LSPR transfers energy to a semiconductor through various mechanisms, which have both advantages and disadvantages. This work points out four critical features for plasmonic photocatalyst design, that is, plasmonic materials, size, shape of plasmonic nanoparticles (PNPs), and the contact between PNPs and semiconductor. Various developed plasmonic photocatalysts, as well as their photocatalytic performance in CO2 photoreduction, are reviewed and discussed. Finally, perspectives of advanced architectures and structural engineering for plasmonic photocatalyst design are put forward with high expectations to achieve an efficient CO2 photoreduction shortly.

Influence of carbonaceous species on aqueous photo-catalytic nitrogen fixation by titania.

For decades, reports have suggested that photo-catalytic nitrogen fixation by titania in an aqueous environment is possible. Yet a consensus does not exist regarding how the reaction proceeds. Furthermore, the presence of an aqueous protonated solvent and the similarity between the redox potential for nitrogen and proton reduction suggest that ammonia production is unlikely. Here, we re-investigate photo-catalytic nitrogen fixation by titania in an aqueous environment through a series of photo-catalytic and electrocatalytic experiments. Photo-catalytic testing reveals that mineral phase and metal dopants play a marginal role in promoting nitrogen photofixation, with ammonia production increasing when the majority phase is rutile and with iron dopants. However, the presence of a trace amount of adsorbed carbonaceous species increased the rate of ammonia production by two times that observed without adsorbed carbon based species. This suggests that carbon species play a potential larger role in mediating the nitrogen fixation process over mineral phase and metal dopants. We also demonstrate an experimental approach aimed to detect low-level ammonia production from photo-catalysts using rotating ring disk electrode experiments conducted with and without illumination. Consistent with the photocatalysis, ammonia is only discernible at the ring with rutile phase titania, but not with mixed-phase titania. Rotating ring disk electrode experiments may also provide a new avenue to attain a higher degree of precision in detecting ammonia at low levels.

Synthesis of g-C3 N4 Nanosheets by Using a Highly Condensed Lamellar Crystalline Melamine-Cyanuric Acid Supramolecular Complex for Enhanced Solar Hydrogen Generation.

A highly condensed lamellar melamine-cyanuric acid supramolecular (MCS) complex was synthesized in an autoclave at high pressure as a precursor for preparing g-C3 N4 nanosheets. Given the distinctive properties of the prepared MCS complex, an efficient g-C3 N4 nanosheet photocatalyst can be obtained by heat treatment of this MCS complex under Ar followed by calcination in air at 400 °C. The resulting nanosheets with in-plane nanoholes showed an extremely high specific surface area (≈270 m2 g-1 ) and significantly enhanced light absorption in the visible region. This phenomenon is observed for the first time in carbon nitride nanosheets. The enhanced light absorption results from the sizeable conjugated system of tri-striazine units in the carbon nitride framework, coupled with the structural defects arising from the presence of oxygen-containing groups induced during the synthesis. Consequently, the obtained carbon nitride nanosheets exhibited excellent performance for hydrogen generation under sunlight and especially under visible light. Its quantum efficiency (QE) of 20.9 % at 420 nm is one of the highest reported values for carbon nitride materials. A QE of 3.5 % could be observed even at 590 nm. The integrated QE of this material in the visible region (420-600 nm) is approximately 1 %. To the best of our knowledge this is the highest value compared to all other the carbon nitride nanosheet materials reported previously.

Materials and Mechanisms of Photo-Assisted Chemical Reactions under Light and Dark Conditions: Can†Day-Night Photocatalysis Be Achieved?

The photoassisted catalytic reaction, conventionally known as photocatalysis, is expanding into the field of energy and environmental applications. It is widely known that the discovery of TiO2 -assisted photochemical reactions has led to several unique applications, such as degradation of pollutants in water and air, hydrogen production through water splitting, fuel conversion, cancer treatment, antibacterial activity, self-cleaning glasses, and concrete. These multifaceted applications of this phenomenon can be enriched and expanded further if this process is equipped with more tools and functions. The term "photoassisted" catalytic reactions clearly emphasizes that photons are required to activate the catalyst; this can be transcended even into the dark if electrons are stored in the material for the later use to continue the catalytic reactions in the absence of light. This can be achieved by equipping the photocatalyst with an electron-storage material to overcome current limitations in photoassisted catalytic reactions. In this context, this article sheds lights on the materials and mechanisms of photocatalytic reactions under light and dark conditions. The manifestation of such systems could be an unparalleled technology in the near future that could influence all spheres of the catalytic sciences.

Ni supported CdIn2S4 spongy-like spheres: a noble metal free high-performance sunlight driven photocatalyst for hydrogen production.

Nickel supported CdIn2S4 (Ni-CIS) spongy-like spheres have been developed using alcoholysis followed by a sulfidation process. The formation of nanocrystalline-single phase CdIn2S4 was confirmed using X-ray diffraction studies. Electron microscopy images showed that the spongy-like spheres are composed of CdIn2S4 nanoparticles with average sizes of around 25 nm. X-ray photoelectron spectra indicated the presence of elements with their respective stable oxidation states that led to the formation of single phase CdIn2S4 with enhanced structural integrity and chemical composition. The absorption spectra indicated the visible light activity of the material and the band gap energy is deduced to be 2.23 eV. The photocatalytic efficiency of the synthesized Ni-CIS in relation to its ability to produce hydrogen under solar light irradiation is estimated to be 1060 µmol g-1 h-1, which is around 5.5 and 3.6 fold higher than that of Pt-CIS (180 µmol g-1 h-1) and Pd-CIS (290 µmol g-1 h-1), respectively, as obtained in this study. Accordingly, the mechanism of the observed efficiency of the Ni-CIS nanoparticles is also proposed. The recyclability test showed consistent hydrogen evolution efficiency over 3 cycles (9 h), which essentially revealed the excellent photo- and chemical-stability of the photocatalyst. The strategy to utilize non-noble metals such as Ni, rather than noble-metals, as a co-catalyst opens up a new possibility to develop low cost and high-performance sunlight-driven photocatalysts as achieved in this study.

A new route to the shape-controlled synthesis of nano-sized γ-alumina and Ag/γ-alumina for selective catalytic reduction of NO in the presence of propene.

We report a new route for the direct synthesis of γ-alumina nanocrystals with size and shape control in the presence of oleylamine as the capping agent. Their morphology can be controlled from nanospheres to nanorods by simply tuning a proper amount of concentrated nitric acid (67%) in the synthetic mixture. The as-made nanoparticle products after calcination show γ-alumina nano-size with unique porosity and high specific surface area and retained morphology. The XRD patterns of these calcined samples exhibit broad diffraction lines which are characteristic of nanocrystal size of γ-alumina. This synthesis procedure has been extended to the one-pot synthesis of nano-alumina based Ag catalysts with spherical and rod-shaped nano-alumina morphologies. Selective catalytic reduction (SCR) of NO with C3H6 over these catalysts was investigated. The results were compared to those of the conventional Ag/γ-Al2O3 and γ-nanoalumina alone. These nano-alumina based Ag catalysts exhibit excellent NO reduction activity in the presence of C3H6. Even in the presence of large oxygen concentration (15%), N2 yields as high as ∼90% at quite low temperature (∼350°C) have been achieved. The significantly high catalytic activity of this new type of nanocatalysts can also be attributed to their high surface area and good dispersion of silver species in the alumina matrix as well as the synergism and new properties that arise at the silver-nanoalumina interface.

Nanocomposite heterojunctions as sunlight-driven photocatalysts for hydrogen production from water splitting.

Hydrogen production via photocatalytic water splitting using sunlight has enormous potential in solving the worldwide energy and environmental crisis. The key challenge in this process is to develop efficient photocatalysts which must satisfy several criteria such as high chemical and photochemical stability, effective charge separation and strong sunlight absorption. The combination of different semiconductors to create composite materials offers a promising way to achieve efficient photocatalysts because doing so can improve the charge separation, light absorption and stability of the photocatalysts. In this review article, we summarized the most recent studies on semiconductor composites for hydrogen production under visible light irradiation. After a general introduction about the photocatalysis phenomenon, typical heterojunctions of widely studied heterogeneous semiconductors, including titanium dioxide, cadmium sulfide and graphitic carbon nitride are discussed in detail.

In situ X-ray diffraction monitoring of a mechanochemical reaction reveals a unique topology metal-organic framework.

Chemical and physical transformations by milling are attracting enormous interest for their ability to access new materials and clean reactivity, and are central to a number of core industries, from mineral processing to pharmaceutical manufacturing. While continuous mechanical stress during milling is thought to create an environment supporting nonconventional reactivity and exotic intermediates, such speculations have remained without proof. Here we use in situ, real-time powder X-ray diffraction monitoring to discover and capture a metastable, novel-topology intermediate of a mechanochemical transformation. Monitoring the mechanochemical synthesis of an archetypal metal-organic framework ZIF-8 by in situ powder X-ray diffraction reveals unexpected amorphization, and on further milling recrystallization into a non-porous material via a metastable intermediate based on a previously unreported topology, herein named katsenite (kat). The discovery of this phase and topology provides direct evidence that milling transformations can involve short-lived, structurally unusual phases not yet accessed by conventional chemistry.

Tailoring the assembly, interfaces, and porosity of nanostructures toward enhanced catalytic activity.

The evolution of nanotechnology has inspired materials scientists to invent nanostructures with achievements in numerous practical applications, particularly in catalysis. The great advancements typically involve flexible control over the unique properties of the nanomaterial through tuning their structural geometries and components. In this Feature Article, we present the recent progress of our recent research and that of other groups in tailoring the assembly, interfaces, and porosity of diverse inorganic nanostructures. The enhanced catalytic properties of the engineered nanostructures are discussed in relation to photocatalysis, with special emphasis on solar energy conversion, including water splitting, CO2 reduction, and organic photodecomposition. Considering their attributes of superior catalytic performance and long-term durability, the development of economical, active nanocatalysts opens up practical opportunities for endeavours in sustainable energy conversion and other applied fields. This review is expected to introduce readers to the general principles of engineering the nanostructured features of the inorganic nanomaterials capable of improving solar photocatalytic efficiency.

Three-dimensional ordered assembly of thin-shell Au/TiO2 hollow nanospheres for enhanced visible-light-driven photocatalysis.

An Au/TiO(2) nanostructure was constructed to obtain a highly efficient visible-light-driven photocatalyst. The design was based on a three-dimensional ordered assembly of thin-shell Au/TiO(2) hollow nanospheres (Au/TiO(2)-3 DHNSs). The designed photocatalysts exhibit not only a very high surface area but also photonic behavior and multiple light scattering, which significantly enhances visible-light absorption. Thus Au/TiO(2)-3 DHNSs exhibit a visible-light-driven photocatalytic activity that is several times higher than conventional Au/TiO(2) nanopowders.

Design of multicomponent photocatalysts for hydrogen production under visible light using water-soluble titanate nanodisks.

We report the design of efficient multicomponent photocatalysts (MPs) for H2 production under visible light by using water-soluble ultrathin titanate nanodisks (TNDs) stabilized by tetraethylammonium cations (TEA(+)) as building blocks. The photocatalysts are designed in such a way to significantly enhance simultaneously the efficiency of the three main steps in the photocatalytic process i.e., light absorption, charge separation and catalytic reaction. We show, as an example, the construction of water-soluble CdS-TND-Ni MPs. The designed CdS-TND-Ni MPs, in which CdS nanoparticles and TNDs are intimately assembled to enhance the charge transfer and surface area, are controlled in composition to optimize visible light absorption. The conception of the MPs allows them to be highly dispersed in water which markedly improves the photocatalytic H2 production process. Most importantly, a Ni co-catalyst is selectively located on the surface of TNDs, enabling vectorial electron transfer from CdS to TND and to Ni, which drastically improves the charge separation. Consequently, under visible light illumination (λ ≥ 420 nm), the optimally designed CdS-TND-Ni MPs could generate H2 from ethanol-water solution with rate as high as 15.326 mmol g(-1) h(-1) during a reaction course of 15 h and with an apparent quantum yield of 24% at 420 nm. Moreover, we also demonstrate that TNDs can be combined with other single or mixed metal sulfide to form water-soluble metal sulfide-TNDs composites which could also be of great interest for photocatalytic H2 production.

Visible light induced hydrogen generation using a hollow photocatalyst with two cocatalysts separated on two surface sides.

A hollow Fe2O3-TiO2-PtOx photocatalyst for visible light H2 generation was prepared from nanosized MIL-88B consisting of coordinatively unsaturated metal centers as a hard template. This photocatalyst is composed of hybrid metal oxide-TiO2 with controllable wall thickness and two different cocatalysts that are separately located on two surface sides.

Controlled synthesis of ceria nanoparticles for the design of nanohybrids.

Ceria nanoparticles were synthesized from reaction mixture of cerium nitrate/hexamethylenediamine/water-ethylene glycol. Lamellar, particle-aggregated array, platelet, rice, cube, quasi-sphere shapes of the ceria nanoparticles can be controlled by tuning reaction parameters (reagent concentration, reagent components, pH, and reaction conditions). Studies on shape-dependent catalysis of the bare ceria samples toward CO oxidation indicated that the cube-shaped ceria nanoparticles show better catalytic activity than the nanospheres and the commercial micropowders. As capped by hexamethylenediamine (HEA) molecules, amine-functionalized ceria nanoparticles act as platforms for depositing copper particles to produce efficient Cu/CeO(2) hybrid nanocatalysts for CO conversion. Coupling of the copper clusters with the HEA-capped ceria nanocubes was achieved with the Cu contents up to 15 wt.%. The Cu/CeO(2) nanohybrids show an enhanced catalytic efficiency of low temperature CO conversion. This could be due to high exposure of the reactive {100} facets in the ceria nanocubes and interfacial copper-ceria interactions.

Synthesis and engineering porosity of a mixed metal Fe2Ni MIL-88B metal-organic framework.

A new rational approach has been developed for the synthesis of a mixed metal MIL-88B metal-organic framework based on a neutral mixed metal cluster, such as Fe(2)Ni(µ(3)-O). Unlike the conventional negative charged single metal cluster, the use of the neutral mixed metal cluster as nodes in the framework avoids the need of a compensating anion inside the porous MIL-88B system; thus the mixed metal MIL-88B becomes porous. The flexibility of the mixed metal MIL-88B can be controlled by terminal ligands with different steric hindrance. This allows us to reversibly customize the porosity of the MIL-88B structure at three levels of specific surface area as well as the pore volume.