Confined Catalysis: Progress and Prospects in Energy Conversion

Space confined catalysis has emerged as viable strategy for achieving potent and efficient catalysts in various important reactions. It offers a means of creating unique nanoscale chemical environments partitioned from the surrounding bulk space. This gives rise to the phenomena of nanoconfinement, where the energetics and kinetics of catalytic reactions can be modulated upon confining the catalysts in a particular site. Various scaffolds have been reported so far for confinement. Among these, void spaces under the cover of 2D materials, van der Waals (vdW) gaps of layered 2D materials, nanotubes, and porous surfaces have recently won copious attention. In this review, the concept of space confinement with respect to its effect on the electronic and structural properties of a catalyst is discussed. Emphasis is devoted to the catalysis of water splitting and CO2 reduction reactions. The progress in the design and applications of space confined catalysts is then traced. Finally, a discussion of emerging issues yet to be explored for this strategy to achieve a high efficiency, and future directions with the potential to become a new hotspots are presented

Carbon Dots for Photocatalytic Degradation of Aqueous Pollutants: Recent Advancements

The immense progress of humanity on the technological, domestic, and industrial fronts comes at the cost of polluting the planet. Aquatic pollution is particularly dangerous since all life forms are directly linked to it. Each year tons of industrial and domestic pollutants make their way into aqueous systems. Efficient removal/degradation of these pollutants is of prime importance for the sustainable future. Among many technologies, photodegradation is an emerging and promising method for the successful removal of aqueous pollutants since it is powered by abundant solar light. The last decade had shown that carbon dots are among the most promising materials that can be utilized as an efficient tool to derive various solar-driven chemical reactions. Carbon dots possess unique photophysical and chemical properties such as light-harvesting over a broad-spectrum region, upconversion photoluminescence, photosensitizers, chemical inertness, and bivalent redox character, etc. The ease of synthesis of carbon dots at low cost also contributes hugely to their utilizations as an efficient photocatalyst for the degradation of aqueous pollutants. This review summarizes the recent progress made in the field of photodegradation of aqueous pollutants with the aid of carbon dots and their hybrids, highlighting the critical role carbon dots can play in the field

Synthesis, optical properties and applications of red/near-infrared carbon dots

Compared to inorganic quantum dots, fluorescent carbon nanomaterials (C-dots) have gained significant attention because of their unique optoelectrical properties and low toxicity. Although many review articles summarized the last research achievements, only a few of them are focusing on red/near-infrared C-dots. Due to their unique optical and optoelectrical properties in the red/near-infrared region, this interesting subclass of C-dots may be applied as important building blocks for several applications spanning from bioimaging and nano-thermometry, to luminescent solar concentrators (LSCs) and photoelectrochemical systems. Therefore, in this review the synthesis and the fluorescence mechanism together with the most important applications in thermometry, bio-imaging, LSCs and photocatalysis of red/near-infrared C-dots are considered. Furthermore, another aim is to highlight the available approaches to improve the carbonization degree and, additionally, to discuss the structure/composition correlated optical properties. Finally, outlooks, future perspectives and challenges are also discussed for these highly promising nanostructures

Facile Electron Transfer in Atomically Coupled Heterointerface for Accelerated Oxygen Evolution

An efficient and cost-effective approach for the development of advanced cata-lysts has been regarded as a sustainable way for green energy utilization. The general guideline to design active and efficient catalysts for oxygen evolution reaction (OER) is to achieve high intrinsic activity and the exposure of more density of the interfacial active sites. The heterointerface is one of the most attractive ways that plays a key role in electrochemical water oxidation. Herein, atomically cluster-based heterointerface catalysts with strong metal support interaction (SMSI) between WMn2O4 and TiO2 are designed. In this case, the WMn2O4 nanoflakes are uniformly decorated by TiO2 particles to create electronic effect on WMn2O4 nanoflakes as confirmed by X-ray absorption near edge fine structure. As a result, the engineered heterointerface requires an OER onset overpotential as low as 200 mV versus reversible hydrogen electrode, which is stable for up to 30 h of test. The outstanding performance and long-term durability are due to SMSI, the exposure of interfacial active sites, and accelerated reaction kinetics. To confirm the synergistic interaction between WMn2O4 and TiO2, and the modification of the electronic structure, high-resolution transmission electron microscopy (HR-TEM), X-ray photoemission spectroscopy (XPS), and X-ray absorption spectroscopy (XAS) are used

Tuning ZnO nanorods photoluminescence through atmospheric plasma treatments

Room temperature atmospheric plasma treatments are widely used to activate and control chemical functionalities at surfaces. Here, we investigated the effect of atmospheric pressure plasma jet (APPJ) treatments in reducing atmosphere (Ar/1 parts per thousand H-2 mixture) on the photoluminescence (PL) properties of single crystal ZnO nanorods (NRs) grown through hydrothermal synthesis on fluorine-doped tin oxide glass substrates. The results were compared with a standard annealing process in air at 300 degrees C. Steady-state photoluminescence showed strong suppression of the defect emission in ZnO NRs for both plasma and thermal treatments. On the other side, the APPJ process induced an increase in PL quantum efficiency (QE), while the annealing does not show any improvement. The QE in the plasma treated samples was mainly determined by the near band-edge emission, which increased 5-6 fold compared to the as-prepared samples. This behavior suggests that the quenching of the defect emission is related to the substitution of hydrogen probably in zinc vacancies (V-Zn), while the enhancement of UV emission is due to doping originated by interstitial hydrogen (H-i), which diffuses out during annealing. Our results demonstrate that atmospheric pressure plasma can induce a similar hydrogen doping as ordinarily used vacuum processes and highlight that the APPJ treatments are not limited to the surfaces but can lead to subsurface modifications. APPJ processes at room temperature and under ambient air conditions are stable, convenient, and efficient methods, compared to thermal treatments to improve the optical and surface properties of ZnO NRs, and remarkably increase the efficiency of UV emission. (c) 2019 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/)

Impact of oxalate ligand in co-precipitation route on morphological properties and phase constitution of undoped and Rh-Doped BaTiO3 nanoparticles

In order to design and tailor materials for a specific application like gas sensors, the synthesis route is of great importance. Undoped and rhodium-doped barium titanate powders were successfully synthesized by two routes; oxalate route and classic route (a modified conventional route where solid-state reactions and thermal evaporation induced precipitation takes place). Both powders were calcined at different temperatures. X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX) and Brunauer-Emmet-Teller (BET) analyses are employed to identify the phases and polymorphs, to determine the morphology, the chemical composition and the specific surface area of the synthesized materials, respectively. The so-called oxalate route yields pure BaTiO3 phase for undoped samples at 700?C and 900?C (containing both cubic and tetragonal structures), while the classic route-synthesized powder contains additional phases such as BaCO3, TiO2 and BaTi2O5. Samples of both synthesis routes prepared by the addition of Rh contain no metallic or oxide phase of rhodium. Instead, it was observed that Ti was substituted by Rh at temperatures 700 °C and 900 °C and there was some change in the composition of BaTiO3 polymorph (increase of tetragonal structure). Heat-treatments above these temperatures show that rhodium saturates out of the perovskite lattice at 1000 °C, yielding other secondary phases such as Ba3RhTi2O9 behind. Well-defined and less agglomerated spherical nanoparticles are obtained by the oxalic route, while the classic route yields particles with an undefined morphology forming very large block-like agglomerates. The surface area of the synthesized materials is higher with the oxalate route than with the classic route (4 times at 900 °C). The presence of the oxalate ligand with its steric hindrance that promotes the uniform distribution and the homogeneity of reactants could be responsible for the great difference observed between the powders prepared by two preparation routes

In Situ-Generated Oxide in Sn-Doped Nickel Phosphide Enables Ultrafast Oxygen Evolution

Water splitting is considered one of the most promising approaches to power the globe without the risk of environmental pollution. The oxygen evolution reaction (OER) is even more challenging because the generation of only one oxygen molecule involves the transfer of four e- and removal of four H+ ions from water. Thus, developing highly efficient catalysts to meet industrial requirements remains a focus of attention. Herein, the prominent role of Sn in accelerating the electron transfer kinetics of Ni5P4 nanosheets in OER is reported. The post catalytic survey elucidates that the electrochemically induced Ni-Sn oxides at the vicinity of phosphides are responsible for the observed catalytic activity, delivering current densities of 10, 30, and 100 mA cm-2 at overpotentials of only 173 ± 5.2, 200 ±7.4, and 310 ± 5.5 mV, respectively. The density functional theory calculation also supports the experimental findings from the basis of the difference observed in density of states at the Fermi level in the presence/absence of Sn. This work underscores the role of Sn in OER and opens a promising avenue toward practical implementation of hydrogen production through water splitting and other catalytic reactions

Nanoscale characterization of an all-oxide core-shell nanorod heterojunction using intermodulation atomic force microscopy (AFM) methods

The electrical properties of an all-oxide core-shell ZnO-Co3O4nanorod heterojunction were studied in the dark and under UV-vis illumination. The contact potential difference and current distribution maps were obtained utilizing new methods in dynamic multifrequency atomic force microscopy (AFM) such as electrostatic and conductive intermodulation AFM. Light irradiation modified the electrical properties of the nanorod heterojunction. The new techniques are able to follow the instantaneous local variation of the photocurrent, giving a two-dimensional (2D) map of the current-voltage curves and correlating the electrical and morphological features of the heterostructured core-shell nanorods

Au-Decorated Ce-Ti Mixed Oxides for Efficient CO Preferential Photooxidation

We investigated the photocatalytic behavior of gold nanoparticles supported on CeO2-TiO2 nanostructured matrixes in the CO preferential oxidation in H2-rich stream (photo-CO-PROX), by modifying the electronic band structure of ceria through addition of titania and making it more suitable for interacting with free electrons excited in gold nanoparticles through surface plasmon resonance. CeO2 samples with different TiO2 concentrations (0-20 wt %) were prepared through a slow coprecipitation method in alkaline conditions. The synthetic route is surfactant-free and environmentally friendly. Au nanoparticles (<1.0 wt % loading) were deposited on the surface of the CeO2-TiO2 oxides by deposition-precipitation. A benchmarking sample was also considered, prepared by standard fast coprecipitation, to assess how a peculiar morphology can affect the photocatalytic behavior. The samples appeared organized in a hierarchical needle-like structure, with different morphologies depending on the Ti content and preparation method, with homogeneously distributed Au nanoparticles decorating the Ce-Ti mixed oxides. The morphology influences the preferential photooxidation of CO to CO2 in excess of H2 under simulated solar light irradiation at room temperature and atmospheric pressure. The Au/CeO2-TiO2 systems exhibit much higher activity compared to a benchmark sample with a non-organized structure. The most efficient sample exhibited CO conversions of 52.9 and 80.2%, and CO2 selectivities equal to 95.3 and 59.4%, in the dark and under simulated sunlight, respectively. A clear morphology-functionality correlation was found in our systematic analysis, with CO conversion maximized for a TiO2 content equal to 15 wt %. The outcomes of this study are significant advancements toward the development of an effective strategy for exploitation of hydrogen as a viable clean fuel in stationary, automotive, and portable power generators

Engineering Cu2O Nanowire Surfaces for Photoelectrochemical Hydrogen Evolution Reaction

Cu2O is a narrow band gap material serving as an important candidate for photoelectrochemical hydrogen evolution reaction. However, the main challenge that hinders its practical exploitation is its poor photostability, due to its oxidation into CuO by photoexcited holes. Here, we thoroughly minimize the photo-oxidation of Cu2O nanowires by growing a thin layer of the TiO2 protective layer and an amorphous layer of the VOx cocatalyst using magnetron sputtering and atomic layer deposition, respectively. After optimization of the protective and the cocatalyst layers, the photoelectrode exhibits a current density of -2.46 mA/cm2 under simulated sunlight (100 mW/cm2) at 0.3 V versus reversible hydrogen electrode, and its performance is stable for an extended illumination time. The chemical stability and the good performance of the engineered photoelectrode demonstrate the potential of using earth-abundant materials as a light-harvesting device for solar hydrogen production