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1.
Proc Natl Acad Sci U S A ; 119(34): e2206399119, 2022 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-35984900

RESUMO

Conversion of naturally occurring sugars, the most abundant biomass resources on Earth, to fuels and chemicals provides a sustainable and carbon-neutral alternative to the current fossil resource-based processes. Tungsten-based catalysts (e.g., WO3) are efficient for selectively cleaving C-C bonds of sugars to C2,3 oxygenate intermediates (e.g., glycolaldehyde) that can serve as platform molecules with high viability and versatility in the synthesis of various chemicals. Such C-C bond cleavage follows a mechanism distinct from the classical retro-aldol condensation. Kinetic, isotope 13C-labeling, and spectroscopic studies and theoretical calculations, reveal that the reaction proceeds via a surface tridentate complex as the critical intermediate on WO3, formed by chelating both α- and ß-hydroxyls of sugars, together with the carbonyl group, with two adjacent tungsten atoms (W-O-W) contributing to the ß-C-C bond cleavage. This mechanism provides insights into sugar chemistry and enables the rational design of catalytic sites and reaction pathways toward the efficient utilization of sugar-based feedstocks.

2.
Small ; 20(29): e2401858, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38693069

RESUMO

The efficient evolution of gaseous hydrogen and oxygen from water is required to realize sustainable energy conversion systems. To address the sluggish kinetics of the multielectron transfer reaction, bifunctional catalyst materials for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) should be developed. Herein, a tailored combination of atomically minimized iridium catalysts and highly conductive black WO3- x nanofiber supports are developed for the bifunctional electrolyzer system. Atomic Ir catalysts, particularly those that activate the OER, minimize the utilization of precious metals. The oxygen-deficient black WO3- x NF support, which boosts the HER, offers increased electronic conductivity and favorable nucleation sites for Ir loading. The Ir-black WO3- x NFs exhibit increased double-layer capacitance, a significantly reduced onset potential, lower Tafel slope, and stable cyclability for both the OER and HER, compared to large-sized Ir catalysts loaded on white WO3 nanofibers. This study offers a strategy for developing an optimal catalyst material with suitable supports for high-performance and economical water electrolysis systems for achieving carbon-negative targets.

3.
Chemistry ; 30(51): e202402020, 2024 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-38981857

RESUMO

Charging power supplies with both fast and visualization functions have a wide range of applications in the information and new energy industries. In this paper, the visualized and contact-type fast charging power supply based on WO3 film and Zn sheet is presented, and the prototype devices are fabricated. Different with the charging method of conventional batteries, charging is achieved by a Zn sheet contacting with a WO3 film moistened with water, resulting in a rapid discoloration of WO3. Theoretical investigation indicates that the interaction between Zn sheet and water molecules is the primary cause of the color change in the WO3 film. The WO3 film completes the colouring state within 10 s in the presence of Zn sheet and water, and the open-circuit voltage of the device is 0.7 V, which can be used to drive various electronics by series-parallel connection. This research introduces a novel method to induce colouring of WO3 films and proposes a fast charging mode different from traditional power sources. It provides valuable insights for the future development of fast charging in the field of electrical energy.

4.
Chemistry ; 30(39): e202401257, 2024 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-38709195

RESUMO

Aqueous proton batteries have received increasing attention due to their outstanding rate performance, stability and high capacity. However, the selection of anode materials in strongly acidic electrolytes poses a challenge in achieving high-performance aqueous proton batteries. This study optimized the proton reaction kinetics of layered metal oxide WO3 by introducing interlayer structural water and coating polyaniline (PANI) on its surface to prepare organic-inorganic hybrid material (WO3 ⋅ 2H2O@PANI). We constructed an aqueous proton battery with WO3 ⋅ 2H2O@PANI anode and MnO2@GF cathode. After 1500 cycles at a current density of 10 A g-1, the capacity retention rate can still reach 80.2 %. These results can inspire the development of new aqueous proton batteries.

5.
Nanotechnology ; 35(47)2024 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-39168138

RESUMO

The objective of this study is to develop an efficient, easily recoverable membrane-based photocatalyst for removing organic pollutants from aqueous solutions. This study documents the effective synthesis of a novel composite photocatalyst comprising WO3/g-C3N4(WCN) loaded onto cellulose acetate (CA). The physicochemical properties of the synthesized nanocomposites were validated using a range of techniques, including Fourier transform infrared spectroscopy, x-ray diffraction, scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy, and UV-visible diffuse reflectance spectroscopy. SEM analysis revealed that the WCN particles exhibited a well-decorated arrangement on the CA surface in the form of spherical particles. The successfully synthesized film was utilized as a potential adsorbent for removing organic pollutants such as Rhodamine B (Rh-B) and Methylene blue (MB) from aqueous solutions under UV light illumination. The results showcased the significant potential of the WCN@CA nanocomposite, achieving a remarkable 83% and 85% efficiency in eliminating Rh-B and MB. The pseudo-first-order kinetic models were found to be appropriate for both dye adsorption onto the WCN@CA nanocomposite. The WCN@CA catalyst, capable of being reused five times without significant loss of efficiency, shows great potential for decomposing toxic organic pollutants. The novelty of this work lies in the innovative combination of WCN with CA, resulting in a highly efficient and reusable photocatalyst for environmental remediation.

6.
Nanotechnology ; 36(1)2024 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-39362237

RESUMO

Fast and accurate detection of light in the near-infrared (NIR) spectral range plays a crucial role in modern society, from alleviating speed and capacity bottlenecks in optical communications to enhancing the control and safety of autonomous vehicles through NIR imaging systems. Several technological platforms are currently under investigation to improve NIR photodetection, aiming to surpass the performance of established III-V semiconductor p-i-n (PIN) junction technology. These platforms includein situ-grown inorganic nanocrystals (NCs) and nanowire arrays, as well as hybrid organic-inorganic materials such as graphene-perovskite heterostructures. However, challenges remain in NC and nanowire growth, large-area fabrication of high-quality 2D materials, and the fabrication of devices for practical applications. Here, we explore the potential for tailored semiconductor NCs to enhance the responsivity of planar metal-semiconductor-metal (MSM) photodetectors. MSM technology offers ease of fabrication and fast response times compared to PIN detectors. We observe enhancement of the optical-to-electric conversion efficiency by up to a factor of ∼2.5 through the application of plasmonically-active semiconductor nanorods and NCs. We present a protocol for synthesizing and rapidly testing the performance of non-stoichiometric tungsten oxide (WO3-x) nanorods and cesium-doped tungsten oxide (CsyWO3-x) hexagonal nanoprisms prepared in colloidal suspensions and drop-cast onto photodetector surfaces. The results demonstrate the potential for a cost-effective and scalable method exploiting tailored NCs to improve the performance of NIR optoelectronic devices.

7.
Environ Res ; 241: 117573, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-37956755

RESUMO

Photocatalytic CO2 reduction to valuable fuels has proved to be a favourable process to produce renewable energy and reduce CO2 emissions, which mostly depends on designing effective photocatalysts with the rapid separation rate of charge carriers. In this contribution, mesoporous n-n heterojunction Li2MnO3/WO3 nanocomposites were designed via a simplistic sol-gel process for CO2 reduction utilizing visible illumination (λ > 420 nm). XRD and TEM measurements confirmed the synthesized Li2MnO3/WO3 nanocomposite is a monoclinic structure, and its particle size is 25 ± 5 nm. The obtained Li2MnO3/WO3 exhibited narrower bandgap energy (1.74 eV), larger surface area (212 m2g-1), exceedingly visible absorbing, and lower recombination of electron and hole. The yield of CH3OH was determined about 198, 871, 1140, 1550 and 1570 mmolg-1 for bare WO3 and 5%, 10%, 15% and 20% Li2MnO3/WO3 nanocomposites, respectively. These results evidenced that the 15% Li2MnO3/WO3 photocatalyst exhibited the best reduction ability compared to other nanocomposites. The CO2 reduction over 15% Li2MnO3/WO3 photocatalyst achieved a maximal CO2 conversion with the substantially boosted CH3OH, i.e., 1550 mmolg-1 after 9 h, which was enhanced 7.8 folds great than of WO3 NPs. Mesoporous Li2MnO3/WO3 nanocomposites, in comparison with bare WO3 NPs, created more active sites for facilitating CO2 and had a specific electric field to more effectively separate charge carriers. The Li2MnO3/WO3 photocatalyst has superior photostability during the continuous reduction of CO2 for 45 h with no remarkable decrease. The possible direct S-scheme mechanism for electron transfer over Li2MnO3/WO3 photocatalyst with the enhanced CO2 reduction ability was discussed. The present work demonstrates an avenue for building highly effective heterostructure photocatalysts in solar-energy-induced potential applications.


Assuntos
Dióxido de Carbono , Iluminação , Luz , Eletricidade , Elétrons , Íons , Lítio
8.
Environ Res ; 260: 119610, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39004393

RESUMO

Photocatalysis has been widely used as one of the most promising approaches to remove various pollutants in liquid or gas phases during the last decade. The main emphasis of the study is on the synergy of vacancy engineering and heterojunction formation, two widely used modifying approaches, to significantly alter photocatalytic performance. The vacancy-induced Ag2CO3/BiOBr/WO3-x heterojunction system has been fabricated using a co-precipitation technique to efficiently abate methylene blue (MB) dye and doxycycline (DC) antibiotic. The as-fabricated Ag2CO3/BiOBr/WO3-x heterojunction system displayed improved optoelectronic characteristic features because of the rational combination of dual charge transferal route and defect modulation. The Ag2CO3/BiOBr/WO3-x system possessed 97% and 74% photodegradation efficacy for MB and DC, respectively, with better charge isolation and migration efficacy. The ternary photocatalyst possessed a multi-fold increase in the reaction rate for both MB and DC, i.e., 0.021 and 0.0078 min-1, respectively, compared to pristine counterparts. Additionally, more insightful deductions about the photodegradation routes were made possible by the structural investigations of MB and DC using density functional theory (DFT) simulations. This study advances the understanding of the mechanisms forming visible light active dual Z-scheme heterojunction for effective environmental remediation.


Assuntos
Poluentes Químicos da Água , Poluentes Químicos da Água/química , Catálise , Teoria da Densidade Funcional , Bismuto/química , Tungstênio/química , Fotólise , Óxidos/química , Azul de Metileno/química , Compostos de Prata/química
9.
Environ Res ; 260: 119676, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39053761

RESUMO

The photoelectrocatalytic advanced oxidation process (PEAOP) necessitates high-performing and stable photoanodes for the effective oxidation of complex pollutants in industrial wastewater. This study presents the construction of 2D WO3/MXene heteronanostructures for the development of efficient and stable photoanode. The WO3/MXene heterostructure features well-ordered WO3 photoactive sites anchored on micron-sized MXene sheets, providing an increased visible light active catalytic surface area and enhanced electrocatalytic activities for pollutant oxidation. Phenol, a highly toxic compound, was completely oxidized at an applied potential of 0.8 V vs. RHE under visible light irradiation. Systematic optimization of operational conditions for the photoelectrocatalytic oxidation of phenol was conducted. The phenol oxidation mechanism was elucidated via high-performance liquid chromatography (HPLC) analysis and the identification of intermediate compounds. Additionally, a mixed model of phenol and arsenic (III) in polluted water demonstrated the capability of WO3/MXene photoanode for the simultaneous oxidation of both organic and inorganic pollutants, achieving complete conversion of phenol and As(III) to non-toxic As(V). The WO3/MXene photoanode facilitated water oxidation, generating a substantial amount of O2•- and •OH oxidative species, which are crucial for the concurrent oxidation of phenol and arsenic. Recyclability tests demonstrated a 99% retention of performance, confirming the WO3/MXene photoanode's suitability for long-term operation in PEAOPs. The findings suggest that integrating WO3/MXene photoanodes into water purification systems can enhance economic feasibility, reduce energy consumption, and improve efficiency. This PEAOP offers a viable solution to the critical issue of heavy metal and organic chemical pollution in various water bodies, given its scalability and ability to preserve ecosystems while conserving clean water resources.


Assuntos
Arsênio , Oxirredução , Fenol , Tungstênio , Águas Residuárias , Poluentes Químicos da Água , Águas Residuárias/química , Poluentes Químicos da Água/química , Poluentes Químicos da Água/análise , Tungstênio/química , Fenol/química , Arsênio/química , Catálise , Óxidos/química , Processos Fotoquímicos , Eletrodos , Técnicas Eletroquímicas/métodos , Eliminação de Resíduos Líquidos/métodos
10.
Mikrochim Acta ; 191(11): 645, 2024 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-39365453

RESUMO

Solvothermal synthesis of 1D n-In2O3@n-WO3 heterojunction nanowires (HNWs) and their NO2 gas sensing characteristics are reported. The n-In2O3@n-WO3 HNWs have been well-characterised using XRD, Raman spectroscopy, XPS, SEM and HRTEM analyses. The NO2 sensing performance of n-In2O3@n-WO3 HNWs showed superior performance compared with pristine WO3 NWs. Due to the distinctive configuration of WO3-In2O3 heterojunctions, the n-In2O3@n-WO3 HNWs demonstrated remarkable sensitivity reaching 182% in response towards 500 ppb of NO2 gas at operating temperature of 200°C which is nearly 3.5 times greater than the response observed with pristine WO3 (50%). Moreover, the n-In2O3@n-WO3 HNWs also exhibited fast response (8-13 s)/recovery (54-62 s) time characteristics. A plausible sensing mechanism has been discussed. The enhancement in sensor characteristics shows that n-In2O3@n-WO3 HNWs could serve as a promising material for high-performance NO2 gas sensors for real-time environmental monitoring applications. This work could provide new understandings of the sensing mechanism of n-In2O3@n-WO3-based heterojunction nanowires, which can be applied to the design of novel n-n type MOS heterojunction materials for the application of low-temperature real-time high-performance NO2 sensors.

11.
Sensors (Basel) ; 24(17)2024 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-39275517

RESUMO

Surface engineering techniques can be used to develop high-performance gas sensing materials and advance the development of sensors. In this study, we improved the gas sensing performance of two-dimensional (2D) WO3 nanoplates by combining surface Zn modification and the in situ formation of ZnWO4/WO3 heterojunctions. Introducing Zn atoms by surface modification can reconstruct the atomic surface of 2D WO3 nanoplates, creating additional active sites. This allowed for the preparation of various types of ZnWO4/WO3 heterojunctions on the surface of the WO3 nanoplates, which improved the selectivity and sensitivity to the target gas triethylamine. The sensor exhibited good gas sensing performance for triethylamine even at low operating temperatures and strongly resisted humidity changes. The ZnWO4/WO3 material we prepared demonstrated a nearly threefold improvement in the triethylamine (TEA) response, with a gas sensing responsivity of 40.75 for 10 ppm of TEA at 250 °C. The sensor based on ZnWO4/WO3 has a limit of detection (LOD) for TEA of 200 ppb in practical measurements (its theoretical LOD is even as low as 31 ppb). The method of growing ZnWO4 on the surface of WO3 nanoplates using surface modification techniques to form surface heterojunctions differs from ordinary composites. The results suggest that the in situ construction of surface heterojunctions using surface engineering strategies, such as in situ modifying, is a practical approach to enhance the gas sensing properties and resistance to the humidity changes of metal oxide materials.

12.
Nano Lett ; 23(10): 4502-4509, 2023 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-37171532

RESUMO

Extending the fabrication methodology of solid-state nanopores in a wide range of materials is significant in the fields of single molecule detection, nanofluidic devices, and nanofiltration membranes. Here, we demonstrate a new method to directly fabricate size- and density-controllable sub-10 nm nanopores in WO3 nanosheets using single swift heavy ions (SHIs) without any chemical etching process. By selecting ions of different electronic energy losses (Se), nanopores with sizes from 1.8 to 7.4 nm can be created in WO3 nanosheets. The creation efficiency of nanopores achieves ∼100% for Se > 20 keV/nm, and there exists a critical thickness below which nanopores can be created. Combined with molecular dynamics simulations, we propose that the viscosity and surface tension of the transient molten phase caused by SHIs are the key factors for the formation of nanopores. This method paves a way to fabricate solid-state nanopores in materials with a low viscosity and surface tension.

13.
Molecules ; 29(19)2024 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-39407493

RESUMO

The large-scale utilization of antibiotics has opened a separate chapter of pollution with the generation of reactive drug-resistant bacteria. To deal with this, in this work, different mass ratios of CoFe2O4/WO3 nanocomposites were prepared following an in situ growth method using the precursors of WO3 and CoFe2O4. The structure, morphology, and optical properties of the nanocomposite photocatalysts were scrutinized by X-ray diffraction (XRD), UV-visible diffuse reflectance spectra (UV-Vis DRS), photoluminescence spectrum (PL), etc. The experimental data signified that the loading of CoFe2O4 obviously changed the optical properties of WO3. The photocatalytic performance of CoFe2O4/WO3 composites was investigated by considering tetracycline as a potential pollutant. The outcome of the analyzed data exposed that the CoFe2O4/WO3 composite with a mass ratio of 5% had the best degradation performance for tetracycline eradication under the solar light, and a degradation efficiency of 77% was achieved in 20 min. The monitored degradation efficiency of the optimized photocatalyst was 45% higher compared with the degradation efficiency of 32% for pure WO3. Capturing experiments and tests revealed that hydroxyl radical (·OH) and hole (h+) were the primary eradicators of the target pollutant. This study demonstrates that a proper mass of CoFe2O4 can significantly push WO3 for enhanced eradication of waterborne pollutants.


Assuntos
Antibacterianos , Cobalto , Nanocompostos , Óxidos , Tetraciclina , Tungstênio , Tungstênio/química , Nanocompostos/química , Catálise , Antibacterianos/química , Antibacterianos/farmacologia , Óxidos/química , Tetraciclina/química , Cobalto/química , Compostos Férricos/química , Fotólise , Poluentes Químicos da Água/química , Difração de Raios X , Processos Fotoquímicos
14.
Environ Geochem Health ; 46(10): 376, 2024 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-39167294

RESUMO

Currently, one of the primary challenges that human society must overcome is the task of decreasing the amount of energy used and the adverse effects that it has on the environment. The daily increase in liquid waste (comprising organic pollutants) is a direct result of the creation and expansion of new companies, causing significant environmental disruption. Water contamination is attributed to several industries such as textile, chemical, poultry, dairy, and pharmaceutical. In this study, we present the successful degradation of methylene blue dye using g-C3N4 (GCN) mixed with WO3 and V2O5 composites (GCN/WO3/V2O5 ternary composite) as a photocatalyst, prepared by a simple mechanochemistry method. The GCN/WO3/V2O5 ternary composite revealed a notable enhancement in photocatalytic performance, achieving around 97% degradation of aqueous methylene blue (MB). This performance surpasses that of the individual photocatalysts, namely pure GCN, GCN/WO3, and GCN/V2O5 composites. Furthermore, the GCN/WO3/V2O5 ternary composite exhibited exceptional stability even after undergoing five consecutive cycles. The exceptional photocatalytic activity of the GCN/WO3/V2O5 ternary composite can be ascribed to the synergistic effect of metal-free GCN and metal oxides, resulting in the alteration of the band gap and suppression of charge recombination in the ternary photocatalyst. This study offers a better platform for understanding the characteristics of materials and their photocatalytic performance under visible light conditions.


Assuntos
Azul de Metileno , Óxidos , Tungstênio , Poluentes Químicos da Água , Tungstênio/química , Óxidos/química , Catálise , Poluentes Químicos da Água/química , Concentração de Íons de Hidrogênio , Azul de Metileno/química , Grafite/química , Purificação da Água/métodos , Processos Fotoquímicos , Fotólise , Compostos de Nitrogênio
15.
J Environ Sci (China) ; 140: 103-112, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38331492

RESUMO

Highly crystalline carbon nitride polymers have shown great opportunities in overall water photosplitting; however, their mission in light-driven CO2 conversion remains to be explored. In this work, crystalline carbon nitride (CCN) nanosheets of poly triazine imide (PTI) embedded with melon domains are fabricated by KCl/LiCl-mediated polycondensation of dicyandiamide, the surface of which is subsequently deposited with ultrafine WO3 nanoparticles to construct the CCN/WO3 heterostructure with a S-scheme interface. Systematic characterizations have been conducted to reveal the compositions and structures of the S-scheme CCN/WO3 hybrid, featuring strengthened optical capture, enhanced CO2 adsorption and activation, attractive textural properties, as well as spatial separation and directed movement of light-triggered charge carriers. Under mild conditions, the CCN/WO3 catalyst with optimized composition displays a high photocatalytic activity for reducing CO2 to CO in a rate of 23.0 µmol/hr (i.e., 2300 µmol/(hr·g)), which is about 7-fold that of pristine CCN, along with a high CO selectivity of 90.6% against H2 formation. Moreover, it also manifests high stability and fine reusability for the CO2 conversion reaction. The CO2 adsorption and conversion processes on the catalyst are monitored by in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), identifying the crucial intermediates of CO2*-, COOH* and CO*, which integrated with the results of performance evaluation proposes the possible CO2 reduction mechanism.


Assuntos
Dióxido de Carbono , Nanopartículas , Nitrilas , Adsorção , Imidas
16.
Angew Chem Int Ed Engl ; 63(11): e202319685, 2024 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-38151975

RESUMO

Glycerol is a byproduct of biodiesel production. Selective photoelectrochemical oxidation of glycerol to high value-added chemicals offers an economical and sustainable approach to transform renewable feedstock as well as store green energy at the same time. In this work, we synthesized monoclinic WO3 nanosheets with exposed (002) facets, which could selectively oxidize glycerol to glyceric acid (GLYA) with a photocurrent density of 1.7 mA cm-2 , a 73 % GLYA selectivity and a 39 % GLYA Faradaic efficiency at 0.9 V vs. reversible hydrogen electrode (RHE) under AM 1.5G illumination (100 mW cm-2 ). Compared to (200) facets exposed WO3 , a combination of experiments and theoretical calculations indicates that the superior performance of selective glycerol oxidation mainly originates from the better charge separation and prolonged carrier lifetime resulted from the plenty of surface trapping states, lower energy barrier of the glycerol-to-GLYA reaction pathway, more abundant active sites and stronger oxidative ability of photogenerated holes on the (002) facets exposed WO3 . Our findings show great potential to significantly contribute to the sustainable and environmentally friendly chemical processes via designing high performance photoelectrochemical cell via facet engineering for renewable feedstock transformation.

17.
Angew Chem Int Ed Engl ; : e202411016, 2024 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-39193810

RESUMO

Photocatalytic water splitting using semiconductors is a promising approach for converting solar energy to clean energy. However, challenges such as sluggish water oxidation kinetics and limited light absorption of photocatalyst cause low solar-to-hydrogen conversion efficiency (STH). Herein, we develop a photocatalytic overall water splitting system using I3-/I- as the shuttle redox couple to bridge the H2-producing half-reaction with the O2-producing half-reaction. The system uses the halide perovskite of benzylammonium lead iodide (PMA2PbI4, PMA = C6H5CH2NH2) loaded with MoS2 (PMA2PbI4/MoS2) as the H2 evolution photocatalyst, and the RuOx-loaded WO3 (WO3/RuOx) as the O2 evolution photocatalyst, achieving a H2/O2 production in stoichiometric ratio with an excellent STH of 2.07%. This work provides a detour route for photocatalytic water splitting with the help of I3-/I- shuttle redox couple in the halide perovskite HI splitting system and enlightens one to integrate and utilize multi catalytic strategies for solar-driven water splitting.

18.
Small ; 19(44): e2302365, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37420328

RESUMO

As representative extended planar defects, crystallographic shear (CS) planes, namely Wadsley defects, play an important role in modifying the physical and chemical properties of metal oxides. Although these special structures have been intensively investigated for high-rate anode materials and catalysts, it is still experimentally unclear how the CS planes form and propagate at the atomic scale. Here, the CS plane evolution in monoclinic WO3 is directly imaged via in situ scanning transmission electron microscope. It is found that the CS planes nucleate preferentially at the edge step defects and proceed by the cooperative migration of WO6 octahedrons along particular crystallographic orientations, passing through a series of intermediate states. The local reconstruction of atomic columns tends to form (102) CS planes featured with four edge-sharing octahedrons in preference to the (103) planes, which matches well with the theoretical calculations. Associated with the structure evolution, the sample undergoes a semiconductor-to-metal transition. In addition, the controlled growth of CS planes and V-shaped CS structures can be achieved by artificial defects for the first time. These findings enable an atomic-scale understanding of CS structure evolution dynamics.

19.
Small ; 19(32): e2301178, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37066750

RESUMO

Pt-based supported materials, a widely used electrocatalyst for hydrogen evolution reaction (HER), often experience unavoidable electron loss, resulting in a mismatching of electronic structure and HER behavior. Here, a Pt/WO3 catalyst consisting of Pt species strongly coupled with defective WO3 polycrystalline nanorods is rationally designed. The electronic structure engineering of Pt sites on WO3 can be systematically regulated, and so that the optimal electron-rich Pt sites on Pt/WO3 -600 present an excellent HER activity with only 8 mV overpotential at 10 mA cm-2 . Particularly, the mass activity reaches 7015 mA mg-1 at the overpotential of 50 mV, up to 26-fold higher than that of the commercial Pt/C. The combination of experimental and theoretical results demonstrates that the O vacancies of WO3 effectively mitigate the tendency of electron transfer from Pt sites to WO3 , so that the d-band center could reach an appropriate level relative to Fermi level, endowing it with a suitable Δ G H ∗ $\Delta {G_{{{\rm{H}}^ * }}}$ . This work identifies the influence of the electronic structure on catalytic activity.

20.
Nanotechnology ; 35(6)2023 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-37918025

RESUMO

In this study, the fabrication of an ultrahigh selective NH3gas sensor based on RGO/WO3nanocomposite has been proposed. The hydrothermal method was employed to synthesize the RGO/WO3nanocomposite. The formation of RGO/WO3nanocomposite and the elemental composition, structure and morphology of the as-synthesized materials were confirmed through an array of analytical techniques, including XRD, Raman, FT-IR, XPS and TEM. For gas sensing applications, pure RGO and RGO/WO3have effectively spin-coated onto the interdigitated electrodes (IDE's) based on fluorine doped tin oxide (FTO) respectively, and their sensitivity towards NH3was tested. Gas sensing characteristics of prepared materials were analyzed at room temperature (25 °C) under different relative humidity (RH) levels. The developed RGO/WO3sensor was subjected to different NH3concentrations, demonstrating a high sensing response of 89% towards 500 ppm NH3under 11%-97%-11% RH conditions. Notably, the sensor exhibited rapid response and recovery times with an average response time of 92 s and recovery time of 26 s when exposed to 500 ppm NH3under the specified RH conditions. To gauge the material selectivity, the prepared nanocomposite was exposed to a range of volatile organic compounds and the results showcased the sensor's remarkable selectivity and sensitivity specifically toward NH3vapor. This superior performance can be attributed to the abundant active sites and the excellent electron transport properties inherent to the RGO component. Importantly, the RGO/WO3sensor displayed high reproducibility and consistent responses, with minimal degradation (1.98% degradation) over 30 d at 11%-97%-11% RH. Furthermore, we examined the sensor's response with varying levels of relative humidity to assess its potential for real-world applications. The sensor exhibited extremely low power consumption, outperforming a commercially available metal oxide sensor while operating at ambient temperature. The robust performance of RGO/WO3coupled with low power requirements and ambient temperature operation, positions it as a promising candidate for next-generation gas sensing technologies.

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