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1.
Nat Commun ; 11(1): 3078, 2020 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-32555382

RESUMO

The exploration of photoanode materials with high efficiency and stability is the eternal pursuit for the realization of practically solar-driven photoelectrochemical (PEC) water splitting. Here we develop a deficient ternary metal sulfide (CdIn2S4) photoanode, and its PEC performance is significantly enhanced by introducing surface sulfur vacancies, achieving a photocurrent density of 5.73 mA cm-2 at 1.23 V vs. RHE and 1 Sun with an applied bias photon-to-current efficiency of 2.49% at 0.477 V vs. RHE. The experimental characterizations and theoretical calculations highlight the enhanced effect of surface sulfur vacancies on the interfacial charge separation and transfer kinetics, which also demonstrate the restrained surface states distribution and the transformation of active sites after introducing surface sulfur vacancies. This work may inspire more excellent work on developing sulfide-based photoanodes.

2.
Artigo em Inglês | MEDLINE | ID: mdl-32202409

RESUMO

Self-detoxifying fabrics are desirable forms for protection against chemical warfare agents (CWAs). Zirconium-based metal-organic frameworks (Zr-MOFs) have emerged as one of the fastest catalysts for nerve-agent hydrolysis, but there is still a lack of reliable methods to integrate them onto fibrous supports, and instantaneous detoxification remains challenging for MOF/fiber composites. Herein, we report a bio-inspired polydopamine (PDA)-mediated strategy for the preparation of Zr-MOF (UiO-66-NH2)-coated nanofiber membranes, which are capable of photothermally catalyzing the degradation of CWA simulants. UiO-66-NH2 nanocrystalline coating with high mass loading, perfect coverage, and good adhesion is readily formed on polyamide (PA)-6 nanofibers with the precoated PDA layer. The prepared PA-6@PDA@UiO-66-NH2 nanofibers display almost an order of magnitude higher turnover frequency (TOF) for the hydrolysis of the nerve agent simulant dimethyl 4-nitrophenylphosphate (DMNP) when irradiated under simulated solar light, with a half-life of only 0.5 min. Such a hydrolysis rate is significantly higher compared to that of the corresponding UiO-66-NH2 powder and UiO-66-NH2/fiber composites reported so far. This strategy may be easily generalized to other MOF/fiber pairs to achieve even higher performance and opens up new opportunities for solar photothermal catalysis in CWA protection.

3.
ACS Appl Mater Interfaces ; 11(36): 33062-33073, 2019 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-31419108

RESUMO

Rational design and construction of interface heterostructures, which can simultaneously accelerate the photoinduced carrier separation and enhance the surface water oxidation kinetics, is of great necessity for photoelectrochemical (PEC) water oxidation. Herein, we report a new strategy for boosting the PEC water oxidation by introducing Schottky junction and semiconductor/water oxidation cocatalysts (SC/WOCs) junction into the TaON photocatalyst. Compared with pristine TaON photoanode, the hierarchical TaON/Au/ZnCo-LDH (LDH = layered double hydroxide) photoanode reveals a cathodic shift of 156 mV for the onset potential and 17.3-fold photocurrent density enhancement at 1.23 V vs RHE, as well as improved long-term stability. Diagnostic efficiencies of the TaON/Au/ZnCo-LDH photoanode demonstrate that the enhanced PEC performance is not dominated by surface electrochemical water oxidation kinetics but largely contributed by the improved charge separation and transfer, indicative of synergistic effects of Au and ZnCo-LDH. Theoretical calculations further reveal that the midgap states introduced by Au and ZnCo-LDH in TaON electronic structures bring about photoexcited electrons concentrated on TaON, while holes accumulated on ZnCo-LDH to achieve efficiently spatial charge separation, which is responsible for the boosted PEC water oxidation performance. The present work highlights the importance and elucidates the mechanism of interface heterojunction in PEC water oxidation, which can provide an efficient approach to design and fabricate a new structural photoanode.

4.
Polymers (Basel) ; 11(3)2019 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-30960518

RESUMO

Responsive polymer-based sensors have attracted considerable attention due to their ability to detect the presence of analytes and convert the detected signal into a physical and/or chemical change. High responsiveness, fast response speed, good linearity, strong stability, and small hysteresis are ideal, but to gain these properties at the same time remains challenging. This paper presents a facile and efficient method to improve the photonic sensing properties of polymeric gels by using non-close-packed monolayer colloidal crystals (ncp MCCs) as the template. Poly-(2-vinyl pyridine) (P2VP), a weak electrolyte, was selected to form the pH-responsive gel material, which was deposited onto ncp MCCs obtained by controlled O2 plasma etching of close-packed (cp) MCCs. The resultant ultrathin photonic polymer gel film (UPPGF) exhibited significant improvement in responsiveness and linearity towards pH sensing compared to those prepared using cp MCCs template, achieving fast visualized monitoring of pH changes with excellent cyclic stability and small hysteresis loop. The responsiveness and linearity were found to depend on the volume and filling fraction of the polymer gel. Based on a simple geometric model, we established that the volume increased first and then decreased with the decrease of template size, but the filling fraction increased all the time, which was verified by microscopy observations. Therefore, the responsiveness and linearity of UPPGF to pH can be improved by simply adjusting the etching time of oxygen plasma. The well-designed UPPGF is reliable for visualized monitoring of analytes and their concentrations, and can easily be combined in sensor arrays for more accurate detection.

5.
ACS Appl Mater Interfaces ; 11(8): 7936-7945, 2019 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-30722660

RESUMO

Rational design and preparation of electrocatalyst with optimal component and interfaces, which can work well for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media, are of great importance in practical water splitting. Herein, a multiscale structure surface engineering approach to construct Co(OH)2/Ag/FeP hybrid as efficient electrocatalysis for water splitting in alkaline media is reported. By optimizing the component ratio and engineering interfacial structure, the Co(OH)2/Ag/FeP hybrid eletrocatalyst exhibits promoted HER and OER activity as well as stability in alkaline media, achieving an overpotential of 118 and 236 mV at a current density of 10 mA cm-2, respectively. Further experimental characterizations demonstrate the electron structure changes in Co(OH)2/Ag/FeP hybrid after constructing the interfaces, which is beneficial to generate low-charge state Fe2+ and high-oxidized Co3+/4+. The first-principle calculations reveal that the dissociation of H2O at the interface region is energetically favorable, which is responsible for the enhanced HER and OER activity. Furthermore, two-electrode alkaline water electrolyzer constructed by Co(OH)2/Ag/FeP hybrid electrocatalysts only requires a voltage of 1.56 V to afford a current density of 10 mA cm-2, which is superior to the commercial Pt/C-IrO2 catalytic couple and makes it a promising material to be employed as effective bifunctional catalysts for overall water splitting.

6.
ACS Appl Mater Interfaces ; 11(8): 7927-7935, 2019 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-30688436

RESUMO

Self-detoxifying materials capable of both capture and destruction of chemical warfare agents (CWAs) are highly desirable for efficient personal protection and safe handling of contaminated materials. Developing new strategies to improve CWA removal efficiency of these materials is highly relevant to CWA purification technology. Herein, we present novel photothermally enhanced catalytic detoxification of CWA simulants and its application in self-detoxifying gas filters. The material design features a well-defined core-shell nanostructure (CSN) consisting of an inner photothermal material and an outer microporous catalyst. As a demonstration, the CSN was obtained by growing a Zr-based metal-organic framework (MOF), UiO-66-NH2, onto bioinspired dopamine-melanin (Dpa) nanoparticles via heterogeneous nucleation induced by metal chelation. The resultant Dpa@UiO-66-NH2 CSN has increased the turnover frequency (TOF) of a nerve agent simulant, 4-nitrophenyl phosphate (DMNP), by 2.9- and 1.7-fold in the presence of NIR laser and simulated solar light, respectively. Further incorporation of Dpa@UiO-66-NH2 CSNs into polymer fibers by electrospinning has led to an even greater photothermal enhancement effect (5.8- and 3.2-fold TOF increase), achieving a faster DMNP degradation rate than the corresponding pure MOF powder for the first time and the shortest half-life of DMNP (1.8 min) among reported MOF-based self-detoxifying fabrics. The significant photothermal enhancement in the detoxification ability of Dpa@UiO-66-NH2 fabrics is attributed to the instantaneous heat transfer from the photothermal core to the catalytic shell and effective heat retention enabled by the surrounding polymer matrix. The Dpa@UiO-66-NH2 fabrics can be easily prepared on a large scale and demonstrate efficient protection against DMNP aerosols as stand-alone gas filters. This strategy of photothermally enhanced catalytic detoxification can be feasibly extended to other catalytic detoxification systems and holds promise for next-generation gas masks.


Assuntos
Substâncias para a Guerra Química/química , Melaninas/química , Estruturas Metalorgânicas/química , Catálise , Raios Infravermelhos , Luz , Nanopartículas/química , Porosidade , Temperatura , Zircônio/química
7.
ChemSusChem ; 11(23): 4150-4155, 2018 Dec 11.
Artigo em Inglês | MEDLINE | ID: mdl-30303629

RESUMO

Co9 S8 crystals can catalyze the growth of thin-walled graphite microtubes (GMTs) through a catalytic chemical vapor deposition (CCVD) process using thiourea as the precursor. The growth of GMTs follows a tip-growth mechanism with tube diameters up to a few micrometer. The hollow interiors of the GMTs are filled with carbon nanotubes and wrinkled graphene layers, which form a unique nanotube/graphene-in-microtube structure. As-formed GMTs are N,S-codoped with lots of Co9 S8 nanoparticles encapsulated in their inner walls. These GMTs are room-temperature ferromagnets and can be loaded on Ni foams to work as binder-free electrocatalysts with low overpotential (310 mV at 50 mA cm-2 for the oxygen evolution reaction (OER) and 284 mV at 50 mA cm-2 for the hydrogen evolution reaction (HER)) and long-term durability (continuous work for 120 h without loss in performance). Our research proves that metal sulfides can catalyze the growth of graphite microtubes and as-formed GMTs may potentially be used as functional building blocks to construct new kinds of electrochemical devices for various energy-related applications.

8.
ACS Appl Mater Interfaces ; 10(24): 20396-20403, 2018 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-29806452

RESUMO

Self-detoxification filters against lethal chemical warfare agents (CWAs) are highly desirable for the protection of human beings and the environment. In this report, flexible self-supported filters of a series of Zr(IV)-based metal-organic frameworks (MOFs) including UiO-66, UiO-67, and UiO-66-NH2 were successfully prepared and exhibited fast and sustained degradation of CWA simulants. A half-life as short as 2.4 min was obtained for the catalytic hydrolysis of dimethyl 4-nitrophenyl phosphate, and the percent conversion remained above 90% over a long-term exposure of 120 min, well exceeding those of the previously reported composite MOF filters and the corresponding MOF powders. The outstanding detoxification performance of the self-supported fibrous filter comes from the exceptionally high surface area, excellent pore accessibility, and hierarchical structure from the nano- to macroscale. This work demonstrates, for the first time, MOF-only filters as efficient self-detoxification media, which will offer new opportunities for the design and fabrication of functional materials for toxic chemical protection.

9.
Chem Asian J ; 13(9): 1129-1137, 2018 May 04.
Artigo em Inglês | MEDLINE | ID: mdl-29573564

RESUMO

Electrochemically active hollow nanostructured materials hold great promise in diverse energy conversion and storage applications, however, intricate synthesis steps and poor control over compositions and morphologies have limited the realization of delicate hollow structures with advanced functional properties. In this study, we demonstrate a one-step wet-chemical strategy for co-engineering the hollow nanostructure and anion intercalation of nickel cobalt layered double hydroxide (NiCo-LDH) to attain highly electrochemical active energy conversion and storage functionalities. Self-templated pseudomorphic transformation of cobalt acetate hydroxide solid nanoprisms using nickel nitrate leads to the construction of well-defined NiCo-LDH hollow nanoprisms (HNPs) with multi-anion intercalation. The unique hierarchical nanosheet-assembled hollow structure and efficiently expanded interlayer spacing offer an increased surface area and exposure of active sites, reduced mass and charge transfer resistance, and enhanced stability of the materials. This leads to a significant improvement in the pseudocapacitive and electrocatalytic properties of NiCo-LDH HNP with respect to specific capacitance, rate and cycling performance, and OER overpotential, outperforming most of the recently reported NiCo-based materials. This work establishes the potential of manipulating sacrificial template transformation for the design and fabrication of novel classes of functional materials with well-defined nanostructures for electrochemical applications and beyond.

10.
ACS Appl Mater Interfaces ; 10(2): 1701-1706, 2018 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-29271199

RESUMO

Owing to its benefits to reducing paper production and consumption, ink-free rewritable paper has attracted great attention and it is desirable to develop rewritable paper based on its low-cost, robust, and environmentally benign color switching systems. Herein, we report the fabrication of a rewritable paper based on novel poly(vinylpyrrolidone)/hexatungstic acid (HTA) hybrids with fast dual-mode color switching. As-prepared rewritable paper shows fast and reversible colorless-blue or blue-colorless color switching upon photo- or hydroprinting, owing to the fast redox transformations of the unique HTA clusters. More interestingly, the rewritable paper can be used as a template for noble-metal reduction and the noble metal can be deposited on the reduced area of the paper to form well-ordered patterns in high resolution. This rewritable paper can be produced in large scale, and the composition can be facilely tuned with various polyoxometalates or polymers. It may not only be an attractive alternative to current paper prints but also be potentially used for noble-metal reduction to prepare photolithographic circuits and optoelectronic devices.

11.
ACS Appl Mater Interfaces ; 9(38): 32418-32423, 2017 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-28876044

RESUMO

In this work, we report the first hybrid nanosized photoinitiators with low cytotoxicity and migration by coupling of polyhedral oligomeric silsesquioxanes (POSS) to benzophenone derivatives. This new series of photoinitiators were fully characterized and showed many favorable properties such as uniform sizes, extremely low tendency to migrate, less effect on resin viscosity, enhanced thermal stability and mechanical strength, increased photoactivity, and significantly lower cell toxicity compared to their corresponding benzophenone molecules. The utility of these hybrid nanosized photoinitiators in 3D printing was demonstrated in printing of various 3D structures with high resolution and accuracy.

12.
Chem Asian J ; 12(17): 2284-2290, 2017 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-28763162

RESUMO

This work demonstrates a facile in situ synthesis of cobalt-manganese mixed sulfide (CoMn-S) nanocages on reduced graphene oxide (RGO) sheets by using a crystalline Co-Mn precursor as the sacrificial template. The CoMn-S/RGO hybrid was applied as the anode for Li-ion storage and exhibited superior specific capacity, excellent cycling performance, and great rate capability. In particular, lithium storage testing revealed that the hybrid delivered high discharge-charge capacities of 670 mA h g-1 at 1.0 A g-1 after 400 cycles and 925 mA h g-1 at 0.1 A g-1 after 300 cycles. The outstanding electrochemical performance of CoMn-S/RGO is attributed to the close entanglement of nanocages with RGO nanosheets achieved by the synthetic method, which greatly improves ion/electron transport along the interfaces and efficiently mitigates volume dilation during lithium reactions. This rational design of both the composition and architecture of mixed metal sulfides can be expanded to other composite systems for high-capacity Li-ion batteries and provides a unique insight into the development of advanced hybrid electrode materials.

13.
Nanoscale ; 9(9): 3206-3211, 2017 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-28221381

RESUMO

Facet-control has been a fascinating method for preparation of highly active photocatalysts. Herein, we report the hydrothermal preparation of single-crystalline ZnGa2O4 nanoprisms with the {111} and {110} facets coexposed. Studies of their photocatalytic performance have revealed that the as-formed nanoprisms exhibit significantly enhanced photocatalytic activities compared with ZnGa2O4 nanocubes with only the {100} facets exposed and nanosheets with the {110} facets exposed for H2 evolution and contaminant degradation. Theoretical calculations combined with valence band XPS results indicate the formation of a surface heterojunction by the coexposed {111} and {110} facets, which promotes the photogenerated electron and hole migration to the {110} and {111} facets, respectively, and enhances the photocatalytic performance.

14.
Beilstein J Nanotechnol ; 8: 2781-2789, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-29354349

RESUMO

A nanostructured plasmonic photocatalyst, silver/silver thiocyanate (Ag@AgSCN), has been prepared by a simple precipitation method followed by UV-light-induced reduction. The ratio of Ag to silver thiocyanate (AgSCN) can be controlled by simply adjusting the photo-induced reduction time. The formation mechanism of the product was investigated based on the time-dependent experiments. Further experiments indicated that the prepared Ag@AgSCN nanostructures with an atomic ratio of Ag/AgSCN = 0.0463 exhibited high photocatalytic activity and long-term stability for the degradation of oxytetracycline (84%) under visible-light irradiation. In addition to the microstructure and high specific surface area, the enhanced photocatalytic activity was mainly caused by the surface plasmon resonance of Ag nanoparticles, and the high stability of AgSCN resulted in the long-term stability of the photocatalyst product.

15.
Chem Asian J ; 12(3): 347-354, 2017 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-27900854

RESUMO

Novel hollow Ag/MnO2 nanostructures with controlled shell composition and structure were designed and synthesized. In the present synthetic procedure, silver nanocrystals were oxidized by KMnO4 , and MnO2 was heterogeneously formed on the surface of silver nanocrystals, then released Ag+ was photoreduced to silver adjacent to MnO2 . By simply changing the photoreduction moment, simultaneously with or after the addition of KMnO4 , hollow Ag/MnO2 structures with different shell architectures-a monolayered shell composed of evenly mixed silver and MnO2 and a double-layered shell composed of an inner MnO2 layer and an outer silver layer-can be obtained. Furthermore, the morphology of the hollow structure can be tuned by selecting different silver precursors, and the ratio of silver to MnO2 in the shell can also be controlled by adjusting the ratio in the original reaction mixture. Electrochemical measurements revealed significantly enhanced catalytic performance in the oxygen reduction reaction for the prepared hollow structures. Compared with the Ag/MnO2 composite, the onset potentials positively shift by about 50.0 mV and limiting current densities are nearly 2.0 times higher.

16.
ACS Appl Mater Interfaces ; 8(43): 29713-29720, 2016 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-27768278

RESUMO

Ink-free rewritable media has attracted great attention as a potential alternative to current paper prints, owing to its benefits to reducing paper production and consumption for environmental protection. It is desirable to develop rewritable media based on cheap, robust, and fast-response photochromic systems. Herein, we report the design and fabrication of flexible and photorewritable PVP/a-WO3 hybrid membranes through electrospinning, on which images with high resolution can be photoprinted and heat-erased for over 40 cycles. The well conjugated organic-inorganic hybrid structure endows a fast "electron-proton double injection" from PVP to a-WO3 in the coloration process and greatly improves the photochromic responses. The coloration times can be as short as tens of seconds and the erasure times can be as long as 10 days in ambient conditions. As-formed photochromic membranes are low-cost, environmental benign and easy for large-scale production, indicate their great potential as flexible rewritable media for practical usage.

17.
Chem Commun (Camb) ; 52(42): 6922-5, 2016 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-27147199

RESUMO

We report the design and fluorescence properties of a novel aggregation-induced emission (AIE) system obtained by grafting carboxyl group conjugated AIE molecules onto monodispersed colloidal GaOOH nanocubes. Compared with nanoaggregates formed in mixed solvents, as-formed nanohybrids avoid contact with a "good" solvent, restrict the molecular motions more efficiently and show a significantly enhanced AIE.

18.
Chemistry ; 22(27): 9321-9, 2016 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-27219903

RESUMO

A facile liquid-phase exfoliation method to prepare few-layer FeOCl nanosheets in acetonitrile by ultrasonication is reported. The detailed exfoliation mechanism and generated products were investigated by combining first-principle calculations and experimental approaches. The similar cleavage energies of FeOCl (340 mJ m(-2) ) and graphite (320 mJ m(-2) ) confirm the experimental exfoliation feasibility. As a Fenton reagent, FeOCl nanosheets showed outstanding properties in the catalytic degradation of phenol in water at room temperature, under neutral pH conditions, and with sunlight irradiation. Apart from the increased surface area of the nanosheets, the surface state change of the nanosheets also plays a key role in improving the catalytic performance. The changes of charge density, density of states (DOS), and valence state of Fe atoms in the exfoliated FeOCl nanosheets versus plates illustrated that surface atomistic relationships made the few-layer nanosheets higher activity, indicating the exfoliation process of the FeOCl nanosheets also brought about surface state changes.

19.
Phys Chem Chem Phys ; 17(41): 27391-8, 2015 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-26420572

RESUMO

In-depth understanding of the sol-gel process plays an essential role in guiding the preparation of new materials. Herein, the effects of different inorganic acids (HCl, HNO3 and H2SO4) and divalent hydrated metal cations (Mg(2+), Ca(2+), Co(2+), Ni(2+)) on γ-AlOOH sol-gel process were studied based on experiments and density functional theory (DFT) calculations. In these experiments, the sol originating from the γ-AlOOH suspension was formed only with the addition of HCl and HNO3, but not with H2SO4. Furthermore, the DFT calculations showed that the strong adsorption of HSO4(-) on the surface of the γ-AlOOH particles, and the hydrogen in HSO4(-) pointing towards the solvent lead to an unstable configuration of electric double layer (EDL). In the experiment, the gelation time sequence of γ-AlOOH sol obtained by adding metal ions changed when the ionic strength was equal to or greater than 0.198 mol kg(-1). The DFT calculations demonstrated that the adsorption energy of hydrated metal ions on the γ-AlOOH surface can actually make a difference in the sol-gel process.

20.
Phys Chem Chem Phys ; 16(12): 5866-74, 2014 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-24549202

RESUMO

Cube-like basic aluminium sulfate crystals were prepared by a facile template-free hydrothermal strategy. The microstructures, morphologies and textural properties of as-synthesized material were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy. X-ray crystallography reveals that cubic basic aluminium sulfate possesses a single crystal nature. Chemical formation mechanism studies of sulfuric acid with γ-AlOOH were performed using a combined experimental and computational approach. Time dependent experiments reveal that formation of basic aluminium sulfate is based on the dissolution-recrystallization process, and the source of Al(3+) is from the dissolution of γ-AlOOH at high H(+) concentration. Moreover, the quantum mechanical calculations reveal that dramatic structural changes occurred in the (100) plane at high H(+) concentration, which is inferred to be the initiation of the source of Al(3+). Meanwhile, surface energy calculations can well explain the exposed plane of basic aluminium sulfate microcubes, which are consistent with the XRD results. Besides, equations to quantitatively describe the relationship between the molar amount of H(+) and the final phase are proposed, which has been confirmed by experimental results.

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