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1.
Artigo em Inglês | MEDLINE | ID: mdl-32233392

RESUMO

Two-dimensional (2D) structured photocatalysts with atomically thin layers, not only have the potential to enhance hydrogen generation efficiency, but also allow more direct investigations of the effects of surface terminations on photocatalytic activity. Taking 2D Bi2WO6 nanosheets as a model system, we found that the configuration of bilayer Bi2O2 sandwiched by alternating WO4 layers enabled the thermodynamic driving potential for efficient electron injection and provided the possibility of hydrogen production by water splitting. Without Pt deposition, the H2 generation efficiency can reach to 56.9 µmol/g/h by 2D Bi2WO6 as compared with no activity of Bi2WO6 nanocrystals under simulated solar light. This configuration is easily functionalized by adsorption of Cl-/Br- to form Bi-Cl/ Bi-Br bonds, result in the decrease of the recombination rate of photogenerated electron-hole pairs and narrower bandgap. This work highlights an effective way to design photocatalysts with efficient hydrogen generation from water splitting by tuning the surface terminations.

2.
Inorg Chem ; 2020 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-32129071

RESUMO

A series of tunnel structured V-substituted silver hollandite (Ag1.2VxMn8-xO16, x = 0-1.4) samples is prepared and characterized through a combination of synchrotron X-ray diffraction (XRD), synchrotron X-ray absorption spectroscopy (XAS), laboratory Raman spectroscopy, and electron microscopy measurements. The oxidation states of the individual transition metals are characterized using V and Mn K-edge XAS data indicating the vanadium centers exist as V5+, and the Mn oxidation state decreases with increased V substitution to balance the charge. Scanning transmission electron microscopy of reduced materials shows reduction-displacement of silver metal at high levels of lithiation. In lithium batteries, the V-substituted tunneled manganese oxide materials reveal previously unseen reversible nonaqueous Ag electrochemistry and exhibit up to 2.5× higher Li storage capacity relative to their unsubstituted counterparts. The highest capacity was observed for the Ag1.2(V0.8Mn7.2)O16·0.8H2O material with an intermediate level of V substitution, likely due to a combination of the atomic composition, the morphology of the particle, and the homogeneous distribution of the active material within the electrode structure where factors over multiple length scales contribute to the electrochemistry.

3.
Nat Mater ; 2020 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-32152562

RESUMO

The electronic, optical and chemical properties of two-dimensional transition metal dichalcogenides strongly depend on their three-dimensional atomic structure and crystal defects. Using Re-doped MoS2 as a model system, here we present scanning atomic electron tomography as a method to determine three-dimensional atomic positions as well as positions of crystal defects such as dopants, vacancies and ripples with a precision down to 4 pm. We measure the three-dimensional bond distortion and local strain tensor induced by single dopants. By directly providing these experimental three-dimensional atomic coordinates to density functional theory, we obtain more accurate electronic band structures than derived from conventional density functional theory calculations that relies on relaxed three-dimensional atomic coordinates. We anticipate that scanning atomic electron tomography not only will be generally applicable to determine the three-dimensional atomic coordinates of two-dimensional materials, but also will enable ab initio calculations to better predict the physical, chemical and electronic properties of these materials.

4.
ChemSusChem ; 13(1): 111-115, 2020 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-31721472

RESUMO

In the present study, a sonochemical-based method for one-pot synthesis of entropy-stabilized perovskite oxide nanoparticle catalysts with high surface area was developed. The high-entropy perovskite oxides were synthesized as monodispersed, spherical nanoparticles with an average crystallite size of approximately 5.9 nm. Taking advantage of the acoustic cavitation phenomenon in the ultrasonication process, BaSr(ZrHfTi)O3 , BaSrBi(ZrHfTiFe)O3 and Ru/BaSrBi(ZrHfTiFe)O3 nanoparticles were crystallized as single-phase perovskite structures through ultrasonication exposure without calcination. Notably, the entropically-driven stability of Ru/BaSrBi(ZrHfTiFe)O3 with excellent dispersion of Ru in the perovskite phase bestowed the nanoparticles of Ru/BaSrBi(ZrHfTiFe)O3 with good catalytic activity for CO oxidation.

5.
J Am Chem Soc ; 142(2): 962-972, 2020 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-31852179

RESUMO

The pursuit of efficient hydrogenation nanocatalysts with a desirable selectivity toward intricate substrates is state-of-the-art research but remains a formidable challenge. Herein, we report a series of novel PdCdx nanocubes (NCs) for ultraselective hydrogenation reactions with flexible tuning features. Obtaining a desirable conversion level of the substrates (e.g., 4-nitrophenylacetylene (NPA), 4-nitrobenzaldehyde (NBAD), and 4-nitrostyrene (NS)) and competitive selectivity for all potential hydrogenation products have been achieved one by one under optimized hydrogenation conditions. The performance of these PdCdx NCs displays an evident dependence on both the composition and the use of Cd and a need for a distinct hydrogen source (H2 or HCOONH4). Additionally, for the selectivity of hydrogen to be suitably high, the morphology of the NCs has a very well-defined effect. Density functional theory calculations confirmed the variation of adsorption energy for the substrate and hydrogenation products by carefully controlled introduction of Cd, leading to a desirable level of selectivity for all potential hydrogenation products. The PdCdx NCs also exhibit excellent reusability with negligible activity/selectivity decay and structural/composition changes after consecutive reactions. The present study provides an advanced strategy for the rational design of superior hydrogenation nanocatalysts to achieve a practical application for desirable and selective hydrogenation reaction efficiency.

6.
Nano Lett ; 20(2): 1252-1261, 2020 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-31887051

RESUMO

Lithium-sulfur (Li-S) batteries are promising next-generation energy storage technologies due to their high theoretical energy density, environmental friendliness, and low cost. However, low conductivity of sulfur species, dissolution of polysulfides, poor conversion from sulfur reduction, and lithium sulfide (Li2S) oxidation reactions during discharge-charge processes hinder their practical applications. Herein, under the guidance of density functional theory calculations, we have successfully synthesized large-scale single atom vanadium catalysts seeded on graphene to achieve high sulfur content (80 wt % sulfur), fast kinetic (a capacity of 645 mAh g-1 at 3 C rate), and long-life Li-S batteries. Both forward (sulfur reduction) and reverse reactions (Li2S oxidation) are significantly improved by the single atom catalysts. This finding is confirmed by experimental results and consistent with theoretical calculations. The ability of single metal atoms to effectively trap the dissolved lithium polysulfides (LiPSs) and catalytically convert the LiPSs/Li2S during cycling significantly improved sulfur utilization, rate capability, and cycling life. Our work demonstrates an efficient design pathway for single atom catalysts and provides solutions for the development of high energy/power density Li-S batteries.

7.
Int J Mol Med ; 44(6): 2276-2288, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31661124

RESUMO

Lung cancer is a malignant tumor responsible for the highest mortality rate in humans. The identification of novel functional genes is of great importance in the treatment of lung cancer. The reported roles of replication factor C subunit 3 (RFC3) in tumorigenesis are contradictory. The present study aimed to explore the role and mechanism of RFC3 in lung cancer cells. An immunohistochemical study of 165 lung cancer and adjacent tissues was conducted (123 lung adenocarcinoma tissues and 42 lung squamous cell carcinoma tissues). Kaplan­Meier analysis and Cox multivariate analysis were employed to explore the relationship between RFC3 and patient prognosis. In addition, the proliferation, cell cycle distribution and apoptosis of A549 and H1299 cells were determined by MTT assay and flow cytometry, respectively, following cell transfection to induce overexpression and knockdown of RFC3. A Boyden chamber assay and wound­healing assay were conducted to determine the invasive and migratory abilities of A549 and H1299 cells. Western blotting was used to analyze the effects of RFC3 overexpression and RFC3 small interfering RNA­induced knockdown, and to explore the potential mechanism and pathway underlying the effects of RFC3. Positive expression of RFC3 was detected in lung adenocarcinoma, and overexpression of RFC3 shortened the survival time of patients with lung adenocarcinoma. Furthermore, overexpression of RFC3 increased the invasion and migration of A549 cells, whereas knockdown of RFC3 significantly reduced the invasion and migration of H1299 cells. Ectopic expression of RFC3 induced epithelial­mesenchymal transition (EMT), as determined by downregulation of E­cadherin, and upregulation of N­cadherin, vimentin and Wnt signaling target genes, including c­MYC, Wnt1 and ß­catenin, and the ratio of phosphorylated­glycogen synthase kinase 3 (GSK3)­ß (Ser9)/GSK3­ß. In conclusion, RFC3 may be considered a coactivator that promotes the Wnt/ß­catenin signaling pathway, and induces EMT and metastasis in lung adenocarcinoma.

9.
Sensors (Basel) ; 19(19)2019 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-31590254

RESUMO

Intrabody communication (IBC) has drawn extensive attention in the field of ubiquitous healthcare, entertainment, and more. Until now, most studies on the modeling and characterization of capacitive coupling IBC have been conducted in open space, while influences when using metallic-enclosed environments such as a car, airplane, or elevator have not yet been considered. In this paper, we aimed to systematically investigate the grounding effect of an enclosed metal wall of a vehicle on the transmission path loss, utilizing the finite element method (FEM) to model capacitive coupling IBC in an in-vehicle scenario. The results of a simulation and experimental validation indicated that the system gain in an in-vehicle scenario increased up to 7 dB compared to in open space. The modeling and characterization achieved in this paper of capacitive coupling IBC could facilitate an intrabody sensor design and an evaluation with great flexibility to meet the performance needs of an in-vehicle use scenario.

10.
Nanoscale ; 11(42): 20301-20306, 2019 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-31633704

RESUMO

Rational designing of catalysts to promote the sluggish kinetics of the cathode oxygen reduction reaction in proton exchange membrane fuel cells is still challenging, yet of crucial importance to its commercial application. In this work, on the basis of theoretical DFT calculations which suggest that order structured fct-phased PtFe (O-PtFe) with an atomic Pt shell exhibits superior electrocatalytic performance towards the ORR, the desired structure was prepared by using a scalable impregnation-reduction method. The as-prepared O-PtFe delivered enhanced activity (0.68 A mg-1Pt) and stability (73% activity retention after 10 000 potential cycles) compared with the corresponding disordered PtFe alloy (D-PtFe) and Pt. To confirm the excellent durability, in situ X-ray absorption fine structure spectroscopy was conducted to probe the local and electronic structure changes of O-PtFe during 10 000 cycle accelerated durability testing. We hope that this facile synthesis method and the in situ XAFS experiment could be readily adapted to other catalyst systems, facilitating the screening of highly efficient ORR catalysts for fuel cell application.

11.
J Am Chem Soc ; 141(35): 13977-13986, 2019 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-31436416

RESUMO

The chemical reactivity and/or the diffusion of Ag atoms or ions during thermal processing can cause irreversible structural damage, hindering the application of Ag nanowires (NWs) in transparent conducting films and other applications that make use of the material's nanoscale properties. Here, we describe a simple and effective method for growing monolayer SnO2 on the surface of Ag nanowires under ambient conditions, which protects the Ag nanowires from chemical and structural damage. Our results show that Sn2+ and Ag atoms undergo a redox reaction in the presence of water. First-principle simulations suggest a reasonable mechanism for SnO2 formation, showing that the interfacial polarization of the silver by the SnO2 can significantly reduce the affinity of Ag to O2, thereby greatly reducing the oxidation of the silver. The corresponding values (for example, before coating: 17.2 Ω/sq at 86.4%, after coating: 19.0 Ω/sq at 86.6%) show that the deposition of monolayer SnO2 enables the preservation of high transparency and conductivity of Ag. In sharp contrast to the large-scale degradation of pure Ag-NW films including the significant reduction of its electrical conductivity when subjected to a series of harsh corrosion environments, monolayer SnO2 coated Ag-NW films survive structurally and retain their electrical conductivity. Consequently, the thermal, electrical, and chemical stability properties we report here, and the simplicity of the technology used to achieve them, are among the very best reported for transparent conductor materials to date.

12.
Nanoscale ; 11(40): 18568-18574, 2019 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-31287484

RESUMO

CO oxidation is an important reaction both experimentally and industrially, and its performance is usually dominated by the charge states of catalysts. For example, CO oxidation on the platinum (Pt) surface requires a properly charged state for the balance of adsorption and activation of CO and O2. Here, we present "Mott-Schottky modulated catalysis" on Pt nanoparticles (NPs) via an electron-donating carbon nitride (CN) support with a tunable Fermi level. We demonstrate that properly-charged Pt presents an excellent catalytic CO oxidation activity with an initial conversion temperature as low as 25 °C and total CO conversion below 85 °C. The tunable electronic structure of Pt NPs, which is regulated by the Fermi level of CN, is a key factor in dominating the catalytic performance. This "Mott-Schottky modulated catalysis" concept may be extended to maneuver the charge state on other metal catalysts for targeted catalytic reactions.

13.
Nat Commun ; 10(1): 2840, 2019 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-31253761

RESUMO

The design of efficient and stable photocatalysts for robust CO2 reduction without sacrifice reagent or extra photosensitizer is still challenging. Herein, a single-atom catalyst of isolated single atom cobalt incorporated into Bi3O4Br atomic layers is successfully prepared. The cobalt single atoms in the Bi3O4Br favors the charge transition, carrier separation, CO2 adsorption and activation. It can lower the CO2 activation energy barrier through stabilizing the COOH* intermediates and tune the rate-limiting step from the formation of adsorbed intermediate COOH* to be CO* desorption. Taking advantage of cobalt single atoms and two-dimensional ultrathin Bi3O4Br atomic layers, the optimized catalyst can perform light-driven CO2 reduction with a selective CO formation rate of 107.1 µmol g-1 h-1, roughly 4 and 32 times higher than that of atomic layer Bi3O4Br and bulk Bi3O4Br, respectively.

14.
Adv Mater ; 31(28): e1807576, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31081183

RESUMO

Solar photocatalysis is a potential solution to satisfying energy demand and its resulting environmental impact. However, the low electron-hole separation efficiency in semiconductors has slowed the development of this technology. The effect of defects on electron-hole separation is not always clear. A model atomically thin structure of single-unit-cell Bi3 O4 Br nanosheets with surface defects is proposed to boost photocatalytic efficiency by simultaneously promoting bulk- and surface-charge separation. Defect-rich single-unit-cell Bi3 O4 Br displays 4.9 and 30.9 times enhanced photocatalytic hydrogen evolution and nitrogen fixation activity, respectively, than bulk Bi3 O4 Br. After the preparation of single-unit-cell structure, the bismuth defects are controlled to tune the oxygen defects. Benefiting from the unique single-unit-cell architecture and defects, the local atomic arrangement and electronic structure are tuned so as to greatly increase the charge separation efficiency and subsequently boost photocatalytic activity. This strategy provides an accessible pathway for next-generation photocatalysts.

15.
Chemistry ; 25(36): 8494-8498, 2019 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-31041807

RESUMO

Ruthenium (Ru)@Ordered mesoporous carbon (OMC) is a key catalyst in fine-chemical production. In general, the OMC support is prepared by a wet self-assembly requiring excessive solvent, toxic phenol-aldehyde precursors and a long reaction time, followed by post-immobilization to load Ru species. Herein, we wish to report a solid-state, rapid, and green strategy for the synthesis of Ru@OMC with biomass tannin as the precursor. The chemistry essence of this strategy lies in the mechanical-force-driven assembly, during which tannin-metal (Zn2+ and Ru3+ ) coordination polymerization and hydrogen-bonding interactions between tannin-block copolymer (PEO-PPO-PEO, F127) simultaneously occur. After thermal treatment, Ru@OMC catalysts with mesoporous channels, narrow pore-size distribution (≈7 nm), and high surface area (up to 779 m2 g-1 ) were directed by F127 micelles. Meanwhile, the Zn2+ ions dilute Ru3+ and avoid the sintering of Ru species, resulting in Ru clusters around 1.4-1.7 nm during carbonization (800 °C). Moreover, the Ru@OMC catalyst afforded a good activity (TOF: up to 4170 h-1 ) in the selective oxidation of benzyl alcohol to benzaldehyde by molecular oxygen.

16.
Adv Sci (Weinh) ; 6(10): 1802066, 2019 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-31131190

RESUMO

Iron single atom catalysts (Fe SACs) are the best-known nonprecious metal (NPM) catalysts for the oxygen reduction reaction (ORR) of polymer electrolyte membrane fuel cells (PEMFCs), but their practical application has been constrained by the low Fe SACs loading (<2 wt%). Here, a one-pot pyrolysis method is reported for the synthesis of iron single atoms on graphene (FeSA-G) with a high Fe SAC loading of ≈7.7 ± 1.3 wt%. The as-synthesized FeSA-G shows an onset potential of 0.950 V and a half-wave potential of 0.804 V in acid electrolyte for the ORR, similar to that of Pt/C catalysts but with a much higher stability and higher phosphate anion tolerance. High temperature SiO2 nanoparticle-doped phosphoric acid/polybenzimidazole (PA/PBI/SiO2) composite membrane cells utilizing a FeSA-G cathode with Fe SAC loading of 0.3 mg cm-2 delivers a peak power density of 325 mW cm-2 at 230 °C, better than 313 mW cm-2 obtained on the cell with a Pt/C cathode at a Pt loading of 1 mg cm-2. The cell with FeSA-G cathode exhibits superior stability at 230 °C, as compared to that with Pt/C cathode. Our results provide a new approach to developing practical NPM catalysts to replace Pt-based catalysts for fuel cells.

17.
J Am Chem Soc ; 141(22): 8928-8936, 2019 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-31090414

RESUMO

The failure to achieve stable Ohmic contacts in two-dimensional material devices currently limits their promised performance and integration. Here we demonstrate that a phase transformation in a region of a layered semiconductor, PdSe2, can form a contiguous metallic Pd17Se15 phase, leading to the formation of seamless Ohmic contacts for field-effect transistors. This phase transition is driven by defects created by exposure to an argon plasma. Cross-sectional scanning transmission electron microscopy is combined with theoretical calculations to elucidate how plasma-induced Se vacancies mediate the phase transformation. The resulting Pd17Se15 phase is stable and shares the same native chemical bonds with the original PdSe2 phase, thereby forming an atomically sharp Pd17Se15/PdSe2 interface. These Pd17Se15 contacts exhibit a low contact resistance of ∼0.75 kΩ µm and Schottky barrier height of ∼3.3 meV, enabling nearly a 20-fold increase of carrier mobility in PdSe2 transistors compared to that of traditional Ti/Au contacts. This finding opens new possibilities in the development of better electrical contacts for practical applications of 2D materials.

18.
Phys Rev Lett ; 122(10): 106101, 2019 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-30932633

RESUMO

In addition to their unique optical and electronic properties, two-dimensional materials provide opportunities to directly observe atomic-scale defect dynamics. Here we use scanning transmission electron microscopy to observe substitutional Re impurities in monolayer MoS_{2} undergo direct exchanges with neighboring Mo atoms in the lattice. Density-functional-theory calculations find that the energy barrier for direct exchange, a process that has only been studied as a diffusion mechanism in bulk materials, is too large for either thermal activation or energy directly transferred from the electron beam. The presence of multiple sulfur vacancies next to the exchanged Re-Mo pair, as observed by electron microscopy, does not lower the energy barrier sufficiently to account for the observed atomic exchange. Instead, the calculations find that a Re dopant and surrounding sulfur vacancies introduce an ever-changing set of deep levels in the energy gap. We propose that these levels mediate an "explosive" recombination-enhanced migration via multiple electron-hole recombination events. As a proof of concept, we also show that Re-Mo direct exchange can be triggered via controlled creation of sulfur vacancies. The present experimental and theoretical findings lay a fundamental framework towards manipulating single substitutional dopants in two-dimensional materials.

19.
Nanotechnology ; 30(30): 305601, 2019 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-30986768

RESUMO

Silver (Ag) nanoparticles can be spontaneously oxidized and present in different oxidized surface phases. The impact of oxidation induced photo absorption property and related photocatalytic activity are still unclear in Ag-decorated semiconductor photocatalysts. Herein, Ag-decorated BiOCl with the metallic Ag0 to oxidized Ag+ were employed to investigate the effect of surface state of Ag on relative photocatalyst properties. A redshift of localized surface plasmon resonance was observed as the Ag0 oxidized to Ag+ and a reversible manipulation was realized in UV light-driven photocatalysis. It is found that the Ag0/BiOCl presents higher photocatalytic activity than Ag+/BiOCl, but this difference is gradually decreasing under UV light irradiation compared with visible light irradiation. A controlled experiment suggests that the reduction of Ag+ under UV light reduced the difference between Ag0/BiOCl and Ag+/BiOCl. The possible mechanism for electron transport and the conversion between Ag+ and Ag0 via the assistance of the photoelectric effect from BiOCl has been elucidated. This photocatalytic reaction assisted reversible tuning the surface state of Ag/BiOCl will open up the possibility of rationally designing Ag-decorated semiconductors for light harvesting.

20.
Nanoscale ; 11(15): 7239-7246, 2019 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-30931452

RESUMO

Highly active, low-cost, and durable electrocatalysts for the water oxidation reaction are pivotal in energy conversion and storage schemes. Here we report a nitride-core, oxide-shell-armor structured FeCoNi oxynitride as an efficient oxygen evolution electrocatalyst with a homogeneous nitride (Fe0.70Co0.56Ni0.92N1.0O0.06) core and an oxide (Fe0.48Co0.1Ni0.21N0.05O1.0) shell. The catalyst demonstrated excellent activity for the oxygen evolution reaction with a current density of 10 mA cm-2 at a low overpotential of 0.291 V in alkaline media (1 M KOH), which is superior to the activities of commercial IrO2, RuO2, and Pt/C catalysts and comparable to those of state-of-the-art catalysts (e.g., NiFe-LDH, NiCo2O4, O-NiCoFe-LDH). Density functional theory simulations suggested that the incorporation of multiple metal elements can indeed improve the reaction energetics with a synergistic effect from the core-shell structure. This unique structure of a nitride-core with a oxide-shell presents a new form of multimetallic oxynitride with compelling performance in electrolytic oxygen evolution.

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