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1.
J Am Chem Soc ; 2020 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-32282192

RESUMO

Sensitization of a wide-gap oxide semiconductor with a visible-light-absorbing dye has been studied for decades as a means of producing H2 from water. However, efficient overall water splitting using a dye-sensitized oxide photocatalyst has remained an unmet challenge. Here we demonstrate visible-light-driven overall water splitting into H2 and O2 using HCa2Nb3O10 nanosheets sensitized by a Ru(II) tris-diimine type photosensitizer, in combination with a WO3-based water oxidation photocatalyst and a triiodide/iodide redox couple. With the use of Pt-intercalated HCa2Nb3O10 nanosheets further modified with amorphous Al2O3 clusters as the H2 evolution component, the dye-based turnover number and frequency for H2 evolution reached 4580 and 1960 h-1, respectively. The apparent quantum yield for overall water splitting using 420 nm light was 2.4%, by far the highest among dye-sensitized overall water splitting systems reported to date. The present work clearly shows that a carefully designed dye/oxide hybrid has great potential for photocatalytic H2 production, and represents a significant leap forward in the development of solar-driven water splitting systems.

2.
Angew Chem Int Ed Engl ; 59(24): 9736-9743, 2020 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-32134159

RESUMO

Undoped layered oxynitrides have not been considered as promising H2 -evolution photocatalysts because of the low chemical stability of oxynitrides in aqueous solution. Here, we demonstrate the synthesis of a new layered perovskite oxynitride, K2 LaTa2 O6 N, as an exceptional example of a water-tolerant photocatalyst for H2 evolution under visible light. The material underwent in-situ H+ /K+ exchange in aqueous solution while keeping its visible-light-absorption capability. Protonated K2 LaTa2 O6 N, modified with an Ir cocatalyst, exhibited excellent catalytic activity toward H2 evolution in the presence of I- as an electron donor and under visible light; the activity was six times higher than Pt/ZrO2 /TaON, one of the best-performing oxynitride photocatalysts for H2 evolution. Overall water splitting was also achieved using the Ir-loaded, protonated K2 LaTa2 O6 N in combination with Cs-modified Pt/WO3 as an O2 evolution photocatalyst in the presence of an I3 - /I- shuttle redox couple.

3.
Inorg Chem ; 58(9): 6161-6166, 2019 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-30990027

RESUMO

Two-dimensional (2D) layered oxynitrides are promising candidates as visible-light-driven photocatalysts, but the actual examples are rare because of the difficulty in synthesizing the 2D oxynitrides. Here a phase-pure layered perovskite, Rb2NdNb2O6N·H2O, that belongs to a tetragonal P4/ mmm space group was successfully synthesized by thermal ammonolysis of a mixture of layered RbNdNb2O7 and Rb2CO3, as revealed by synchrotron X-ray diffraction, elemental analyses, and atomic-scale electron microscopy observation. The synthesized Rb2NdNb2O6N·H2O had an absorption edge at around 500 nm and a sufficiently high conduction-band potential to allow for proton reduction. With modification by a platinum cocatalyst, Rb2NdNb2O6N·H2O became photocatalytically active for H2 evolution in the presence of triethanolamine as an electron donor under visible light (λ > 400 nm).

4.
J Am Chem Soc ; 141(6): 2446-2450, 2019 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-30563330

RESUMO

Infrared (IR) light represents an untapped energy source accounting for almost half of all solar energy. Thus, there is a need to develop systems to convert IR light to fuel and make full use of this plentiful resource. Herein, we report photocatalytic H2 evolution driven by near- to shortwave-IR light (up to 2500 nm) irradiation, based on novel CdS/Cu7S4 heterostructured nanocrystals. The apparent quantum yield reached 3.8% at 1100 nm, which exceeds the highest efficiencies achieved by IR light energy conversion systems reported to date. Spectroscopic results revealed that plasmon-induced hot-electron injection at p-n heterojunctions realizes exceptionally long-lived charge separation (>273 µs), which results in efficient IR light to hydrogen conversion. These results pave the way for the exploration of undeveloped low-energy light for solar fuel generation.

5.
Nanoscale Res Lett ; 13(1): 403, 2018 Dec 11.
Artigo em Inglês | MEDLINE | ID: mdl-30539346

RESUMO

Inefficient Mg-induced p-type doping has been remained a major obstacle in the development of GaN-based electronic devices for solid-state lighting and power applications. This study reports comparative structural analysis of defects in GaN layers on freestanding GaN substrates where Mg incorporation is carried out via two approaches: ion implantation and epitaxial doping. Scanning transmission electron microscopy revealed the existence of pyramidal and line defects only in Mg-implanted sample whereas Mg-doped sample did not show presence of these defects which suggests that nature of defects depends upon incorporation method. From secondary ion mass spectrometry, a direct correspondence is observed between Mg concentrations and location and type of these defects. Our investigations suggest that these pyramidal and line defects are Mg-rich species and their formation may lead to reduced free hole densities which is still a major concern for p-GaN-based material and devices. As freestanding GaN substrates offer a platform for realization of p-n junction-based vertical devices, comparative structural investigation of defects originated due to different Mg incorporation processes in GaN layers on such substrates is likely to give more insight towards understanding Mg self-compensation mechanisms and then optimizing Mg doping and/or implantation process for the advancement of GaN-based device technology.

6.
J Am Chem Soc ; 140(48): 16396-16401, 2018 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-30444605

RESUMO

Optical properties of aqueous colloidal dispersions of 2D electrolytes, if their aspect ratios are extra-large, can be determined by their orientation preferences. Recently, we reported that a colloidal dispersion of diamagnetic titanate(IV) nanosheets (TiIVNSs), when placed in a magnetic field, is highly anisotropic because TiIVNS anomalously orients its 2D plane orthogonal to the magnetic flux lines due to its large anisotropic magnetic susceptibility. Herein, we report a serendipitous finding that TiIVNSs can be in situ photochemically reduced into a paramagnetic species (TiIV/IIINSs), so that their preference of magnetic orientation changes from orthogonal to parallel. This transition distinctly alters the structural anisotropy and therefore optical appearance of the colloidal dispersion in a magnetic field. We also found that TiIV/IIINSs is autoxidized back to TiIVNSs under non-deaerated conditions. By using an elaborate setup, the dispersion of TiIVNSs serves as an optical switch remotely operable by magnet and light.

7.
Sci Rep ; 8(1): 12325, 2018 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-30120323

RESUMO

Annular dark-field (ADF) imaging by scanning transmission electron microscopy (STEM) is a common technique for material characterization with high spatial resolution. It has been reported that ADF signal is proportional to the nth power of the atomic number Z, i.e., the Z contrast in textbooks and papers. Here we first demonstrate the deviation from the power-law model by quantitative experiments of a few 2D materials (graphene, MoS2 and WS2 monolayers). Then we elucidate ADF signal of single atoms using simulations to clarify the cause of the deviation. Two major causes of the deviation from the power-law model will be pointed out. The present study provides a practical guideline for the usage of the conventional power-law model for ADF imaging.

8.
Adv Mater ; 30(31): e1801968, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-29920799

RESUMO

Thin-film photovoltaics (PV) have emerged as a technology that can meet the growing demands for efficient and low-cost large-scale cells. However, the photoabsorbers currently in use contain expensive or toxic elements, and the difficulty in bipolar doping, particularly in a device structure, requires elaborate optimization of the heterostructures for improving the efficiency. This study shows that bipolar doping with high hole and electron mobilities in copper nitride (Cu3 N), composed solely of earth-abundant and environmentally benign elements, is readily available through a novel gaseous direct nitriding reaction applicable to uniform and large-area deposition. A high-quality undoped Cu3 N film is essentially an n-type semiconductor, while p-type conductivity is realized by interstitial fluorine doping, as predicted using density functional theory calculations and directly proven by atomically resolved imaging. The synthetic methodology for high-quality p-type and n-type films paves the way for the application of Cu3 N as an alternative absorber in thin-film PV.

9.
Angew Chem Int Ed Engl ; 57(27): 8154-8158, 2018 07 02.
Artigo em Inglês | MEDLINE | ID: mdl-29737628

RESUMO

Oxynitrides are promising visible-light-responsive photocatalysts, but their structures are almost confined with three-dimensional (3D) structures such as perovskites. A phase-pure Li2 LaTa2 O6 N with a layered perovskite structure was successfully prepared by thermal ammonolysis of a lithium-rich oxide precursor. Li2 LaTa2 O6 N exhibited high crystallinity and visible-light absorption up to 500 nm. As opposed to well-known 3D oxynitride perovskites, Li2 LaTa2 O6 N supported by a binuclear RuII complex was capable of stably and selectively converting CO2 into formate under visible light (λ>400 nm). Transient absorption spectroscopy indicated that, as compared to 3D oxynitrides, Li2 LaTa2 O6 N possesses a lower density of mid-gap states that work as recombination centers of photogenerated electron/hole pairs, but a higher density of reactive electrons, which is responsible for the higher photocatalytic performance of this layered oxynitride.

10.
Inorg Chem ; 57(11): 6686-6691, 2018 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-29750517

RESUMO

We synthesized a silver iron oxyfluoride AgFeOF2 by using a high-pressure reaction. Synchrotron X-ray and neutron diffraction, X-ray absorption, and 57Fe Mössbauer spectroscopy indicate that AgFeOF2 crystallizes in the ideal perovskite structure with iron in a trivalent state, although electron microscopy revealed weak super-reflections. A possible partial ordering in the FeO2F4 octahedron is inferred from Mössbauer spectroscopy. The synthesis of the fluorine-rich sample offers an opportunity to study a composition-property relation in AFeIIIO3- nF n ( n = 0, 1, and 2). AgFeOF2 exhibits a G-type antiferromagnetic ordering below TN ≈ 480 K, which is much lower than the n = 0 and 1 cases, suggesting a weaker superexchange interaction between Fe moments via F 2p orbitals (vs O 2p orbitals).

11.
Microscopy (Oxf) ; 67(suppl_1): i72-i77, 2018 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-29370378

RESUMO

Chemical bonding state of sodium borosilicide Na8B74.5Si17.5, which is a new member of B12-cluster materials, is investigated by soft X-ray emission spectroscopy. The material is composed of B12 cluster network and characteristic silicon chains of [-Si-(Si-Si)3-Si-] connected by sp3 bonding, in which bonding distances and bonding angles are close to those in cubic Si crystal. B K-emission spectrum of the material showed a similar but a broader intensity distribution with those of B12 cluster materials of α-r-B, B4C and ß-r-B. The broader intensity distribution can be due to a variation of B-B bond length in B12 cluster. The density of states (DOS) of silicon chains of [-Si-(Si-Si)3-Si-] was experimentally derived. It shows a similar energy width, and peak or shoulder structures in intensity distribution with those of L-emission spectrum of cubic Si. From comparisons between experimental spectra and corresponding calculated DOS, covalent bonding between Si chain and B12 cluster network is suggested. Those are discussed by using a theoretically calculated density of state of Na8B74.5Si17.5 by using WIEN2k code.

12.
Ultramicroscopy ; 180: 59-65, 2017 09.
Artigo em Inglês | MEDLINE | ID: mdl-28343726

RESUMO

The aberrations of the objective lens should be measured and adjusted to realize high spatial resolution in scanning transmission electron microscopy (STEM). Here we report a method of measuring low-order aberrations using the Fourier transforms of Ronchigrams of an arbitrary crystal such as a specimen of interest. We have applied this technique to measure first- and second-order geometrical aberrations using typical standard specimens. Focus and twofold astigmatism are measured using two Ronchigrams obtained under different foci. Axial coma and threefold astigmatism are evaluated using the Fourier transforms of small subareas of a Ronchigram. The time dependences of focus and twofold astigmatism are examined using this technique for an aberration-corrected microscope.

13.
Micron ; 93: 52-56, 2017 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-27923156

RESUMO

This paper describes the effective solid angle improvement achieved using a large-area silicon drift detector together with a virtual-pivot double-tilt specimen holder. The virtual-pivot mechanism enables various designs of specimen-retaining and can reduce the shadowing effect. Energy-dispersive X-ray spectra were measured and converted into effective solid angles using different types of specimen holders and specimens. The investigated shadowing-free mechanical system yielded effective solid angles approaching the nominal solid angle of 0.464sr. In addition, we have demonstrated the availability of the plastic (polyetheretherketone) specimen holder for low system noise.

14.
Microsc Microanal ; 22(5): 971-980, 2016 10.
Artigo em Inglês | MEDLINE | ID: mdl-27786152

RESUMO

The resolution of high-resolution transmission electron microscopes (TEM) has been improved down to subangstrom levels by correcting the spherical aberration (Cs) of the objective lens, and the information limit is thus determined mainly by partial temporal coherence. As a traditional Young's fringe test does not reveal the true information limit for an ultra-high-resolution electron microscope, new methods to evaluate temporal coherence have been proposed based on a tilted-beam diffractogram. However, the diffractogram analysis cannot be applied when the nonlinear contribution becomes significant. Therefore, we have proposed a method based on the three-dimensional (3D) Fourier transform (FT) of through-focus TEM images, and evaluated the performance of some Cs-corrected TEMs at lower voltages. In this report, we generalize the 3D FT analysis and derive the 3D transmission cross-coefficient. The profound difference of the 3D FT analysis from the diffractogram analysis is its capability to extract linear image information from the image intensity, and further to evaluate two linear image contributions separately on the Ewald sphere envelopes. Therefore, contrary to the diffractogram analysis the 3D FT analysis can work with a strong scattering object. This is the necessary condition if we want to directly observe the linear image transfer down to a few tens of picometer.

15.
Nanoscale ; 8(18): 9517-20, 2016 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-27118533

RESUMO

We synthesized a heterotetrapod composed of a chalcopyrite(ch)-CuInS2 core and wurtzite(w)-CdS arms and elucidated its optical properties and light-stimulated carrier dynamics using fs-laser flash photolysis. The CuInS2/CdS heterotetrapod possessed quasi-type II band alignment, which caused much longer-lived charge separation than that in the isolated CuInS2 nanocrystal.

16.
Sci Rep ; 6: 24616, 2016 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-27087005

RESUMO

The lateral distribution and coverage of Ru-based dye molecules, which are used for dye-sensitized solar cells (DSCs), were directly examined on a titania surface using high-resolution scanning transmission electron microscopy (STEM). The clean surface of a free-standing titania nanosheet was first confirmed with atomic resolution, and then, the nanosheet was used as a substrate. A single dye molecule on the titania nanosheet was visualized for the first time. The quantitative STEM images revealed an inhomogeneous dye-molecule distribution at the early stage of its absorption, i.e., the aggregation of the dye molecules. The majority of the titania surface was not covered by dye molecules, suggesting that optimization of the dye molecule distribution could yield further improvement of the DSC conversion efficiencies.

17.
J Chem Phys ; 144(11): 114703, 2016 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-27004889

RESUMO

Triphenylphosphine ligand-protected Au9 clusters deposited onto titania nanosheets show three different atomic configurations as observed by scanning transmission electron microscopy. The configurations observed are a 3-dimensional structure, corresponding to the previously proposed Au9 core of the clusters, and two pseudo-2-dimensional (pseudo-2D) structures, newly found by this work. With the help of density functional theory (DFT) calculations, the observed pseudo-2D structures are attributed to the low energy, de-ligated structures formed through interaction with the substrate. The combination of scanning transmission electron microscopy with DFT calculations thus allows identifying whether or not the deposited Au9 clusters have been de-ligated in the deposition process.

18.
Microscopy (Oxf) ; 64(6): 409-18, 2015 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-26347577

RESUMO

We have investigated how accurately atomic-resolution annular dark-field (ADF) images match between experiments and simulations to conduct more reliable crystal structure analyses. Quantitative ADF imaging, in which the ADF intensity at each pixel represents the fraction of the incident probe current, allows us to perform direct comparisons with simulations without the use of fitting parameters. Although the conventional comparison suffers from experimental uncertainties such as an amorphous surface layer and specimen thickness, in this study we eliminated such uncertainties by using a single-layer graphene as a specimen. Furthermore, to reduce image distortion and shot noises in experimental images, multiple acquisitions with drift correction were performed, and the atomic ADF contrast was quantitatively acquired. To reproduce the experimental ADF contrast, we used three distribution functions as the effective source distribution in simulations. The optimum distribution function and its full-width at half-maximum were evaluated by measuring the residuals between the experimental and simulated images. It was found that the experimental images could be explained well by a linear combination of a Gaussian function and a Lorentzian function with a longer tail than the Gaussian function.

19.
Chem Commun (Camb) ; 51(43): 8974-7, 2015 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-25930246

RESUMO

Here, we report the synthesis of semiconducting single-walled carbon nanotubes with a narrow diameter distribution between 0.67 and 1.1 nm via chemical vapour deposition on graphene layers using Pt catalysts.

20.
Phys Rev Lett ; 114(10): 107601, 2015 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-25815966

RESUMO

Spatially resolved electron-energy-loss spectroscopy (EELS) is performed at diffuse interfaces between MoS2 and MoSe2 single layers. With a monochromated electron source (20 meV) we successfully probe excitons near the interface by obtaining the low loss spectra at the nanometer scale. The exciton maps clearly show variations even with a 10 nm separation between measurements; consequently, the optical band gap can be measured with nanometer-scale resolution, which is 50 times smaller than the wavelength of the emitted photons. By performing core-loss EELS at the same regions, we observe that variations in the excitonic signature follow the chemical composition. The exciton peaks are observed to be broader at interfaces and heterogeneous regions, possibly due to interface roughness and alloying effects. Moreover, we do not observe shifts of the exciton peak across the interface, possibly because the interface width is not much larger than the exciton Bohr radius.

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