9 research outputs found
Solution-Processed Planar Perovskite Solar Cell Without a Hole Transport Layer
Solar
cells with a structure of ITO/ZnO/CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub>/graphite/carbon black electrode were fabricated by
spin coating at ambient conditions. PbI<sub>2</sub> thin films were
converted into CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> perovskite
by reacting with CH<sub>3</sub>NH<sub>3</sub>I in solution. The incorporation
of electrochemically exfoliated graphite improved the fill factor,
open circuit potential and short circuit current density. The best
device yielded 10.2% power conversion efficiency
Three Unique Barium Manganese Vanadates from High-Temperature Hydrothermal Brines
Three
new barium manganese vanadates, all containing hexagonal barium chloride
layers interpenetrated by [V<sub>2</sub>O<sub>7</sub>]<sup>4–</sup> groups, were synthesized using a high-temperature (580 °C)
hydrothermal method. Two of the compounds were prepared from a mixed
BaCl<sub>2</sub>/Ba(OH)<sub>2</sub> mineralizer, and the third compound
was prepared from BaCl<sub>2</sub> mineralizer. An interesting structural
similarity exists between two of the compounds, Ba<sub>2</sub>Mn(V<sub>2</sub>O<sub>7</sub>)(OH)Cl and Ba<sub>4</sub>Mn<sub>2</sub>(V<sub>2</sub>O<sub>7</sub>)(VO<sub>4</sub>)<sub>2</sub>O(OH)Cl. These two
compounds crystallize in the orthorhombic space group <i>Pnma</i>, <i>Z</i> = 4, and are structurally related by a nearly
doubled <i>a</i> axis. The first structure, Ba<sub>2</sub>Mn(V<sub>2</sub>O<sub>7</sub>)(OH)Cl (<b>I</b>) (<i>a</i> = 15.097(3) Å, <i>b</i> = 6.1087(12) Å, <i>c</i> = 9.5599(19) Å), consists of octahedral manganese(II)
edge-sharing chains linked by pyrovanadate [V<sub>2</sub>O<sub>7</sub>] groups, generating a three-dimensional structure. Compound <b>II</b>, Ba<sub>4</sub>Mn<sub>2</sub>(V<sub>2</sub>O<sub>7</sub>)(VO<sub>4</sub>)<sub>2</sub>O(OH)Cl (<i>a</i> = 29.0814(11)
Å, <i>b</i> = 6.2089(2) Å, <i>c</i> =
9.5219(4) Å), is composed of manganese(III) edge-sharing chains
that are coordinated to one another through pyrovanadate groups in
a nearly identical way as in <b>I</b>, forming a zigzag layer.
A key difference in <b>II</b> is that these layers are capped
on either end by two monomeric [VO<sub>4</sub>] groups that directly
replace one [V<sub>2</sub>O<sub>7</sub>] group in <b>I</b>.
The third compound, Ba<sub>5</sub>Mn<sub>3</sub>(V<sub>2</sub>O<sub>7</sub>)<sub>3</sub>(OH,Cl)Cl<sub>3</sub> (<b>III</b>), crystallizes
in the trigonal space group <i>R</i>32 (<i>a</i> = 9.7757(4) Å, <i>c</i> = 22.4987(10) Å) and
is composed of manganese(II) trimeric units, [Mn<sub>3</sub>O<sub>12</sub>(OH,Cl)], coordinated to one another through pyrovanadate
[V<sub>2</sub>O<sub>7</sub>] groups to form a three-dimensional structure.
The unusual manganese trimers are built of three square pyramids all
linked by a central (OH/Cl) atom. The key factor directing the formation
of the different structures appears to be the identity and concentration
of the halide brine mineralizer fluid. The ability of such brines
to induce the formation of interpenetrated salt lattices in the present
study is suggestive of a versatile realm of descriptive synthetic
inorganic chemistry
Three Unique Barium Manganese Vanadates from High-Temperature Hydrothermal Brines
Three
new barium manganese vanadates, all containing hexagonal barium chloride
layers interpenetrated by [V<sub>2</sub>O<sub>7</sub>]<sup>4–</sup> groups, were synthesized using a high-temperature (580 °C)
hydrothermal method. Two of the compounds were prepared from a mixed
BaCl<sub>2</sub>/Ba(OH)<sub>2</sub> mineralizer, and the third compound
was prepared from BaCl<sub>2</sub> mineralizer. An interesting structural
similarity exists between two of the compounds, Ba<sub>2</sub>Mn(V<sub>2</sub>O<sub>7</sub>)(OH)Cl and Ba<sub>4</sub>Mn<sub>2</sub>(V<sub>2</sub>O<sub>7</sub>)(VO<sub>4</sub>)<sub>2</sub>O(OH)Cl. These two
compounds crystallize in the orthorhombic space group <i>Pnma</i>, <i>Z</i> = 4, and are structurally related by a nearly
doubled <i>a</i> axis. The first structure, Ba<sub>2</sub>Mn(V<sub>2</sub>O<sub>7</sub>)(OH)Cl (<b>I</b>) (<i>a</i> = 15.097(3) Å, <i>b</i> = 6.1087(12) Å, <i>c</i> = 9.5599(19) Å), consists of octahedral manganese(II)
edge-sharing chains linked by pyrovanadate [V<sub>2</sub>O<sub>7</sub>] groups, generating a three-dimensional structure. Compound <b>II</b>, Ba<sub>4</sub>Mn<sub>2</sub>(V<sub>2</sub>O<sub>7</sub>)(VO<sub>4</sub>)<sub>2</sub>O(OH)Cl (<i>a</i> = 29.0814(11)
Å, <i>b</i> = 6.2089(2) Å, <i>c</i> =
9.5219(4) Å), is composed of manganese(III) edge-sharing chains
that are coordinated to one another through pyrovanadate groups in
a nearly identical way as in <b>I</b>, forming a zigzag layer.
A key difference in <b>II</b> is that these layers are capped
on either end by two monomeric [VO<sub>4</sub>] groups that directly
replace one [V<sub>2</sub>O<sub>7</sub>] group in <b>I</b>.
The third compound, Ba<sub>5</sub>Mn<sub>3</sub>(V<sub>2</sub>O<sub>7</sub>)<sub>3</sub>(OH,Cl)Cl<sub>3</sub> (<b>III</b>), crystallizes
in the trigonal space group <i>R</i>32 (<i>a</i> = 9.7757(4) Å, <i>c</i> = 22.4987(10) Å) and
is composed of manganese(II) trimeric units, [Mn<sub>3</sub>O<sub>12</sub>(OH,Cl)], coordinated to one another through pyrovanadate
[V<sub>2</sub>O<sub>7</sub>] groups to form a three-dimensional structure.
The unusual manganese trimers are built of three square pyramids all
linked by a central (OH/Cl) atom. The key factor directing the formation
of the different structures appears to be the identity and concentration
of the halide brine mineralizer fluid. The ability of such brines
to induce the formation of interpenetrated salt lattices in the present
study is suggestive of a versatile realm of descriptive synthetic
inorganic chemistry
Honeycomb-like S = 5/2 Spin–Lattices in Manganese(II) Vanadates
New
complex manganese vanadate materials were synthesized as high-quality
single crystals in multi-millimeter lengths using a high-temperature,
high-pressure hydrothermal method. One compound, Mn<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, was grown from Mn<sub>2</sub>O<sub>3</sub> and V<sub>2</sub>O<sub>5</sub> in 3 M CsOH at 580 °C
and 1.5 kbar. Changing the mineralizer to 1 M CsOH/3MCsCl leads to
the formation of another product, Mn<sub>6</sub>O(VO<sub>4</sub>)<sub>2</sub>(OH). Both compounds were structurally characterized by single-crystal
X-ray diffraction (Mn<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>: <i>C</i>2/<i>m</i>, <i>Z</i> = 2, <i>a</i> = 9.6568(9) Å, <i>b</i> =
9.5627(9) Å, <i>c</i> = 5.4139(6) Å, β =
98.529(8)°; Mn<sub>6</sub>O(VO<sub>4</sub>)<sub>2</sub>(OH): <i>P</i>2<sub>1</sub>/<i>m</i>, <i>Z</i> =
2, <i>a</i> = 8.9363(12) Å, <i>b</i> = 6.4678(8)
Å, <i>c</i> = 10.4478(13) Å, β = 99.798(3)°),
revealing interesting low-dimensional transition-metal features. Mn<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub> possesses complex
honeycomb-type Mn–O layers, built from edge-sharing [MnO<sub>6</sub>] octahedra in the <i>bc</i> plane, with bridging
vanadate groups connecting these layers along the <i>a</i>-axis. Mn<sub>6</sub>O(VO<sub>4</sub>)<sub>2</sub>(OH) presents a
more complicated structure with both octahedral [MnO<sub>6</sub>]
and trigonal bipyramidal [MnO<sub>5</sub>] units. A different pattern
of planar honeycomb sheets are formed by edge-shared [MnO<sub>6</sub>] octahedra, and these sublattices are connected through edge-shared
dimers of [MnO<sub>5</sub>] trigonal bipyramids to form corrugated
sheets. Vanadate groups again condense the sheets into a three-dimensional
framework. Infrared and Raman spectroscopies indicated the presence
of OH groups and displayed characteristic Raman scattering due to
vanadate groups. Temperature-dependent magnetic studies indicated
Curie–Weiss behavior above 100 K with significant anti-ferromagnetic
coupling for both compounds, with further complex magnetic behavior
at lower temperatures. The data indicate canted anti-ferromagnetic
order below 57 K in Mn<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub> and below 45 K in Mn<sub>6</sub>O(VO<sub>4</sub>)<sub>2</sub>(OH). Members of another class of compounds, K<sub>2</sub>M<sub>3</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>2</sub> (M = Mn, Co), also containing
a honeycomb-type sublattice, were also synthesized to allow a comparison
of the structural features across all three structure types and to
demonstrate extension to other transition metals
Honeycomb-like S = 5/2 Spin–Lattices in Manganese(II) Vanadates
New
complex manganese vanadate materials were synthesized as high-quality
single crystals in multi-millimeter lengths using a high-temperature,
high-pressure hydrothermal method. One compound, Mn<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>, was grown from Mn<sub>2</sub>O<sub>3</sub> and V<sub>2</sub>O<sub>5</sub> in 3 M CsOH at 580 °C
and 1.5 kbar. Changing the mineralizer to 1 M CsOH/3MCsCl leads to
the formation of another product, Mn<sub>6</sub>O(VO<sub>4</sub>)<sub>2</sub>(OH). Both compounds were structurally characterized by single-crystal
X-ray diffraction (Mn<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub>: <i>C</i>2/<i>m</i>, <i>Z</i> = 2, <i>a</i> = 9.6568(9) Å, <i>b</i> =
9.5627(9) Å, <i>c</i> = 5.4139(6) Å, β =
98.529(8)°; Mn<sub>6</sub>O(VO<sub>4</sub>)<sub>2</sub>(OH): <i>P</i>2<sub>1</sub>/<i>m</i>, <i>Z</i> =
2, <i>a</i> = 8.9363(12) Å, <i>b</i> = 6.4678(8)
Å, <i>c</i> = 10.4478(13) Å, β = 99.798(3)°),
revealing interesting low-dimensional transition-metal features. Mn<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub> possesses complex
honeycomb-type Mn–O layers, built from edge-sharing [MnO<sub>6</sub>] octahedra in the <i>bc</i> plane, with bridging
vanadate groups connecting these layers along the <i>a</i>-axis. Mn<sub>6</sub>O(VO<sub>4</sub>)<sub>2</sub>(OH) presents a
more complicated structure with both octahedral [MnO<sub>6</sub>]
and trigonal bipyramidal [MnO<sub>5</sub>] units. A different pattern
of planar honeycomb sheets are formed by edge-shared [MnO<sub>6</sub>] octahedra, and these sublattices are connected through edge-shared
dimers of [MnO<sub>5</sub>] trigonal bipyramids to form corrugated
sheets. Vanadate groups again condense the sheets into a three-dimensional
framework. Infrared and Raman spectroscopies indicated the presence
of OH groups and displayed characteristic Raman scattering due to
vanadate groups. Temperature-dependent magnetic studies indicated
Curie–Weiss behavior above 100 K with significant anti-ferromagnetic
coupling for both compounds, with further complex magnetic behavior
at lower temperatures. The data indicate canted anti-ferromagnetic
order below 57 K in Mn<sub>5</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>4</sub> and below 45 K in Mn<sub>6</sub>O(VO<sub>4</sub>)<sub>2</sub>(OH). Members of another class of compounds, K<sub>2</sub>M<sub>3</sub>(VO<sub>4</sub>)<sub>2</sub>(OH)<sub>2</sub> (M = Mn, Co), also containing
a honeycomb-type sublattice, were also synthesized to allow a comparison
of the structural features across all three structure types and to
demonstrate extension to other transition metals
Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba<sub>2</sub>M(VO<sub>4</sub>)<sub>2</sub>(OH), M = V<sup>3+</sup>, Mn<sup>3+</sup>, and Fe<sup>3+</sup>, with Interesting Jahn–Teller and Spin-Liquid Behavior
A new
series of transition metal vanadates, namely, Ba<sub>2</sub>M(VO<sub>4</sub>)<sub>2</sub>(OH) (M = V<sup>3+</sup>, Mn<sup>3+</sup>, and
Fe<sup>3+</sup>), was synthesized as large single crystals hydrothermally
in 5 M NaOH solution at 580 °C and 1 kbar. This new series of
compounds is structurally reminiscent of the brackebuschite mineral
type. The structure of Ba<sub>2</sub>V(VO<sub>4</sub>)<sub>2</sub>(OH) is monoclinic in space group <i>P</i>2<sub>1</sub>/<i>m</i>, <i>a</i> = 7.8783(2) Å, <i>b</i> = 6.1369(1) Å, <i>c</i> = 9.1836(2) Å,
β = 113.07(3)°, <i>V</i> = 408.51(2) Å<sup>3</sup>. The other structures are similar and consist of one-dimensional
trans edge-shared distorted octahedral chains running along the <i>b</i>-axis. The vanadate groups bridge across edges of their
tetrahedra. Structural analysis of the Ba<sub>2</sub>Mn(VO<sub>4</sub>)<sub>2</sub>(OH) analogue yielded a new understanding of the
Jahn–Teller effect in this structure type. Raman and infrared
spectra were investigated to observe the fundamental vanadate and
hydroxide vibrational modes. Single-crystal temperature-dependent
magnetic studies on Ba<sub>2</sub>V(VO<sub>4</sub>)<sub>2</sub>(OH) reveal a broad feature over a wide temperature range with maximum
at ∼100 K indicating that an energy gap could exist between
the antiferromagnetic singlet ground state and excited triplet states,
making it potentially of interest for quantum magnetism studies
Tuning Localized Surface Plasmon Resonance Wavelengths of Silver Nanoparticles by Mechanical Deformation
We
describe a simple technique to alter the shape of silver nanoparticles
(AgNPs) by rolling a glass tube over them to mechanically compress
them. The resulting shape change in turn induces a red-shift in the
localized surface plasmon resonance scattering spectrum and exposes
new surface area. The flattened particles were characterized by optical
and electron microscopy, single-nanoparticle scattering spectroscopy,
and surface-enhanced Raman spectroscopy (SERS). Atomic force microscopy
and scanning electron microscopy images show that the AgNPs deform
into discs; increasing the applied load from 0 to 100 N increases
the AgNP diameter and decreases the height. This deformation caused
a dramatic red shift in the nanoparticle scattering spectrum and also
generated new surface area to which thiolated molecules could attach,
as evident from SERS measurements. The simple technique employed here
requires no lithographic templates and has potential for rapid, reproducible,
inexpensive, and scalable tuning of nanoparticle shape, surface area,
and resonance while preserving particle volume
One-Pot Hydrothermal Synthesis of Tb<sup>III</sup><sub>13</sub>(GeO<sub>4</sub>)<sub>6</sub>O<sub>7</sub>(OH) and K<sub>2</sub>Tb<sup>IV</sup>Ge<sub>2</sub>O<sub>7</sub>: Preparation of a Stable Terbium(4+) Complex
Two
terbium germanates have been synthesized via high-temperature and
high-pressure hydrothermal synthesis with 20 M KOH as a mineralizer
using Tb<sub>4</sub>O<sub>7</sub> as a starting material. Tb<sub>13</sub>(GeO<sub>4</sub>)<sub>6</sub>O<sub>7</sub>(OH) crystallizes in trigonal
space group <i>R</i>3̅, is built up of isolated GeO<sub>4</sub> units, and contains a complex arrangement of terbium oxide
polyhedra. K<sub>2</sub>TbGe<sub>2</sub>O<sub>7</sub> is a terbium(4+)
pyrogermanate that is isostructural with K<sub>2</sub>ZrGe<sub>2</sub>O<sub>7</sub> and displays a rare stable Tb<sup>4+</sup> oxidation
state in the solid state
Highly Conductive and Transparent Reduced Graphene Oxide Nanoscale Films via Thermal Conversion of Polymer-Encapsulated Graphene Oxide Sheets
Despite
noteworthy progress in the fabrication of large-area graphene sheetlike
nanomaterials, the vapor-based processing still requires sophisticated
equipment and a multistage handling of the material. An alternative
approach to manufacturing functional graphene-based films includes
the employment of graphene oxide (GO) micrometer-scale sheets as precursors.
However, search for a scalable manufacturing technique for the production
of high-quality GO nanoscale films with high uniformity and high electrical
conductivity is still continuing. Here we show that conventional dip-coating
technique can offer fabrication of high quality mono- and bilayered
films made of GO sheets. The method is based on our recent discovery
that encapsulating individual GO sheets in a nanometer thick molecular
brush copolymer layer allows for the nearly perfect formation of the
GO layers via dip coating from water. By thermal reduction the bilayers
(cemented by a carbon-forming polymer linker) are converted into highly
conductive and transparent reduced GO films with a high conductivity
up to 10<sup>4</sup> S/cm and optical transparency on the level of
90%. The value is the highest electrical conductivity reported for
thermally reduced nanoscale GO films and is close to the conductivity
of indium tin oxide currently in use for transparent electronic devices,
thus making these layers intriguing candidates for replacement of
ITO films