2017 New's Items

Dendrimer-Stabilized Metal Nanoparticles as Efficient Catalysts for Reversible Dehydrogenation/Hydrogenation of N-Heterocycles

C. Deraedt
R. Ye
W. T. Ralston
F. D. Toste
G. A. Somorjai
2017

Nanoparticles (Pd, Pt, Rh) stabilized by G4OH PAMAM dendrimers and supported in SBA-15 (MNPs/SBA-15 with M = Pd, Pt, Rh) were efficiently used as catalysts in the acceptorless dehydrogenation of tetrahydroquinoline/indoline derivatives in toluene (release of H2) at 130 °C. These catalysts are air stable, very active, robust, and recyclable during the process. The reverse hydrogenation reaction of quinoline derivatives (H2 storage) was also optimized and successfully performed in the presence of the same...

Snapshot Transient Absorption Spectroscopy of Carotenoid Radical Cations in High-Light-Acclimating Thylakoid Membranes

S. Park
A. L. Fischer
Z. Li
R. Bassi
K. K. Niyogi
G. R. Fleming
2017

Nonphotochemical quenching mechanisms regulate light harvesting in oxygenic photosynthesis. Measurement techniques for nonphotochemical quenching have typically focused on downstream effects of quenching, such as measuring reduced chlorophyll fluorescence. Here, to directly measure a species involved in quenching, we report snapshot transient absorption (TA) spectroscopy, which rapidly tracks carotenoid radical cation signals as samples acclimate to excess light. The formation of zeaxanthin radical cations, which is possible evidence of zeaxanthin-chlorophyll charge-transfer (CT)...

Discovery and Characterization of a Pourbaix-Stable, 1.8 eV Direct Gap Bismuth Manganate Photoanode

P. Newhouse
S. Reyes-Lillo
G. Li
L. Zhou
A. Shinde
D. Guevarra
S. Suram
E. Soedarmadji
M. Richter
X. Qu
K. Persson
J. B. Neaton
J. M. Gregoire
2017

Solar-driven oxygen evolution is a critical technology for renewably synthesizing hydrogen- and carbon-containing fuels in solar fuel generators. New photoanode materials are needed to meet efficiency and stability requirements, motivating materials explorations for semiconductors with (i) band-gap energy in the visible spectrum and (ii) stable operation in aqueous electrolyte at the electrochemical potential needed to evolve oxygen from water. Motivated by the oxygen evolution competency of many Mn-based oxides, the existence of several Bi-containing ternary oxide photoanode...

Fabrication of Subnanometer-Precision Nanopores in Hexagonal Boron Nitride

Gilbert
Dunn
Azizi
Pham
Shevitski
et al.
2017

We demonstrate the fabrication of individual nanopores in hexagonal boron nitride (h-BN) with atomically precise control of the pore shape and size. Previous methods of pore production in other 2D materials typically create pores with irregular geometry and imprecise diameters. In contrast, other studies have shown that with careful control of electron irradiation, defects in h-BN grow with pristine zig-zag edges at quantized triangular sizes, but they have failed to demonstrate production and control of isolated defects. In this work, we combine these techniques to yield a method in...

Inserting Porphyrin Quantum Dots in Bottom-Up Synthesized Graphene Nanoribbons

W. Perkins
F. R. Fischer
2017

Diels–Alder copolymerization of tetraphenylcyclopentadienone, a precursor for cove graphene nanoribbons (cGNRs), with bifunctional porphyrins yields defined nanostructures comprised of a single cGNR‐porphyrin‐cGNR heterojunction within each ribbon. 13C NMR labeling and high‐resolution mass spectrometry of solubilized polymer intermediates indicates that every porphyrin is covalently linked to two extended segments of cGNRs. UV/Vis absorption and fluorescence emission spectroscopy reveal a strong electronic correlation between the porphyrin and the adjacent...

A Reversible Single-Molecule Switch Based on Activated Antiaromaticity

X. Yin
Y. Zang
L. Zhu
J. Z. Low
Z. Liu
J. Cui
J. B. Neaton
L. Venkataraman
L. M. Campos
2017

Single-molecule electronic devices provide researchers with an unprecedented ability to relate novel physical phenomena to molecular chemical structures. Typically, conjugated aromatic molecular backbones are relied upon to create electronic devices, where the aromaticity of the building blocks is used to enhance conductivity. We capitalize on the classical physical organic chemistry concept of Hückel antiaromaticity by demonstrating a single-molecule switch that exhibits low conductance in the neutral state and, upon electrochemical oxidation, reversibly switches to an antiaromatic...

Cluster Decomposition of Full Configuration Interaction Wave Functions: A Tool for Chemical Interpretation of Systems with Strong Correlation

Lehtola S
Tubman NM
Whaley KB
Head-Gordon M
2017
Approximate full configuration interaction (FCI) calculations have recently become tractable for systems of unforeseen size, thanks to stochastic and adaptive approximations to the exponentially scaling FCI problem. The result of an FCI calculation is a weighted set of electronic configurations, which can also be expressed in terms of excitations from a reference configuration. The excitation amplitudes contain information on the complexity of the electronic wave function, but this information is contaminated by contributions from disconnected excitations, i.e., those excitations that are...

Ultraslow Waves on the Nanoscale

K. L. Tsakmakidis
O. Hess
R. W. Boyd
X. Zhang
2017

There has recently been a surge of interest in the physics and applications of broadband ultraslow waves in nanoscale structures operating below the diffraction limit. They range from light waves or surface plasmons in nanoplasmonic devices to sound waves in acoustic-metamaterial waveguides, as well as fermions and phonon polaritons in graphene and van der Waals crystals and heterostructures. We review the underlying physics of these structures, which upend traditional wave-slowing approaches based on resonances or on periodic configurations above the diffraction limit. Light can now...

Structural Phase Transition in Monolayer MoTe2 Driven by Electrostatic Doping

Y. Wang
J. Xiao
H. Zhu
Y. Li
Y. Alsaid
K. Fong
Y. Zhou
S. Wang
W. Shi
Y. Wang
A. Zettl
E. J. Reed
X. Zhang
2017

Monolayers of transition-metal dichalcogenides (TMDs) exhibit numerous crystal phases with distinct structures, symmetries and physical properties1,2,...

Topological Materials Discovery Using Electron Filling Constraints

R. Chen
H. C. Po
J. B. Neaton
A. Vishwanath
2017

Nodal semimetals are classes of topological materials that have nodal-point or nodal-line Fermi surfaces, which give them novel transport and topological properties. Despite being highly sought after, there are currently very few experimental realizations, and identifying new materials candidates has mainly relied on exhaustive database searches. Here we show how recent studies on the interplay between electron filling and nonsymmorphic space-group symmetries can guide the search for filling-enforced nodal semimetals. We recast the previously derived constraints on the allowed band-...