2018 New's Items

Secondary Building Units as the Turning Point in the Development of the Reticular Chemistry of MOFs

M. J. Kalmutzki
N. Hanikel
O. M. Yaghi
2018

The secondary building unit (SBU) approach was a turning point in the discovery of permanently porous metal-organic frameworks (MOFs) and in launching the field of reticular chemistry. In contrast to the single-metal nodes known in coordination networks, the polynuclear nature of SBUs allows these structures to serve as rigid, directional, and stable building units in the design of robust crystalline materials with predetermined structures and properties. This concept has also enabled the development of MOFs with ultra-high porosity and structural complexity. The architectural,...

Cytoprotective Metal-organic Frameworks for Anaerobic Bacteria

Z. Ji
H. Zhang
H. Liu
O. M. Yaghi
P. Yang
2018

We report a strategy to uniformly wrap Morella thermoacetica bacteria with a metal-organic framework (MOF) monolayer of nanometer thickness for cytoprotection in artificial photosynthesis. The catalytic activity of the MOF enclosure toward decomposition of reactive oxygen species (ROS) reduces the death of strictly anaerobic bacteria by fivefold in the presence of 21% O2, and enables the cytoprotected bacteria to continuously produce acetate from CO2 fixation under oxidative stress. The high definition of the...

Bacteria Photosensitized by Intracellular Gold Nanoclusters for Solar Fuel Production

Hao Zhang
Hao Liu
Zhiquan Tian
Dylan Lu
Yi Yu
Stefano Cestellos-Blanco
Kelsey Sakimoto
Peidong Yang
2018

The demand for renewable and sustainable fuel has prompted the rapid development of advanced nanotechnologies to effectively harness solar power. The construction of photosynthetic biohybrid systems (PBSs) aims to link preassembled biosynthetic pathways with inorganic light absorbers. This strategy inherits both the high light-harvesting efficiency of solid-state semiconductors and the superior catalytic performance of whole-cell microorganisms. Here, we introduce an intracellular, biocompatible light absorber, in the form of gold nanoclusters (AuNCs), to circumvent the sluggish...

Quantitative modeling of energy dissipation in Arabidopsis thaliana

J. M. Morris
G. R. Fleming
2018

In photosynthesis, solar energy is absorbed and converted into chemical energy. Chlorophyll embedded in proteins absorb light and transfer excitation energy to reaction centers where charge separation occurs. However, the solar flux incident on photosynthetic organisms is highly variable, requiring complex feedback systems to regulate the excitation pressure on reaction centers and prevent excess absorbed energy from causing damage. During periods of transient high light, excess absorbed energy is dissipated as heat. This is routinely observed as the quenching of chlorophyll...

Giant Light-Emission Enhancement in Lead Halide Perovskites by Surface Oxygen Passivation

D. Lu
Y. Zhang
M. Lai
A. Lee
C. Xie
J. Lin
T. Lei
Z. Lin
C. Kley
J. Huang
E. Rabani
P. Yang
2018

Surface condition plays an important role in the optical performance of semiconductor materials. As new types of semiconductors, the emerging metal-halide perovskites are promising for next-generation optoelectronic devices. We discover significantly improved light-emission efficiencies in lead halide perovskites due to surface oxygen passivation. The enhancement manifests close to 3 orders of magnitude as the perovskite dimensions decrease to the nanoscale, improving external quantum efficiencies from <0.02% to over 12%. Along with about a 4-fold increase in spontaneous carrier...

Dynamics of Nanoscale Dendrite Formation in Solution Growth Revealed Through in Situ Liquid Cell Electron Microscopy

M. R. Hauwiller
X. Zhang
W-I. Liang
C.-H. Chiu
Q. Zhang
W. Zheng
C. Ophus
E. M. Chan
C. Czarnik
M. Pan
F. M. Ross
W.-W. Wu
Y.-H. Chu
M. Asta
P. W. Voorhees
A. P. Alivisatos
H. Zheng
2018

Formation mechanisms of dendrite structures have been extensively explored theoretically, and many theoretical predictions have been validated for micro- or macroscale dendrites. However, it is challenging to determine whether classical dendrite growth theories are applicable at the nanoscale due to the lack of detailed information on the nanodendrite growth dynamics. Here, we study iron oxide nanodendrite formation using liquid cell transmission electron microscopy (TEM). We observe “seaweed”-like iron oxide nanodendrites growing predominantly in two dimensions on the membrane of a...

Crystalline Dioxin-Linked Covalent Organic Frameworks from Irreversible Reactions

B. Zhang
M. Wei
H. Mao
X. Pei
S. A. Alshmimri
J. A. Reimer
O. M. Yaghi
2018

Triangular 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and linear tetrafluorophthalonitrile (TFPN) or 2,3,5,6-tetrafluoro-4-pyridinecarbonitrile (TFPC) were linked by 1,4-dioxin linkages to form crystalline 2D covalent organic frameworks, termed COF-316 and -318. Unlike the condensation reactions commonly used to crystallize the great majority of COFs, the reactions used in this report are based on nucleophilic aromatic substitution reactions (SNAr) that are considered irreversible. Our studies show that the reactivity of TFPN and TFPC with HHTP is enhanced...

Exciton and Phonon Dynamics in Highly Aligned 7-Atom Wide Armchair Graphene Nanoribbons as Seen by Time-Resolved Spontaneous Raman Scattering

Zhu, J.
German, R.
Senkovsky, B. V.
Haberer, D.
Fischer, F. R.
Grüneis, A.
Van Loosdrecht, P. H. M.
2018

The opening of a band gap in graphene nanoribbons induces novel optical and electronic properties, strongly enhancing their application potential in nanoscale devices. Knowledge of the optical excitations and associated relaxation dynamics are essential for developing and optimizing device designs and functionality. Here we report on the optical excitations and associated relaxation dynamics in surface aligned 7-atom wide armchair graphene nanoribbons as seen by time-resolved spontaneous Stokes and anti-Stokes Raman scattering spectroscopy. On the anti-Stokes side we observe an...

Formation of the Layered Conductive Magnet CrCl2(pyrazine)2 Through Redox-Active Coordination Chemistry

K. Pedersen
P. Perlepe
M. Aubrey
D. N. Woodruff
S. Reyes-Lillo
A. Reinholdt
L. Voig
Z. Li
K. Borup
M. Rouzieres
D. Samohvalov
F. Wilhelm
A. Rogalev
J. B. Neaton
2018

The unique properties of graphene, transition-metal dichalcogenides and other two-dimensional (2D) materials have boosted interest in layered coordination solids. In particular, 2D materials that behave as both conductors and magnets could find applications in quantum magnetoelectronics and spintronics. Here, we report the synthesis of CrCl2(pyrazine)2, an air-stable layered solid, by reaction of CrCl2 with pyrazine (pyz). This compound displays a ferrimagnetic order below 55 K,...

Effects of Ambient Humidity and Temperature on the NO2 Sensing Characteristics of WS2/Graphen Aerogel

W. Yan
M. Worsley
T. Pham
A. Zettl
C. Carraro
R. Maboudian
2018

The effects of ambient humidity and temperature on the NO2 sensing characteristics of WS2/graphene aerogel (WS2/GA) composite are investigated. In order to probe the gas sensing performances of WS2/GA, the sensor is fabricated by integrating WS2/GA with a microfabricated two-electrode device. The WS2/GA is characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray...