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Title: Addition of Monovalent Silver Cations to CH 3 NH 3 PbBr 3 Produces Crystallographically Oriented Perovskite Thin Films
Authors:
; ; ; ; ; ; ; ; ; ; ; ; ;
Award ID(s):
1702944 1822206 1540028 1624659
Publication Date:
NSF-PAR ID:
10155536
Journal Name:
ACS Applied Energy Materials
Volume:
2
Issue:
8
Page Range or eLocation-ID:
6087 to 6096
ISSN:
2574-0962
Sponsoring Org:
National Science Foundation
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  1. Abstract

    Carbonyl-bearing complex organic molecules (COMs) in the interstellar medium (ISM) are of significant importance due to their role as potential precursors to biomolecules. Simple aldehydes and ketones like acetaldehyde, acetone, and propanal have been recognized as fundamental molecular building blocks and tracers of chemical processes involved in the formation of distinct COMs in molecular clouds and star-forming regions. Although previous laboratory simulation experiments and modeling established the potential formation pathways of interstellar acetaldehyde and propanal, the underlying formation routes to the simplest ketone—acetone—in the ISM are still elusive. Herein, we performed a systematic study to unravel the synthesis of acetone, its propanal and propylene oxide isomers, as well as the propenol tautomers in interstellar analog ices composed of methane and acetaldehyde along with isotopic-substitution studies to trace the reaction pathways of the reactive intermediates. Chemical processes in the ices were triggered at 5.0 K upon exposure to proxies of Galactic cosmic rays in the form of energetic electrons. The products were detected isomer-selectively via vacuum ultraviolet (VUV) photoionization reflectron time-of-flight mass spectrometry. In our experiments, the branching ratio of acetone (CH3COCH3):propylene oxide (c-CH3CHOCH2):propanal (CH3CH2CHO) was determined to be (4.82 ± 0.05):(2.86 ± 0.13):1. The radical–radical recombination reaction leading tomore »acetone emerged as the dominant channel. The propenols appeared only at a higher radiation dose via keto–enol tautomerization. The current study provides mechanistic information on the fundamental nonequilibrium pathways that may be responsible for the formation of acetone and its (enol) isomers inside the interstellar icy grains.

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  2. Two new alkali vanadate carbonates with divalent transition metals have been synthesized as large single crystals via a high-temperature (600 °C) hydrothermal technique. Compound I , Rb 2 Mn 3 (VO 4 ) 2 CO 3 , crystallizes in the trigonal crystal system in the space group P 3̄1 c , and compound II , K 2 Co 3 (VO 4 ) 2 CO 3 , crystallizes in the hexagonal space group P 6 3 / m . Both structures contain honeycomb layers and triangular lattices made from edge-sharing MO 6 octahedra and MO 5 trigonal bipyramids, respectively. The honeycomb and triangular layers are connected along the c -axis through tetrahedral [VO 4 ] groups. The MO 5 units are connected with each other by carbonate groups in the ab -plane by forming a triangular magnetic lattice. The difference in space groups between I and II was also investigated with Density Functional Theory (DFT) calculations. Single crystal magnetic characterization of I indicates three magnetic transitions at 77 K, 2.3 K, and 1.5 K. The corresponding magnetic structures for each magnetic transition of I were determined using single crystal neutron diffraction. At 77 K the compound orders in the MnO 6more »-honeycomb layer in a Néel-type antiferromagnetic orientation while the MnO 5 triangular lattice ordered below 2.3 K in a colinear ‘up–up–down’ fashion, followed by a planar ‘Y’ type magnetic structure. K 2 Co 3 (VO 4 ) 2 CO 3 ( II ) exhibits a canted antiferromagnetic ordering below T N = 8 K. The Curie–Weiss fit (200–350 K) gives a Curie–Weiss temperature of −42 K suggesting a dominant antiferromagnetic coupling in the Co 2+ magnetic sublattices.« less