skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Photocatalytic hydrogen evolution on Si photocathodes modified with bis(thiosemicarbazonato)nickel( ii )/Nafion
The molecular catalyst diacetyl-bis( N -4-methyl-3-thiosemi-carbazonato)nickel( ii ) (NiATSM) was integrated with Si for light-driven hydrogen evolution from water. Compared to an equivalent loading of Ni metal, the NiATSM/p-Si electrode performed better. Durability of the surface-bound catalyst under operation in acid was achieved without covalent attachment by using Nafion binding.  more » « less
Award ID(s):
1665136 1800245
PAR ID:
10163197
Author(s) / Creator(s):
; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Chemical Communications
Volume:
55
Issue:
64
ISSN:
1359-7345
Page Range / eLocation ID:
9440 to 9443
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. PurposeTo determine if contemporary 0.55 T MRI supports the use of contrast‐optimal flip angles (FA) for simultaneous multi‐slice (SMS) balanced SSFP (bSSFP) cardiac function assessment, which is impractical at conventional field strengths because of excessive SAR and/or banding artifacts. MethodsBlipped‐CAIPI bSSFP was combined with spiral sampling for ventricular function assessment at 0.55 T. Cine movies with single band and SMS factors of 2 and 3 (SMS 2 and 3), and FA ranging from 60° to 160°, were acquired in seven healthy volunteers. Left ventricular blood and myocardial signal intensity (SI) normalized by background noise and blood–myocardium contrast were measured and compared across acquisition settings. ResultsMyocardial SI was slightly higher in single band than in SMS and decreased with an increasing FA. Blood SI increased as the FA increased for single band, and increment was small for FA ≥120°. Blood SI for SMS 2 and 3 increased with an increasing FA up to ∼100°. Blood–myocardium contrast increased with an increasing FA for single band, peaked at FA = 160° (systole: 28.43, diastole: 29.15), attributed mainly to reduced myocardial SI when FA ≥120°. For SMS 2, contrast peaked at 120° (systole: 21.43, diastole: 19.85). For SMS 3, contrast peaked at 120° in systole (16.62) and 100° in diastole (19.04). ConclusionsContemporary 0.55 T MR scanners equipped with high‐performance gradient systems allow the use of contrast‐optimal FA for SMS accelerated bSSFP cine examinations without compromising image quality. The contrast‐optimal FA was found to be 140° to 160° for single band and 100° to 120° for SMS 2 and 3. 
    more » « less
  2. A uranium(iii) silylate complex [K(DME)4]-[UI2{(Si(SiMe3)2SiMe2)2O}] (1) was stabilized by the addition of 18-crown-6 to form [K(18-crown-6)][UI2{(Si(SiMe3)2SiMe2)2O}]. This species was fully characterized using multinuclear NMR spectroscopy, electronic absorption spectroscopy and X-ray crystallography. 
    more » « less
  3. Abstract The catalytic hydrothermal liquefaction of biomass under a hydrogen atmosphere is a promising technology to produce stable biocrude oil as a sustainable alternative to petroleum crude. A series of iron‐based non‐noble mix metal‐oxide‐on‐silica catalysts were evaluated to mimic the natural transformation that may have led to the conversion of terrestrial biomass to fossilized fuels. Switchgrass powder was liquefied to a stable bio‐oil with a 71.2% yield by using FeOx/SiO2catalyst in ethanol under a 5.5 MPa hydrogen atmosphere at 210 °C. The use of Fe‐MOx/SiO2(M = V, Mn, Co, Ni, Cu and Mo) type bimetallic oxide catalysts instead of FeOx/SiO2can produce improvements in liquefaction yields by using Mn, Co, Ni, and Cu as the second metal. The highest liquefaction yield of 78.8% was observed with the Fe‐CuOx/SiO2catalyst. Liquefaction oils were formed that were composed of complex mixtures of C6‐C12 alcohols, esters, aldehydes, and phenols. The lignin products:holocellulose products ratio changed in the range 0.35 to 0.15 and the composition of oils changed significantly with the use of mixed metal oxides in place of single metal FeOx/SiO2The most effective catalyst, Fe‐CuOx/SiO2could be reused in five cycles with a small loss in liquefaction yield from 78.8% to 70.0% after four reuse cycles and after regeneration of the catalyst at 500 °C for 3 h in air. 
    more » « less
  4. Indium on silica, alumina and zeolite chabazite (CHA), with a range of In/Al ratios and Si/Al ratios, have been investigated to understand the effect of the support on indium speciation and its corresponding influence on propane dehydrogenation (PDH). It is found that In 2 O 3 is formed on the external surface of the zeolite crystal after the addition of In(NO 3 ) 3 to H-CHA by incipient wetness impregnation and calcination. Upon reduction in H 2 gas (550 °C), indium displaces the proton in Brønsted acid sites (BASs), forming extra-framework In + species (In-CHA). A stoichiometric ratio of 1.5 of formed H 2 O to consumed H 2 during H 2 pulsed reduction experiments confirms the indium oxidation state of +1. The reduced indium is different from the indium species observed on samples of 10In/SiO 2 , 10In/Al 2 O 3 ( i.e. , 10 wt% indium) and bulk In 2 O 3 , in which In 2 O 3 was reduced to In(0), as determined from the X-ray diffraction patterns of the product, H 2 temperature-programmed reduction (H 2 -TPR) profiles, pulse reactor investigations and in situ transmission FTIR spectroscopy. The BASs in H-CHA facilitate the formation and stabilization of In + cations in extra-framework positions, and prevent the deep reduction of In 2 O 3 to In(0). In + cations in the CHA zeolite can be oxidized with O 2 to form indium oxide species and can be reduced again with H 2 quantitatively. At comparable conversion, In-CHA shows better stability and C 3 H 6 selectivity (∼85%) than In 2 O 3 , 10In/SiO 2 and 10In/Al 2 O 3 , consistent with a low C 3 H 8 dehydrogenation activation energy (94.3 kJ mol −1 ) and high C 3 H 8 cracking activation energy (206 kJ mol −1 ) in the In-CHA catalyst. A high Si/Al ratio in CHA seems beneficial for PDH by decreasing the fraction of CHA cages containing multiple In + cations. Other small-pore zeolite-stabilized metal cation sites could form highly stable and selective catalysts for this and facilitate other alkane dehydrogenation reactions. 
    more » « less
  5. This research reports the development of 3D carbon nanostructures that can provide unique capabilities for manufacturing carbon nanotube (CNT) electronic components, electrochemical probes, biosensors, and tissue scaffolds. The shaped CNT arrays were grown on patterned catalytic substrate by chemical vapor deposition (CVD) method. The new fabrication process for catalyst patterning based on combination of nanoimprint lithography (NIL), magnetron sputtering, and reactive etching techniques was studied. The optimal process parameters for each technique were evaluated. The catalyst was made by deposition of Fe and Co nanoparticles over an alumina support layer on a Si/SiO2 substrate. The metal particles were deposited using direct current (DC) magnetron sputtering technique, with a particle ranging from 6 nm to 12 nm and density from 70 to 1000 particles/micron. The Alumina layer was deposited by radio frequency (RF) and reactive pulsed DC sputtering, and the effect of sputtering parameters on surface roughness was studied. The pattern was developed by thermal NIL using Si master-molds with PMMA and NRX1025 polymers as thermal resists. Catalyst patterns of lines, dots, and holes ranging from 70 nm to 500 nm were produced and characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Vertically aligned CNTs were successfully grown on patterned catalyst and their quality was evaluated by SEM and micro-Raman. The results confirm that the new fabrication process has the ability to control the size and shape of CNT arrays with superior quality. 
    more » « less