- Anisotropy of piezocaloric effect at ferroelectric phase transitions in ammonium hydrogen sulphate
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The role of anisotropy of the thermal expansion in formation of piezocaloric effect (PCE) near ferroelectric phase transitions in NH4HSO4 was studied. Strong difference in linear baric coefficients and as a result in intensive and extensive PCE associated with the different crystallographic axes was found. PCE giving the main contribution to the barocaloric effect were determined at both phase transitions. Rather strong effect of the lattice dilatation on the tuning of PCE was observed. Comparative analysis of PCE at the phase transitions in different materials showed that NH4HSO4 can be considered as a promising solid-state refrigerant. A hypothetical cooling cycle based on alternate using uniaxial pressure along two axes was considered.
- Flerov, Igor N.,Gorev, Mikhail V.,Kartashev, Andrey V.,Mikhaleva, Ekaterina A.,Molokeev, Maxim S.
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- Boosting the acidic electrocatalytic nitrogen reduction performance of MoS2 by strain engineering
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It has been widely confirmed that expanding the layer spacing of layer-structured MoS2 can boost the hydrogen evolution reaction (HER) activity of MoS2. Inspired by this, a strain engineering strategy was applied to defect-rich MoS2 nanosheets by facilely substituting F to compress the interlayer space of MoS2. Because of the smaller size and higher electronegativity of F as compared to S, the catalytic HER was remarkably suppressed. By considering the strongly reduced uphill energy for the hydrogenation of adsorbed N2 on MoS2 due to the introduction of F ions, as revealed by first-principles calculations, electrochemical nitrogen reduction reaction (NRR) activity and selectivity on the F-doped MoS2 (F-MoS2) catalyst under acidic conditions can be significantly boosted. Faradaic efficiency toward the NRR on F-MoS2 was therefore enhanced to 20.6% with a maximum NH3 yield of 35.7 μg h-1 mgcat-1 at -0.2 V vs. RHE during long-term operation.
- Cai, Weiwei,Li, Jing,Liang, Jiawei,Liu, Zhao,Ma, Shuangxiu,Qu, Konggang,Wang, Yangang,Wu, Junli,Yang, Zehui,Zhang, Quan
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supporting information
p. 10426 - 10432
(2020/06/09)
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- Heptanuclear antiferromagnetic Fe(III)-d-(-)-quinato assemblies with an S = 3/2 ground state - PH-specific synthetic chemistry, spectroscopic, structural, and magnetic susceptibility studies
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Iron is an essential metal ion with numerous roles in biological systems and advanced abiotic materials. d-(-)-Quinic acid is a cellular metal ion chelator, capable of promoting reactions with metal M(II,III) ions under pH-specific conditions. In an effort to comprehend the chemical reactivity of well-defined forms of Fe(III)/Fe(II) toward α-hydroxycarboxylic acids, pH-specific reactions of: (a) [Fe3O(CH3COO) 6(H2O)3]·(NO3)·4H 2O with d-(-)-quinic acid in a molar ratio 1:3 at pH 2.5 and (b) Mohr's salt with d-(-)-quinic acid in a molar ratio 1:3 at pH 7.5, respectively, led to the isolation of the first two heptanuclear Fe(III)-quinato complexes, [Fe7O3(OH)3(C7H10O 6)6]·20.5H2O (1) and (NH 4)[Fe7(OH)6(C7H10O 6)6]·(SO4)2·18H 2O (2). Compounds 1 and 2 were characterized by analytical, spectroscopic (UV-vis, FT-IR, EPR, and Moessbauer) techniques, CV, TGA-DTG, and magnetic susceptibility measurements. The X-ray structures of 1 and 2 reveal heptanuclear assemblies of six Fe(III) ions bound by six doubly deprotonated quinates and one Fe(III) ion bound by oxido- and hydroxido-bridges (1), and hydroxido-bridges (2), all in an octahedral fashion. Moessbauer spectroscopy on 1 and 2 suggests the presence of Fe(III) ions in an all-oxygen environment. EPR measurements indicate that 1 and 2 retain their structure in solution, while magnetic measurements reveal an overall antiferromagnetic behavior with a ground state S = 3/2. The collective physicochemical properties of 1 and 2 suggest that the (a) nature of the ligand, (b) precursor form of iron, (c) pH, and (d) molecular stoichiometry are key factors influencing the chemical reactivity of the binary Fe(II,III)-hydroxycarboxylato systems, their aqueous speciation, and ultimately through variably emerging hydrogen bonding interactions, the assembly of multinuclear Fe(III)-hydroxycarboxylato clusters with distinct lattice architectures of specific dimensionality (2D-3D) and magnetic signature.
- Menelaou,Vournari,Psycharis,Raptopoulou,Terzis,Tangoulis,Sanakis,Mateescu,Salifoglou
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p. 13849 - 13860
(2014/01/06)
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