Catalysts for oxygen evolution reactions (OER) and hydrogen evolution reactions (HER) are central to key renewable energy technologies, including fuel cells and water splitting. Despite tremendous effort, the development of low-cost electrode catalysts with high activity remains a great challenge. In this study, we report the synthesis of CoSe2 and NiSe2 nanocrystals (NCs) as excellent bifunctional catalysts for simultaneous generation of H2 and O2 in water-splitting reactions. NiSe2 NCs exhibit superior electrocatalytic efficiency in OER, with a Tafel slope (b) of 38 mV dec(-1) (in 1 M KOH), and HER, with b = 44 mV dec(-1) (in 0.5 M H2SO4). In comparison, CoSe2 NCs are less efficient for OER (b = 50 mV dec(-1)), but more efficient for HER (b = 40 mV dec(-1)). It was found that CoSe2 NCs contained more metallic metal ions than NiSe2, which could be responsible for their improved performance in HER. Robust evidence for surface oxidation suggests that the surface oxide layers are the actual active sites for OER, and that CoSe2 (or NiSe2) under the surface act as good conductive layers. The higher catalytic activity of NiSe2 is attributed to their oxide layers being more active than those of CoSe2. Furthermore, we fabricated a Si-based photoanode by depositing NiSe2 NCs onto an n-type Si nanowire array, which showed efficient photoelectrochemical water oxidation with a low onset potential (0.7 V versus reversible hydrogen electrode) and high durability. The remarkable catalytic activity, low cost, and scalability of NiSe2 make it a promising candidate for practical water-splitting solar cells.
Abstract:The levels of aspartate aminotransferase (AST/GOT) and alanine aminotransferase (ALT/GPT) in serum can help people diagnose body tissues especially the heart and the liver are injured or not. This article provides a comprehensive review of research activities that concentrate on AST/GOT and ALT/GPT detection techniques due to their clinical importance. The detection techniques include colorimetric, spectrophotometric, chemiluminescence, chromatography, fluorescence and UV absorbance, radiochemical, and electrochemical techniques. We devote the most attention on experimental principle. In some methods a few representative devices and important conclusions are presented.
Graphene-like two-dimensional (2D) nanostructures have attracted significant attention because of their unique quantum confinement effect at the 2D limit. Multilayer nanosheets of GaS-GaSe alloy are found to have a band gap (Eg) of 2.0-2.5 eV that linearly tunes the emission in red-to-green. However, the epitaxial growth of monolayers produces a drastic increase in this Eg to 3.3-3.4 eV, which blue-shifts the emission to the UV region. First-principles calculations predict that the Eg of these GaS and GaSe monolayers should be 3.325 and 3.001 eV, respectively. As the number of layers is increased to three, both the direct/indirect Eg decrease significantly; the indirect Eg approaches that of the multilayers. Oxygen adsorption can cause the direct/indirect Eg of GaS to converge, resulting in monolayers with a strong emission. This wide Eg tuning over the visible-to-UV range could provide an insight for the realization of full-colored flexible and transparent light emitters and displays.
Sn-based nanostructures have emerged as promising alternative materials for commercial lithium-graphite anodes in lithium ion batteries (LIBs). However, there is limited information on their phase evolution during the discharge/charge cycles. In the present work, we comparatively investigated how the phases of Sn, tin sulfide (SnS), and tin oxide (SnO2) nanocrystals (NCs) changed during repeated lithiation/delithiation processes. All NCs were synthesized by a convenient gas-phase photolysis of tetramethyl tin. They showed excellent cycling performance with reversible capacities of 700 mAh/g for Sn, 880 mAh/g for SnS, and 540 mAh/g for SnO2 after 70 cycles. Tetragonal-phase Sn (β-Sn) was produced upon lithiation of SnS and SnO2 NCs. Remarkably, a cubic phase of diamond-type Sn (α-Sn) coexisting with β-Sn was produced by lithiation for all NCs. As the cycle number increased, α-Sn became the dominant phase. First-principles calculations of the Li intercalation energy of α-Sn (Sn8) and β-Sn (Sn4) indicate that Sn4Li(x) (x ≤ 3) is thermodynamically more stable than Sn8Li(x) (x ≤ 6) when both have the same composition. α-Sn maintains its crystalline form, while β-Sn becomes amorphous upon lithiation. Based on these results, we suggest that once α-Sn is produced, it can retain its crystallinity over the repeated cycles, contributing to the excellent cycling performance.
Various germanium-based nanostructures have recently demonstrated outstanding lithium ion storage ability and are being considered as the most promising candidates to substitute current carbonaceous anodes of lithium ion batteries. However, there is limited understanding of their structure and phase evolution during discharge/charge cycles. Furthermore, the theoretical model of lithium insertion still remains a challenging issue. Herein, we performed comparative studies on the cycle-dependent lithiation/delithiation processes of germanium (Ge), germanium sulfide (GeS), and germanium oxide (GeO2) nanocrystals (NCs). We synthesized the NCs using a convenient gas phase laser photolysis reaction and attained an excellent reversible capacity: 1100-1220 mAh/g after 100 cycles. Remarkably, metastable tetragonal (ST12) phase Ge NCs were constantly produced upon lithiation and became the dominant phase after a few cycles, completely replacing the original phase. The crystalline ST12 phase persisted through 100 cycles. First-principles calculations on polymorphic lithium-intercalated structures proposed that the ST12 phase Ge12Lix structures at x ≥ 4 become more thermodynamically stable than the cubic phase Ge8Lix structures with the same stoichiometry. The production and persistence of the ST12 phase can be attributed to a stronger binding interaction of the lithium atoms compared to the cubic phase, which enhanced the cycling performance.
Germanium-tin (Ge(1-x)Sn(x)) alloy nanocrystals were synthesized using a gas-phase laser photolysis reaction of tetramethyl germanium and tetramethyl tin. A composition tuning was achieved using the partial pressure of precursors in a closed reactor. For x < 0.1, cubic phase alloy nanocrystals were exclusively produced without separation of the tetragonal phase Sn metal. In the range of x = 0.1-0.4, unique Ge(1-x)Sn(x)-Sn alloy-metal hetero-junction nanocrystals were synthesized, where the Sn metal domain becomes dominant with x. Thin graphitic carbon layers usually sheathed the nanocrystals. We investigated the composition-dependent electrochemical properties of these nanocrystals as anode materials of lithium ion batteries. Incorporation of Sn (x = 0.05) significantly increased the capacities (1010 mA h g(-1) after 50 cycles) and rate capabilities, which promises excellent electrode materials for the development of high-performance lithium batteries.
Catalysts for the oxygen reduction and evolution reactions are central to key renewable-energy technologies including fuel cells and water splitting. Despite tremendous effort, the development of oxygen electrode catalysts with high activity at low cost remains a great challenge. In this study, we report a generalized sol–gel method for the synthesis of various oxide nanocrystals (TiO2, ZnO, Nb2O5, In2O3, SnO2, and Ta2O5) with appropriate transition metal dopants for an efficient electrocatalytic oxygen evolution reaction (OER). Although TiO2 and ZnO nanocrystals alone have little activity, all the Mn-, Fe-, Co-, and Ni-doped nanocrystals exhibit greatly enhanced OER activity. A remarkable finding is that Co dopant produces higher OER activity than the other doped metals. X-ray photoelectron and X-ray absorption spectroscopies revealed the highly oxidized metal ions that are responsible for the enhanced catalytic reactivity. The excellent OER activity of the Co-doped nanocrystals was explained by a synergistic effect in which the oxide matrix effectively guards the most active Co dopants at higher oxidation states by withdrawing the electrons from the metal dopants. The metal-doped NCs exhibit enhanced catalytic activity under visible light irradiation, suggesting their potential as efficient solar-driven OER photoelectrocatalysts.
Germanium sulfide (GeS and GeS2) nanoparticles were synthesized by novel gas-phase laser photolysis and subsequent thermal annealing. They showed excellent cycling performance for lithium ion batteries, with a maximum capacity of 1010 mA h g(-1) after 100 cycles. Metastable tetragonal phase Ge nanoparticles were suggested as active materials for a reversible lithium insertion-extraction process.
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