Browsing by Author "Chuang, Yu-Chun"

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Au-BINOL Hybrid Nanocatalysts: Insights into the Structure-Based Enhancement of Catalytic and Photocatalytic Performance
(2019-04-10)
Patolla, Shashank Reddy
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Kao, Chen-Rui
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Chen, Guan-Wei
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Huang, Yu-Cheng
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Chuang, Yu-Chun
Advances in new systems of organic-inorganic hybrid nanocomposites are less prevalent, owing to a lack of facile strategies for precise control of their structures, compositions, and, hence, their properties. In this work, Au-BINOL hybrid nanocomposites with eccentric and concentric nanostructures were produced. The hybrid nanocomposites containing two distinct moieties of inorganic Au nanocrystals and organic BINOL nanospheres were applied to the catalytic hydrogenation of 4-nitrophenol with NaBH4 in the aqueous phase with and without the illumination of visible light. Here, we demonstrate that the existence of Au-BINOL interfaces offers benefits to their performance. The eccentric nanostructures made with CTAC show the superior activity from large Au-BINOL interfaces formed between the BINOL nano spheres and the faces of Au nanoplates. They further exhibit a high Au localized surface plasmon resonance (LSPR)-enhancement effect on the photoreduction of 4-nitrophenol, which is attributed to the strong LSPR absorption of exposed Au nanocrystals unaffected by the coverage of BINOL shells.
Degradable NIR-PTT Nanoagents with a Potential Cu@Cu2O@Polymer Structure
(2018-02-14)
Tai, Yu-Wei
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Chiu, Yi-Chun
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Wu, Po-Ting
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Yu, Jiashing
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Chin, Yu-Cheng
Cu@Cu2O@PSMA polymer nanoparticles (Cu@Cu2O@polymer NPs) with near-infrared (NIR) absorption were successfully synthesized in a single-step oxidation reaction of Cu@PSMA polymer NPs at 100 degrees C for 20 min. The shape, structure, and optical properties of the Cu@Cu2O@polymer NPs were tailorable by controlling the reaction parameters, for example, using the initial Cu@PSMA polymer NP as a template and varying the halide ion content, heating temperature, and reaction time. The Cu@Cu2O@polymer NPs exhibited robust NIR absorption between 650 and 710 nm and possessed superior oxidation resistance in water and culture media. In vitro assays demonstrated the low cytotoxicity of the Cu@Cu2O@PSMA polymer NPs to HeLa cells through an improved cell viability, high IC50, low injury incidence from the supernatant of the partly dissociated Cu@Cu2O@PSMA polymer NPs, and minor generation of reactive oxygen species. More importantly, we demonstrated that the inorganic Cu-based nanocomposite [+0.34 V vs normal hydrogen electrode (NHE)] was degradable in an endogenous H2O2 (+1.78 V vs NHE) environment. Cu ions were detected in the urine of mice, which illustrates the possibility of extraction after the degradation of the Cu-based particles. 'After an treatment of the HeLa cells with the Cu@Cu2O@polymer NPs and a 660 nm light-emitting diode, the photoablation of 50 and 90% cells was observed at NP doses of 20 and 50 ppm, respectively. These results demonstrate that NIR-functional and moderate redox-active Cu@Cu2O@polymer NPs are potential next-generation photothermal therapy (PTT) nanoagents because of combined features of degradation resistance in the physiological environment, enabling the delivery of efficient PTT, a possibly improved ability to selectively harm cancer cells by releasing Cu ions under high-H2O2 and/or low-pH conditions, and ability to be extracted from the body after biodegradation.
Deviatoric deformation kinetics in high entropy alloy under hydrostatic compression
(2019-07-05)
Huang, E-Wen
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Lin, Chih-Ming
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Juang, Jenh-Yih
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Chang, Yao-Jen
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Chang, Yuan-Wei
An equiatomic CoCrFeMnNi high-entropy alloy under hydrostatic compression is investigated using insitu angular-dispersive X-ray diffraction to explore the polymorphism in high entropy alloy systems. The metallic system is of face-centered-cubic structure at ambient condition and applied hydrostatic pressures up to 20 GPa via diamond anvil cell. The angle-resolved diffraction-intensity evolutions of multiple diffraction peaks were collected simultaneously to elucidate the phase stability examinations. The phase transformation from face-centered-cubic to hexagonal-close-packed structure was evidently observed in CoCrFeMnNi alloy accompanied by a deviatoric strain subjected to the hydrostatic compression. We found lattice-asymmetric crossover before and after the phase transformation subjected to hydrostatic compression surroundings. Deviatoric strain triggers fcc-hcp phase transformation as local heterogeneity-driven lattice distortion is significant for CoCrFeMnNi alloy. (c) 2019 The Authors. Published by Elsevier B.V.
Interface-Controlled Synthesis of Au-BINOL Hybrid Nanostructures and Mechanism Study
(2018-11-13)
Patlolla, Shashank Reddy
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Kao, Chen-Rui
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Yeh, Ai-Hsuan
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Lin, Hung-Min
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Chuang, Yu-Chun
The combined functionality of components in organic inorganic hybrid nanomaterials render them efficient nanoreactors. However, the development in this field is limited due to a lack of synthetic avenues and systematic control of the growth kinetics of hybrid structures. In this work, we take advantage of an ionic switch for regio-control of Au-BINOL(1,1'-Bi-2-naphthol) hybrid nanostructures. Aromatic BINOL molecules assemble into nanospheres, concomitant with the growth of the Au nanocrystals. The morphological evolution of Au nanocrystals is solely controlled by the presence of halides in the synthetic system. Here we show that quaternary ammonium surfactants (CTAB or CTAC), not only bridging Au and BINOL, but also contributing to the formation of concentric or eccentric structures when their concentrations are tuned to the range of 10(-5) to 10(-3) M. This facile strategy offers the potential advantage of scalable production, with diverse functional organic inorganic hybrid nanocomposites being produced based on the specific archetype of Au-BINOL hybrid nano composites.
Irreversible phase transformation in a CoCrFeMnNi high entropy alloy under hydrostatic compression
(2018-03-01)
Huang, E-Wen
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Lin, Chih-Ming
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Jain, Jayant
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Shieh, Sean R.
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Wang, Ching-Pao
An equal-molar CoCrFeMnNi, face-centered-cubic high-entropy alloy system is investigated using in-situ angular-dispersive X-ray diffraction under hydrostatic compression up to 20 GPa via diamond anvil cell. The evolutions of multiple diffraction peaks are collected simultaneously to elucidate the phase stability field. The results indicated that an irreversible phase transformation had occurred in the high entropy alloy upon decompression to ambient pressure. A reference material (n-type silicon-doped gallium arsenide) was investigated following the same protocol to demonstrate the different deformation mechanisms. It is suggested that the atomic bonding characteristics on the phase stability may play an important role in the high entropy alloys.
Metal substituted pyrochlore phase LixLa2-xCe1.8Ru0.2O7- (x=0.0-0.6) as an effective catalyst for oxidative and auto-thermal steam reforming of ethanol
(2019-03-21)
Hsieh, Ho-Chen
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Chang, Yuan-Chia
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Tsai, Ping-Wen
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Lin, Yen-Yu
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Chuang, Yu-Chun
Pyrochlore phase LixLa2-xCe1.8Ru0.2O7- (x = 0.0-0.6) [LLCRO] substituted by Li and Ru in A and B sites was synthesized and studied for performance in oxidative steam and auto-thermal reforming of ethanol (OSRE, ATR). The samples were characterized by powder X-ray diffraction (PXRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS) to examine the effect of substituted Li+ and Run+ on OSRE performance. The results indicated that the substituted Li ions modified the oxidation states of Ru and Ce in LLCRO, which led to oxygen vacancies/mobility and played an important role in the catalytic performance of OSRE. Using LLCRO as the catalyst and supported by Al2O3, La2Zr2O7 (LZO) was investigated for its hydrogen production performance. The catalytic stability of the LLCRO (x = 0.6)/LZO catalysts was tested at 350 degrees C under oxidative steam conditions (OSRE) and showed a stable ethanol conversion and hydrogen production (X-EtOH = 98(3)%; S-H2 = 95(3)%). Under autothermal conditions (ATR), the LLCRO (x = 0.6) catalyst supported by LZO exhibited a stable catalytic performance with an average ethanol conversion and hydrogen selectivity of 90(3)% and 71(4)%, respectively. Carbon deposition was significantly suppressed during the OSRE and ATR processes on LLCRO (x = 0.6) catalysts supported by LZO, whereas, a significant carbon deposition was observed for LLCRO (x = 0.6)/Al2O3 as the catalyst. These results indicate that LLCRO (x = 0.6) supported by LZO is an effective catalyst for hydrogen production. The enhanced activity was attributed to the effectively suppressed carbon deposition and the sintering of highly dispersed Ru ions in the LLCRO catalyst, which may be due to the strong binding between the catalyst and LZO.
Oxidative steam reforming of ethanol over MxLa2-xCe1.8Ru0.2O7-delta (M = Mg, Ca) catalysts: effect of alkaline earth metal substitution and support on stability and activity
(2019-12-02)
Hsieh, Ho-Chen
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Tsai, Ping-Wen
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Chang, Yuan-Chia
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Weng, Sheng-Feng
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Sheu, Hwo-Shuenn
Alkaline earth metal substitutions on the A-site of pyrochlore oxide MxLa2-xCe1.8Ru0.2O7-delta (M = Mg, Ca) were studied as catalyst materials for oxidative/autothermal steam reforming of ethanol (OSRE/ATR). The as-prepared oxides were synthesized by a combustion method and characterized using powder X-ray diffraction (PXRD), and X-ray photoelectron and absorption spectroscopy (XPS and XAS). PXRD Rietveld analysis and elemental analysis (ICP-AES) support the formation of a pyrochlore-type structure (space group Fd3m) with a distorted coordination environment. The substitution of Mg²⁺ and Ca²⁺ ions affects the oxidation states of Ce^4+/3+ and Ruⁿ⁺ ions and creates oxygen vacancies, which leads to enhanced catalytic activity and reduced ethylene selectivity. A long-term stability test showed optimized catalysts Mg0.3La1.7Ce1.8Ru0.2O7-delta and Ca0.2La1.8Ce1.8Ru0.2O7-delta with SH2 = 101(1)% and SH2 = 91(2)% under OSRE conditions. The initial operation temperatures were lower than that of the unsubstituted catalyst La2Ce1.8Ru0.2O7-delta. Catalysts supported on La2Zr2O7 showed stable OSRE/ATR performance and low carbon deposition compared to catalysts supported on Al2O3. We ascribe the enhanced activity to well-dispersed alkaline earth metal and Ru ions in a solid solution structure, synergistic effects of (Mg, Ca)²⁺/Ce^3+/4+/Ruⁿ⁺ ions, and a strong catalyst-support interaction that optimized the ethanol conversion and hydrogen production.
Pressure effect on impurity local vibrational mode and phase transitions in n-type iron-doped indium phosphide
(2018-01-19)
Lin, Chih-Ming
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Hsu, I-Jui
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Lin, Sin-Cheng
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Chuang, Yu-Chun
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Chen, Wei-Ting
The evolution of iron local vibrational mode (Fe LVM) and phase transitions in n-type iron-doped indium phosphide (InP:Fe) were investigated at ambient temperature. In-situ angle-dispersive X-ray diffraction measurements revealed that InP: Fe starts to transform from zinc-blende (ZB) to rock-salt (RS) structure around 8.2(2) GPa and completes around 16.0(2) GPa. The Raman shift of both transverse and longitudinal optical modes increases monotonically with increasing pressure, while their intensities become indiscernible at 11.6(2) GPa, suggesting that the pressure-induced phase transition is accompanied by significant metallization. In contrast, originally absent at ambient pressure, the Raman shift of Fe LVM appears at similar to 420 cm(-1) near 1.2 GPa and exhibits a dome shape behavior with increasing pressure, reaching a maximum value of similar to 440 cm-1 around 5 GPa, with an apparent kink occurring around the ZB-RS transition pressure of similar to 8.5(2) GPa. The Fe K-edge X-ray absorption near edge structure (XANES) confirmed the tetrahedral site occupation of Fe3+ with a crystal field splitting parameter Delta(t)=38k . mole(-1). Our calculations indicate that the energy parameters governing the phase transition are Delta(t)=0.49 and Delta(o) =1.10 kJ . mole(-1),respectively, both are much smaller than Delta(t) = 38 kJ . mole(-1) at ambient.
Pressure-Induced Phase Transitions in InAs Studied by Angular-Dispersive X-ray Diffraction and Raman Spectroscopy
(2015-06-01)
Lin, Chih-Ming
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Lin, Kung-Liang
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Chern, Yu-Ker
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Lin, Yu-Kun
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Chuang, Yu-Chun
Pressure-induced phase transitions in indium arsenide (In As) at ambient temperature were investigated by using angular-dispersive X-ray diffraction (ADXRD) and Raman scattering under high pressure up to around 9.8(1) and 9.9(2) GPa, respectively, with a 4:1 (in volume ratio) methanol-ethanol mixture as the pressure transmitting medium (PTM). In situ ADXRD measurements revealed that In As starts to transform from zinc blende (ZB) structure to rock-salt (RS) phase at 6.7(1) GPa, consistent with most previously reported studies. The phase transition proceeds steadily over a wide range of pressures and reaches completion at the highest applied pressure of 9.8 GPa with significant metallization, as suggested by the disappearance of Raman modes. In contrast to previous studies, our data did not show evidence of structural transition to Cnncm phase, presumably due to the different PTMs used and/or insufficient pressure applied. The order of appearance of the major diffraction peaks of RS phase In As with increasing pressure and intensity are explained by the binding energy density of the corresponding plane families. The zero-pressure isothermal bulk moduli (B-0) and its first-pressure derivatives (B-0\') for the ZB In As are 64(4) GPa and 3.8(2), respectively. The intensity of both the LO and TO phonon modes of ZB phase In As exhibits an abrupt decrease at 7.7(1) GPa, where equal weight fractions of ZB and RS phases are identified, suggesting the metallic nature of the RS phase.
Structural properties of pressure-induced structural phase transition of Si-doped GaAs by angular-dispersive X-ray diffraction
(2016-02)
Lin, Kung-Liang
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Lin, Chih-Ming
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Lin, Yu-Sheng
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Jian, Sheng-Rui
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Liao, Yen-Fa
Pressure-induced phase transitions in n-type silicon-doped gallium arsenide (GaAs: Si) at ambient temperature were investigated by using angular-dispersive X-ray diffraction (ADXRD) under high pressure up to around 18.6 (1) GPa, with a 4:1 (in volume ratio) methanol-ethanol mixture as the pressure-transmitting medium. In situ ADXRD measurements revealed that n-type GaAs: Si starts to transform from zinc-blende structure to an orthorhombic structure [GaAs-II phase], space group Pmm2, at 16.4 (1) GPa. In contrast to previous studies of pure GaAs under pressure, our results show no evidence of structural transition to Fmmm or Cmcm phase. The fitting of volume compression data to the third-order Birch-Murnaghan equation of state yielded that the zero-pressure isothermal bulk moduli and the first-pressure derivatives were 75 (3) GPa and 6.4 (9) for the B3 phase, respectively. After decompressing to the ambient pressure, the GaAs: Si appears to revert to the B3 phase completely. By fitting to the empirical relations, the Knoop microhardness numbers are between H-PK = 6.21 and H-A = 5.85, respectively, which are substantially smaller than the values of 7-7.5 for pure GaAs reported previously. A discontinuous drop in the pressure-dependent lattice parameter, N-N distances, and V/V-0 was observed at a pressure of 11.5 (1) GPa, which was tentatively attributed to the pressure-induced dislocation activities in the crystal grown by vertical gradient freeze method.
Structural Transitions in Nanosized Zn0.97Al0.030 Powders under High Pressure Analyzed by in Situ Angle-Dispersive X-ray Diffraction
(2016-07-01)
Lin, Chih-Ming
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Liu, Hsin-Tzu
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Zhong, Shi-Yao
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Hsu, Chia-Hung
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Chiu, Yi-Te
Nanosized aluminum-doped zinc oxide Zn1-xAlxO (AZO) powders (AZO-NPs) with x = 0.01, 0.03, 0.06, 0.09 and 0.11 were synthesized by chemical precipitation method. The thermogravimetric analysis (TGA) indicated that the precursors were converted to oxides from hydroxides near 250 degrees C, which were then heated to 500 degrees C for subsequent thermal processes to obtain preliminary powders. The obtained preliminary powders were then calcined at 500 degrees C for three hours. The structure and morphology of the products were measured and characterized by angle -dispersive X-ray diffraction (ADXRD) and scanning electron microscopy (SEM). ADXRD results showed that AZO-NPs with Al content less than 11% exhibited wurtzite zinc oxide structure and there was no other impurity phase in the AZO-NPs, suggesting substitutional doping of Al on Zn sites. The Zn0.97Al0.030 powders (A3ZO-NPs) with grain size of about 21.4 nm were used for high-pressure measurements. The in situ ADXRD measurements revealed that, for loading run, the pressure-induced wurtzite (B4)-to-rocksalt (B1) structural phase transition began at 9.0(1) GPa. Compared to the predicted phase-transition pressure of 12.7 GPa for pristine ZnO nanocrystals of similar grain size (similar to 21.4 nm), the transition pressure for the present A(3)ZO-NPs exhibited a reduction of 3.7 GPa. The significant reduction in phase -transition pressure is attributed to the effects of highly selective site occupation, namely Zn2+ and Al3+, were mainly found in tetrahedral and octahedral sites, respectively.