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2019
Chen, J-C, Hsiao Y-R, Liu Y-C, Chen P-Y, Chen K-H.  2019.  Polybenzimidazoles containing heterocyclic benzo[c]cinnoline structure prepared by sol-gel process and acid doping level adjustment for high temperature PEMFC application, 2019. 182:121814. AbstractWebsite

Polybenzimidazoles containing heterocyclic benzo[c]cinnoline structure are synthesized from 3,8-benzo[c]cinnoline dicarboxylic acid, terephthalic acid and 3,3′-diaminobenzidine. Their membranes are prepared by sol-gel process, involving the conversion of polymer solution in polyphosphoric acid to phosphoric acid. The acid doping levels of the as-prepared membranes increase as the contents of benzo[c]cinnoline increase, indicating good interaction between phosphoric acid and benzo[c]cinnoline structure. The as-prepared membranes with high acid doping levels might lead to the dissolution of membranes in phosphoric acid at temperature higher than 120 °C. A new method is proposed to adjust acid doping levels by immersing the as-prepared membranes in diluted phosphoric acid solutions of various concentrations. The adjusted membranes (acid doping levels around 30 PA RU−1) exhibit enhanced mechanical properties with tensile strength in the range of 4.1–5.2 MPa. The proton conductivity of adjusted membranes maintain at 0.15–0.17 S cm−1 at 160 °C under ambient atmosphere without humidification. The single cells based on the adjusted membranes exhibit open circuit voltages and peak power densities from 0.89 to 0.91 V and 691–1253 mW cm−2 at 160 °C, respectively. Compared to other polybenzimidazole membranes prepared by sol-gel process, the adjusted polybenzimidazoles show higher mechanical strength and better single cell performance.

Prem Kumar, DS, Tippireddy S, Ramakrishnan A, Chen K-H, Malar P, Mallik RC.  2019.  Thermoelectric and electronic properties of chromium substituted tetrahedrite, 2019. Semiconductor Science and Technology. 34(3):035017.: IOP Publishing AbstractWebsite

Cr substituted tetrahedrites with the chemical formula Cu12−xCrxSb4S13 (x = 0.15, 0.25, 0.35, 0.5, 0.75, 1.0) have been synthesised for thermoelectric study. Cr substitutes at the Cu site to optimize the thermoelectric properties and achieve a higher figure of merit (zT). X-Ray diffraction (XRD) analysis revealed that the tetrahedrite is the major phase with minor impurity phases. Electron probe microanalysis (EPMA) shows the formation of tetrahedrite main phase with near stoichiometry and the presence of Cu3SbS4, CuSbS2 and Sb as secondary phases. X-ray photoelectron spectroscopy (XPS) shows the oxidation state of Cu, Sb and S as +1, +3 and −2, respectively, whereas for Cr, it could not be identified. Temperature-dependent magnetic susceptibility of sample x = 0.75 shows antiferromagnetic correlation originating from the Cr ion. The calculated effective magnetic moment of 2.83 μB per Cr atom indicates the presence of Cr+4 in this sample. The decrease in the electrical resistivity upon doping indicates the compensation of holes due to the substitution of Cr at the Cu site. But the x = 0.35 sample is not following the trend due to larger compensation of holes with an activation energy of 124.6 meV. The temperature-dependent behaviour of electrical resistivity shows the shift in the Fermi level from the valance band towards the band gap. The absolute Seebeck coefficient is positive throughout the temperature range and follows a similar trend as that of electrical resistivity, with the exception of the x = 0.35 sample. The electronic thermal conductivity reduces due to hole compensation caused by Cr substitution. Moreover, the substitution of Cr effectively reduces the lattice thermal conductivity due to point defect scattering of phonons. A maximum zT of 1.0 is achieved for sample x = 0.35 at 700 K.

Das, S, Valiyaveettil SM, Chen K-H, Suwas S, Mallik RC.  2019.  Thermoelectric properties of Mn doped BiCuSeO, 2019. Materials Research Express. 6(8):086305.: IOP Publishing AbstractWebsite

BiCuSeO is a promising thermoelectric material having earth-abundant non-toxic constituents and favourable thermoelectric properties like ultra-low thermal conductivity. In this study, Mn+2 has been introduced at the Bi+3 site to increase hole concentration as well as Seebeck coefficient, through aliovalent doping and magnetic impurity incorporation respectively. Samples were prepared through two-step solid state synthesis with the composition Bi1-xMnxCuSeO (x = 0.0, 0.04, 0.06, 0.08, 0.10 and 0.12). X-ray diffraction patterns confirmed the tetragonal (space group: P4/nmm) crystal structure of BiCuSeO as well as phase purity of the samples. The Seebeck coefficient and electrical resistivity had a decreasing trend with increasing doping fraction owing to the generation of charge carriers. The samples with x = 0.04 and 0.06 showed temperature independent Seebeck coefficient above 523 K, which is a signature of small polaron hopping. While the Seebeck coefficient of the samples with x = 0.08, 0.10 and 0.12 increased above 523 K due to the combination of localized and extended states. The thermal conductivity was dominated by the lattice part of the thermal conductivity. As a result of moderate Seebeck coefficient and low electrical resistivity, the highest power factor of 0.284 mW m−1-K2 was obtained for the Bi0.92Mn0.08CuSeO at 773 K, leading to a maximum zT of 0.4 at 773.

Roy, P, Kumar, Haider G, Chou T-chin, Chen K-H, Chen L-C, Chen Y-F, Liang C-T.  2019.  Ultrasensitive Gas Sensors Based on Vertical Graphene Nanowalls/SiC/Si Heterostructure, 2019. ACS SensorsACS Sensors. 4(2):406-412.: American Chemical Society AbstractWebsite
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2020
Yang, J, Wang C-Y, Wang C-C, Chen K-H, Mou C-Y, Wu H-L.  2020.  Advanced nanoporous separators for stable lithium metal electrodeposition at ultra-high current densities in liquid electrolytes, 2020. Journal of Materials Chemistry A. 8(10):5095-5104.: The Royal Society of Chemistry AbstractWebsite

Lithium metal anodes form a dendritic structure after cycling which causes an internal short circuit in flammable electrolytes and results in battery fires. Today's separators are insufficient for suppressing the formation of lithium dendrites. Herein, we report on the use of mesoporous silica thin films (MSTFs) with perpendicular nanochannels (pore size ∼5 nm) stacking on an anodic aluminum oxide (AAO) membrane as the MSTF⊥AAO separator for advancing Li metal batteries. The nanoporous MSTF⊥AAO separator with novel inorganic structures shows ultra-long term stability of Li plating/stripping in Li–Li cells at an ultra-high current density and capacity (10 mA cm−2 and 5 mA h cm−2). A significant improvement over the state-of-the-art separator is evaluated based on three performance indicators, e.g. cycle life, current density and capacity. In Li–Cu cells, the MSTF⊥AAO separator shows a coulombic efficiency of >99.9% at a current density of 10 mA cm−2 for more than 250 h of cycling. The separator gives improved rate capability in Li–LiFePO4 (LFP) batteries. The excellent performance of the MSTF⊥AAO separator is due to good wetting of electrolytes, straight nanopores with negative charges, uniform Li deposition and blocking the finest dendrite.

Chang, M-C, Ho P-H, Tseng M-F, Lin F-Y, Hou C-H, Lin I-K, Wang H, Huang P-P, Chiang C-H, Yang Y-C, Wang I-T, Du H-Y, Wen C-Y, Shyue J-J, Chen C-W, Chen K-H, Chiu P-W, Chen L-C.  2020.  Fast growth of large-grain and continuous MoS2 films through a self-capping vapor-liquid-solid method, 2020. 11(1):3682. AbstractWebsite

Most chemical vapor deposition methods for transition metal dichalcogenides use an extremely small amount of precursor to render large single-crystal flakes, which usually causes low coverage of the materials on the substrate. In this study, a self-capping vapor-liquid-solid reaction is proposed to fabricate large-grain, continuous MoS2 films. An intermediate liquid phase-Na2Mo2O7 is formed through a eutectic reaction of MoO3 and NaF, followed by being sulfurized into MoS2. The as-formed MoS2 seeds function as a capping layer that reduces the nucleation density and promotes lateral growth. By tuning the driving force of the reaction, large mono/bilayer (1.1 mm/200 μm) flakes or full-coverage films (with a record-high average grain size of 450 μm) can be grown on centimeter-scale substrates. The field-effect transistors fabricated from the full-coverage films show high mobility (33 and 49 cm2 V−1 s−1 for the mono and bilayer regions) and on/off ratio (1 ~ 5 × 108) across a 1.5 cm × 1.5 cm region.

Chang, H-C, Chen T-H, Sankar R, Yang Y-J, Chen L-C, Chen K-H.  2020.  Highly improved thermoelectric performance of BiCuTeO achieved by decreasing the oxygen content, 2020. 15:100248. AbstractWebsite

BiCuTeO is a promising thermoelectric material owing to its intrinsically low thermal conductivity and high carrier concentration. This study investigated the influence of stoichiometric oxygen deficiencies on the thermoelectric performance of BiCuTeO. Bulk BiCuTeO1−x (0.16 ≥ x) samples were prepared by a conventional solid state reaction and pelleted by hot pressing. Synchrotron X-ray diffraction, electron probe X-ray microanalysis, scanning electron microscopy, and transmission electron microscopy characterized the samples. A maximum value of 1.06 was achieved for the dimensionless figure of merit ZT at 673 K for BiCuTeO0.88, which is approximately 49% better than the current maximal ZT value for BiCuTeO. The power factor was noticeably improved owing to increases in the electrical conductivity and Seebeck coefficient. Moreover, the optimal oxygen deficiency could introduce nanoparticles, resulting in reduced thermal conductivity. The findings will be important for the future development of metal oxide thermoelectric materials for use in practical thermoelectric devices.

Shit, SC, Shown I, Paul R, Chen K-H, Mondal J, Chen L-C.  2020.  Integrated nano-architectured photocatalysts for photochemical CO2 reduction, 2020. Nanoscale. 12(46):23301-23332.: The Royal Society of Chemistry AbstractWebsite

Recent advances in nanotechnology, especially the development of integrated nanostructured materials, have offered unprecedented opportunities for photocatalytic CO2 reduction. Compared to bulk semiconductor photocatalysts, most of these nanostructured photocatalysts offer at least one advantage in areas such as photogenerated carrier kinetics, light absorption, and active surface area, supporting improved photochemical reaction efficiencies. In this review, we briefly cover the cutting-edge research activities in the area of integrated nanostructured catalysts for photochemical CO2 reduction, including aqueous and gas-phase reactions. Primarily explored are the basic principles of tailor-made nanostructured composite photocatalysts and how nanostructuring influences photochemical performance. Specifically, we summarize the recent developments related to integrated nanostructured materials for photocatalytic CO2 reduction, mainly in the following five categories: carbon-based nano-architectures, metal–organic frameworks, covalent-organic frameworks, conjugated porous polymers, and layered double hydroxide-based inorganic hybrids. Besides the technical aspects of nanostructure-enhanced catalytic performance in photochemical CO2 reduction, some future research trends and promising strategies are addressed.

Thang, NQ, Sabbah A, Chen L-C, Chen K-H, Hai LV, Thi CM, Viet PV.  2020.  Localized surface plasmonic resonance role of silver nanoparticles in the enhancement of long-chain hydrocarbons of the CO2 reduction over Ag-gC3N4/ZnO nanorods photocatalysts, 2020. :116049. AbstractWebsite

The conversion of CO2 into hydrocarbon fuels via the photocatalytic reaction route is considered a potential strategy to concurrently address serious energy crisis and greenhouse gas emission problems. Nevertheless, the generation of long-chain hydrocarbon products (Cn, n ≥ 2) from the visible-light-reactive photocatalytic CO2 reduction has also been considering a contemporary challenge. Herein, we indicate that Ag nanoparticles (Ag NPs) loaded gC3N4/ZnO nanorods heterojunction (Ag-gC3N4/ZnO NRs abbreviation) has extended photoactive range and enhanced specific surface area. The combination of Ag NPs and gC3N4/ZnO NRs significantly enhances photocatalytic CO2 reduction efficiency to form the acetone product. Detail, the acetone production efficiency of Ag-gC3N4/ZnO NRs is 8.4 and 7.5 times higher than pure ZnO NRs and gC3N4/ZnO NRs at the same condition, respectively. This study represents a potential approach toward higher-energy-value hydrocarbons production and greenhouse gas emission mitigation.

Billo, T, Shown I, kumar Anbalagan A, Effendi TA, Sabbah A, Fu F-Y, Chu C-M, Woon W-Y, Chen R-S, Lee C-H, Chen K-H, Chen L-C.  2020.  A mechanistic study of molecular CO2 interaction and adsorption on carbon implanted SnS2 thin film for photocatalytic CO2 reduction activity, 2020. 72:104717. AbstractWebsite

Gas-phase photocatalytic reactions to convert carbon dioxide and water into oxygen and hydrocarbons are the foundation of life on earth. However, the efficiency of photosynthesis is relatively low (~1%), which leaves much room for artificial photosynthesis to reach the benchmark of the solar cells (>15%). In this work, carbon implanted SnS2 thin films (C–SnS2) were prepared to study photocatalytic activity and adsorbate-catalyst surface interactions during CO2 photoreduction. The electron density distribution in C–SnS2 and its contribution toward the photogenerated charge transfer process has been analyzed by the angle-dependent X-ray absorption near-edge structure (XANES) study. The C–SnS2 surface affinity toward the CO2 molecule was monitored by in-situ dark current and Raman spectroscopy measurements. By optimizing the dose during ion implantation, SnS2 thin film with 1 wt% carbon incorporation shows 108 times enhancement in the CO2 conversion efficiency and more than 89% product selectivity toward CH4 formation compared with the as-grown SnS2 without carbon incorporation. The improved photocatalytic activity can be ascribed to enhanced light harvesting, pronounced charge-transfer between SnS2 and carbon with improved carrier separation and the availability of highly active carbon sites that serve as favorable CO2 adsorption sites.

Howlader, S, Vasudevan R, Jarwal B, Gupta S, Chen K-H, Sachdev K, Banerjee MK.  2020.  Microstructure and mechanical stability of Bi doped Mg2Si0.4Sn0.6 thermoelectric material, 2020. 818:152888. AbstractWebsite

Bi doped Mg2Si0.4Sn0.6 had been synthesised in a high energy ball mill followed by compaction using a sintering hot press. The structural and compositional characterization of sintered mass indicated the formation of a highly densified single-phase product. The microstructure of the hot-pressed samples had been critically assessed. Thermoelectric properties were measured between room temperature and 723 K. A decrease in electrical conductivity was found with the increase in temperature but the Seebeck coefficient showed a reverse trend justifying the attainment of degenerate semiconducting behaviour. Meanwhile, the lattice thermal conductivity was subdued to 1.5 W/mK at 623 K. However, the highest zT value of 0.8 was achieved at 723 K. Moreover, the detailed X-ray photoelectron spectroscopic analysis was carried for the determination of binding energy of the constituent elements in the experimental alloy; it also provided the correct estimation of atomic percentage of the concerned elements. The Raman spectrum revealed a shift in F2g peak with respect to that of Mg2Sn and Mg2Si in correspondence with the composition of the synthesised alloy. The synthesised alloy showed micro and nano hardness of 3.7 and 4.03 GPa respectively, which implies that good mechanical strength could be achieved in the synthesised alloy.

Huang, W-F, Chang S-T, Huang H-C, Wang C-H, Chen L-C, Chen K-H, Lin MC.  2020.  On the Reduction of O2 on Cathode Surfaces of Co–Corrin and Co–Porphyrin: A Computational and Experimental Study on Their Relative Efficiencies in H2O/H2O2 Formation, 2020. The Journal of Physical Chemistry CThe Journal of Physical Chemistry C. 124(8):4652-4659.: American Chemical Society AbstractWebsite
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Lien, H-T, Chang S-T, Chen P-T, Wong DP, Chang Y-C, Lu Y-R, Dong C-L, Wang C-H, Chen K-H, Chen L-C.  2020.  Probing the active site in single-atom oxygen reduction catalysts via operando X-ray and electrochemical spectroscopy, 2020. 11(1):4233. AbstractWebsite

Nonnoble metal catalysts are low-cost alternatives to Pt for the oxygen reduction reactions (ORRs), which have been studied for various applications in electrocatalytic systems. Among them, transition metal complexes, characterized by a redox-active single-metal-atom with biomimetic ligands, such as pyrolyzed cobalt–nitrogen–carbon (Co–Nx/C), have attracted considerable attention. Therefore, we reported the ORR mechanism of pyrolyzed Vitamin B12 using operando X-ray absorption spectroscopy coupled with electrochemical impedance spectroscopy, which enables operando monitoring of the oxygen binding site on the metal center. Our results revealed the preferential adsorption of oxygen at the Co2+ center, with end-on coordination forming a Co2+-oxo species. Furthermore, the charge transfer mechanism between the catalyst and reactant enables further Co–O species formation. These experimental findings, corroborated with first-principle calculations, provide insight into metal active-site geometry and structural evolution during ORR, which could be used for developing material design strategies for high-performance electrocatalysts for fuel cell applications.

Bayikadi, KS, Wu CT, Chen L-C, Chen K-H, Chou F-C, Sankar R.  2020.  Synergistic optimization of thermoelectric performance of Sb doped GeTe with a strained domain and domain boundaries, 2020. Journal of Materials Chemistry A. 8(10):5332-5341.: The Royal Society of Chemistry AbstractWebsite

In addition to the Ge-vacancy control of GeTe, the antimony (Sb) substitution of GeTe for the improvement of thermoelectric performance is explored for Ge1−xSbxTe with x = 0.08–0.12. The concomitant carrier concentration (n) and the aliovalent Sb ion substitution led to an optimal doping level of x = 0.10 to show ZT ∼ 2.35 near ∼800 K, which is significantly higher than those single- and multi-element substitution studies of the GeTe system reported in the literature. In addition, Ge0.9Sb0.1Te demonstrates an impressively high power factor of ∼36 μW cm−1 K−2 and a low thermal conductivity of ∼1.1 W m−1 K−1 at 800 K. The enhanced ZT level for Ge0.9Sb0.1Te is explained through a systematic investigation of micro-structural change and strain analysis from room temperature to 800 K. A significant reduction of lattice thermal conductivity (κlat) is identified and explained by the Sb substitution-introduced strained and widened domain boundaries for the herringbone domain structure of Ge0.9Sb0.1Te. The Sb substitution created multiple forms of strain near the defect centre, the herringbone domain structure, and widened tensile/compressive domain boundaries to support phonon scattering that covers a wide frequency range of the phonon spectrum to reduce lattice thermal conductivity effectively.

2021
Samireddi, S, Aishwarya V, Shown I, Muthusamy S, Unni SM, Wong K-T, Chen K-H, Chen L-C.  2021.  Synergistic Dual-Atom Molecular Catalyst Derived from Low-Temperature Pyrolyzed Heterobimetallic Macrocycle-N4 Corrole Complex for Oxygen Reduction. Small. 17:2103823., Number 46 AbstractWebsite

Abstract A heterobimetallic corrole complex, comprising oxygen reduction reaction (ORR) active non-precious metals Co and Fe with a corrole-N4 center (PhFCC), is successfully synthesized and used to prepare a dual-atom molecular catalyst (DAMC) through subsequent low-temperature pyrolysis. This low-temperature pyrolyzed electrocatalyst exhibited impressive ORR performance, with onset potentials of 0.86 and 0.94 V, and half-wave potentials of 0.75 and 0.85 V, under acidic and basic conditions, respectively. During potential cycling, this DAMC displayed half-wave potential losses of only 25 and 5 mV under acidic and alkaline conditions after 3000 cycles, respectively, demonstrating its excellent stability. Single-cell Nafion-based proton exchange membrane fuel cell performance using this DAMC as the cathode catalyst showed a maximum power density of 225 mW cm−2, almost close to that of most metal–N4 macrocycle-based catalysts. The present study showed that preservation of the defined CoN4 structure along with the cocatalytic Fe–Cx site synergistically acted as a dual ORR active center to boost overall ORR performance. The development of DAMC from a heterobimetallic CoN4-macrocyclic system using low-temperature pyrolysis is also advantageous for practical applications.

Huang, Y-F, Liao K-W, Fahmi FRZ, Modak VA, Tsai S-H, Ke S-W, Wang C-H, Chen L-C, Chen K-H.  2021.  Thickness-Dependent Photocatalysis of Ultra-Thin MoS2 Film for Visible-Light-Driven CO2 Reduction. Catalysts. 11, Number 11 AbstractWebsite

The thickness of transition metal dichalcogenides (TMDs) plays a key role in enhancing their photocatalytic CO2 reduction activity. However, the optimum thickness of the layered TMDs that is required to achieve sufficient light absorption and excellent crystallinity has still not been definitively determined. In this work, ultra-thin molybdenum disulfide films (MoS2TF) with 25 nm thickness presented remarkable photocatalytic activity, and the product yield increased by about 2.3 times. The photocatalytic mechanism corresponding to the TMDs’ thickness was also proposed. This work demonstrates that the thickness optimization of TMDs provides a cogent direction for the design of high-performance photocatalysts.

Huang, S-J, Muneeb A, Sabhapathy P, Bayikadi KS, Murtaza T, Raju K, Chen L-C, Chen K-H, Sankar R.  2021.  Two-Dimensional Layered NiLiP2S6 Crystals as an Efficient Bifunctional Electrocatalyst for Overall Water Splitting. Catalysts. 11, Number 7 AbstractWebsite

The quest of earth-abundant bifunctional electrocatalysts for highly efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is essential for clean and renewable energy systems. Herein, directed by the experimental analysis, we demonstrate layered nickel lithium phosphosulfide (NiLiP2S6) crystal as a highly efficient water-splitting catalyst in alkaline media. With strained lattice due to stacked layers as observed by TEM and electronic structure analysis performed by XPS showed mixed Ni2+,3+ oxidation states induced by addition of Li as a cation, NiLiP2S6 displays excellent OER (current density of 10 mA cm–2 showed an overpotential of 303 mV vs. RHE and a Tafel slope of 114 mV dec–1) and HER activity (current density of −10 mA cm–2 showed an overpotential of 184 mV vs. RHE and a Tafel slope of 94.5 mV dec–1). Finally, an alkaline media was employed to demonstrate the overall water splitting using NiLiP2S6 as both the anode and the cathode, which attained a 50 mA cm−2 current density at 1.68 V. This bimetallic phosphosulfide, together with long-term stability and enhanced intrinsic activity, shows enormous potential in water splitting applications.

Syum, Z, Billo T, Sabbah A, Venugopal B, Yu S-Y, Fu F-Y, Wu H-L, Chen L-C, Chen K-H.  2021.  Copper Zinc Tin Sulfide Anode Materials for Lithium-Ion Batteries at Low Temperature, 2021. ACS Sustainable Chemistry & EngineeringACS Sustainable Chemistry & Engineering. : American Chemical Society AbstractWebsite
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Sabhapathy, P, Shown I, Sabbah A, Raghunath P, Chen J-L, Chen W-F, Lin M-C, Chen K-H, Chen L-C.  2021.  Electronic structure modulation of isolated Co-N4 electrocatalyst by sulfur for improved pH-universal hydrogen evolution reaction, 2021. Nano Energy. 80:105544. AbstractWebsite

Exploring an efficient platinum group metal (PGM) free electrocatalyst with superior activity and stability for hydrogen evolution reaction (HER) in a wide pH range is desirable for low-cost hydrogen production. Here, we report atomically dispersed cobalt on nitrogen and sulfur co-doped graphene (N-Co-S/G) for HER. Remarkably, the prepared N-Co-S/G electrocatalyst shows a small overpotential of 67.7 mV vs. reversible hydrogen electrode (RHE) at a current density of 10 mA cm−2 and exceptional durability over 100 h at 10 mA cm−2 under acidic conditions. Moreover, we found that the HER activity of N-Co-S/G is close to 20% Pt/C at all pH levels (0–14) and superior activity at high current density (>100 mA cm−2). Experimental and theoretical calculations reveal that the S atom in N-Co-S/G form Co-S bond, resulting new Co-N3S1 active site, which optimizes Gibbs free energy for hydrogen adsorption (∆GH*) close to zero, while water adsorption and dissociation enhanced by S modulation for neutral and basic media HER.

Thang, NQ, Sabbah A, Chen L-C, Chen K-H, Thi CM, Viet PV.  2021.  High-efficient photocatalytic degradation of commercial drugs for pharmaceutical wastewater treatment prospects: A case study of Ag/g-C3N4/ZnO nanocomposite materials, 2021. Chemosphere. 282:130971. AbstractWebsite

Pharmaceutical drugs' removal from wastewater by photocatalytic oxidation process is considered as an attractive approach and environmentally friendly solution. This report aims to appraise the practical application potential of Ag/g-C3N4/ZnO nanorods toward the wastewater treatment of the pharmaceutical industry. The catalysts are synthesized by straightforward and environmentally-friendly strategies. Specifically, g-C3N4/ZnO nanorods heterostructure is constructed by a simple self-assembly method, and then Ag nanoparticles are decorated on g-C3N4/ZnO nanorods by a photoreduction route. The results show that three commercial drugs (paracetamol, amoxicillin, and cefalexin) with high concentration (40 mg L−1) are significantly degraded in the existence of a small dosage of Ag/g-C3N4/ZnO nanorods (0.08 g L−1). The Ag/g-C3N4/ZnO nanorods photocatalyst exhibits degradation performance of paracetamol higher 3.8, 1.8, 1.3 times than pristine g-C3N4, ZnO nanorods, and g-C3N4/ZnO nanorods. Furthermore, Ag/g-C3N4/ZnO nanorods have an excellent reusability and a chemical stability that achieved paracetamol degradation efficiency of 78% and remained chemical structure of the photocatalyst after five cycles. In addition, the photocatalytic mechanism explanation and comparison of photocatalytic drugs’ degradation ability have also been discussed in this study.

Quadir, S, Qorbani M, Lai Y-R, Sabbah A, Thong H–T, Hayashi M, Chen C–Y, Chen K–H, Chen L–C.  2021.  Impact of Cation Substitution in (AgxCu1−x)2ZnSnSe4 Absorber-Based Solar Cells toward 10% Efficiency: Experimental and Theoretical Analyses, 2021. Solar RRLSolar RRL. n/a(n/a):2100441.: John Wiley & Sons, Ltd AbstractWebsite

Solar cells based on kesterite Cu2ZnSnSe4 (CZTSe) compounds with earth-abundant elements are highly desirable for the low-cost and high-efficiency production of renewable energy. However, the occurrence of intrinsic defects substantially impairs the photovoltaic properties of CZTSe. Herein, a cation substitution method to control and passivate the defect states in bandgap of kesterite CZTSe by incorporating Ag ions is introduced. Intensity-dependent low-temperature photoluminescence measurements show that Ag incorporation can reduce the density and depth of intrinsic defects in CZTSe. The results reveal that 10% Ag-alloyed CZTSe provides the shallowest defect states and less nonradiative recombination. It is also confirmed by first-principles calculations that Ag incorporation enables the formation and suppresses the beneficial and detrimental defects, respectively. Based on the theoretical results, the observed subband photoluminescence peaks can be assigned to the intrinsic point and cluster defects. The best power conversion efficiency of 10.2% is achieved for the 10% Ag-alloyed CZTSe cell, along with an enhanced open-circuit voltage. These results open up a new avenue for further improving the performances of CZTSe-based device via defect engineering.

Kamal Hussien, M, Sabbah A, Qorbani M, Hammad Elsayed M, Raghunath P, Lin T-Y, Quadir S, Wang H-Y, Wu H-L, Tzou D-LM, Lin M-C, Chung P-W, Chou H-H, Chen L-C, Chen K-H.  2021.  Metal-free four-in-one modification of g-C3N4 for superior photocatalytic CO2 reduction and H2 evolution, 2021. Chemical Engineering Journal. :132853. AbstractWebsite

Utilization of g-C3N4 as a single photocatalyst material without combination with other semiconductor remains challenging. Herein, we report a facile green method for synthesizing a metal free modified g-C3N4 photocatalyst. The modification process combines four different strategies in a one-pot thermal reaction: non-metal doping, porosity generation, functionalization with amino groups, and thermal oxidation etching. The as-prepared amino-functionalized ultrathin nanoporous boron-doped g-C3N4 exhibited a high specific surface area of 143.2 m2 g−1 which resulted in abundant adsorption sites for CO2 and water molecules. The surface amino groups act as Lewis basic sites to adsorb acidic CO2 molecules, which can also serve as active sites to facilitate hydrogen generation. Besides, the simultaneous use of ammonium chloride as a dynamic gas bubble template along with thermal oxidation etching efficiently boosts the delamination of the g-C3N4 layers to produce ultrathin sheets; this leads to stronger light–matter interactions and efficient charge generation. Consequently, the newly modified g-C3N4 achieved selective gas-phase CO2 reduction into CO with a production yield of 21.95 µmol g-1, in the absence of any cocatalyst. Moreover, a high hydrogen generation rate of 3800 µmol g-1 h-1 and prominent apparent quantum yield of 10.6% were recorded. This work opens up a new avenue to explore different rational modifications of g-C3N4 nanosheets for the efficient production of clean energy.

Venugopal, B, Shown I, Samireddi S, Syum Z, Krishnamoorthy V, Wu H-L, Chu C-W, Lee C-H, Chen L-C, Chen K-H.  2021.  Microstructural intra-granular cracking in Cu2ZnSnS4@C thin-film anode enhanced the electrochemical performance in lithium-ion battery applications, 2021. Materials Advances. 2(17):5672-5685.: RSC AbstractWebsite

Cu2ZnSnS4 (CZTS) has demonstrated excellent performance as an anode material for lithium-ion batteries. However, the repeated lithiation and delithiation create a cracking pattern and lead to island formation in the thin-film electrode, resulting in a capacity fading over cycling in lithium-ion batteries (LIB's). In order to control this crack behaviour, we introduce carbon into CZTS thin-films by a hydrothermal method to form CZTS@C composite. CZTS@C significantly reduced the crack pattern formation on the electrode surface as well as improved the conductivity of the CZTS@C electrode. At the early stages of lithiation and delithiation, the volume expansion and contraction of Li–CZTS@C create intra-granular cracking only at the surface level, and it offers a high capacity of about 785 mA h g−1 after 150 cycles at 1000 mA g−1 charging rate, excellent rate capability (942 mA h g−1, 678 mA h g−1 and 435 mA h g−1 at 500 mA g−1, 2000 mA g−1 and 5000 mA g−1), and superior cyclability (925 mA h g−1 even after 200 cycles at 500 mA g−1). The excellent electrochemical performance at high-current rates can be attributed to intra-granular cracking together with carbon coating that provides a short transportation length for both lithium ions and electrons. Moreover, the controlled cracking pattern formation in CZTS@C facilitates faster reaction kinetics, which open up a new solution for the development of high-power thin-film anodes for next-generation LIBs applications.

Du, H-Y, Huang Y-F, Wong D, Tseng M-F, Lee Y-H, Wang C-H, Lin C-L, Hoffmann G, Chen K-H, Chen L-C.  2021.  Nanoscale redox mapping at the MoS2-liquid interface, 2021. 12(1):1321. AbstractWebsite

Layered MoS2 is considered as one of the most promising two-dimensional photocatalytic materials for hydrogen evolution and water splitting; however, the electronic structure at the MoS2-liquid interface is so far insufficiently resolved. Measuring and understanding the band offset at the surfaces of MoS2 are crucial for understanding catalytic reactions and to achieve further improvements in performance. Herein, the heterogeneous charge transfer behavior of MoS2 flakes of various layer numbers and sizes is addressed with high spatial resolution in organic solutions using the ferrocene/ferrocenium (Fc/Fc+) redox pair as a probe in near-field scanning electrochemical microscopy, i.e. in close nm probe-sample proximity. Redox mapping reveals an area and layer dependent reactivity for MoS2 with a detailed insight into the local processes as band offset and confinement of the faradaic current obtained. In combination with additional characterization methods, we deduce a band alignment occurring at the liquid-solid interface.

Lee, S-W, Abdi ZG, Chen J-C, Chen K-H.  2021.  Optimal method for preparing sulfonated polyaryletherketones with high ion exchange capacity by acid-catalyzed crosslinking for proton exchange membrane fuel cells, 2021. Journal of Polymer ScienceJournal of Polymer Science. 59(8):706-720.: John Wiley & Sons, Ltd AbstractWebsite

Abstract Sulfonated polyaryletherketones (SPAEK) bearing four sulfonic acid groups on the phenyl side groups were synthesized. The benzophenone moiety of polymer backbone was further reduced to benzydrol group with sodium borohydride. The membranes were crosslinked by acid-catalyzed Friedel-Crafts reaction without sacrifice of sulfonic acid groups and ion exchange capacity (IEC) values. Crosslinked membranes with the same IEC value but different water uptake could be prepared. The optimal crosslinking condition was investigated to achieve lower water uptake, better chemical stability (Fenton's test), and higher proton conductivity. In addition, the hydrophilic ionic channels from originally course and disordered could be modified to be narrow and continuous by this crosslinking method. The crosslinked membranes, CS4PH-40-PEKOH (IEC = 2.4 meq./g), reduced water uptake from 200 to 88% and the weight loss was reduced from 11 to 5% during the Fenton test compared to uncrosslinked one (S4PH-40-PEK). The membrane showed comparable proton conductivity (0.01?0.19?S/cm) to Nafion 212 at 80°C from low to high relative humidity (RH). Single H2/O2 fuel cell based on the crosslinked SPAEK with catalyst loading of 0.25?mg/cm2 (Pd/C) exhibited a peak power density of 220.3 mW/cm2, which was close to that of Nafion 212 (214.0 mW/cm2) at 80°C under 53% RH. These membranes provide a good option as proton exchange membrane with high ion exchange capacity for fuel cells.