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Book
Chen, L, Chen W.  2024.  Applications Of X-ray Techniques To Nanomaterials For Energy Research. : World Scientific Publishing Company AbstractWebsite
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Book Chapter
Shown, I, Chen W-F, Chen K-H, Chen L-C.  2023.  Applications of X-ray Spectroscopy in Carbon Dioxide Reduction, 2023/08/30. Applications of X-ray Techniques to Nanomaterials for Energy Research. Volume 24:155-186.: WORLD SCIENTIFIC Abstract

The following sections are included: Introduction XAS for CO2 Reduction Electrochemical CO2 Reduction Photochemical CO2 Reduction Summary and Proposed Research Prospects Acknowledgments ReferencesThe following sections are included: Introduction XAS for CO2 Reduction Electrochemical CO2 Reduction Photochemical CO2 Reduction Summary and Proposed Research Prospects Acknowledgments References

Conference Proceedings
Wen, CY, Wu JJ, Lo HJ, Chen LC, Chen KH, Lin ST, Yu Y-C, Wang C-W, Lin E-K.  2000.  Methylamine growth of SiCN films using ECR-CVD. Mat. Res. Soc. Symp.. :606,115-120.
Kichambare, PD, Tarntair FG, Wang TY, Chen LC, Chen KH, Cheng HC.  1999.  Enhancement in Field Emission of Silicon Micro-tips by Bias-assisted Carburization. the Appl. Diamond Conference and Frontier Carbon Tech. Joint Conference 1999. :353-358., Tsukuba, Japan
Chen, KH, Bhusari DM, Wu JJ, Wei SL, Liu RL, Chen LC.  1998.  Silicon-containing Crystalline Carbon Nitride: a Novel Wide Band Gap Material. the symposium on Light Emitting Devices for Optoelectronic Applications, Electrochemical Society. :Vol98-2,417-433.
Chen, LC, Chen CK, Bhusari DM, Chen KH, Wei SL, Chen YF, Jong YC, Lin DY, Li CF, Huang YS.  1997.  Growth of Ternary Silicon Carbon Nitride as a New Wide Band Gap Material. MRS Symp.. :Vol.468,31.
Chen, KH, Chao CH, Chuang TJ.  1996.  GaN Growth by Nitrogen ECR-CVD Method. MRS Symp. . :Vol.423,377.
Chen, LC, Juan CC, Wu JY, Chen KH, Teng JW.  1996.  On the Optimized Nucleation of Near-Single-Crystal CVD Diamond Film. MRS Symp.. :Vol.416,81.
Chen, KH, Wu JY, Chen LC, Juan CC, Hsu T.  1995.  Epitaxial Growth of Diamond Films for Electronic Applications. the 188th Meeting of the Electrochemical Society. :Vol95-21,p55-69., Chicago
J. Wang, K.H. Chen, ME.  1988.  Energy Llocalization in Infrared Multiphoton Excited CF2Cl2 Studied by Time Resolved Raman Spectroscopy. Int. Conf. Quantum Electronics. :496., Tokyo Japan: Tech. Digest
Mazur, E, Chen KH, Wang J.  1986.  The Interaction of Infrared Radiation with Isolated Molecules: intramolecular nonequilibrium. Int. Conf. on Lasers 6. :359., Orlando
Chen, KH, Wang J, Mazur E.  1986.  Raman Spectroscopy of Infrared Multiphoton Excited Molecules. Int. Quantum Electronics Conf.. , San Francisco
Journal Article
Jarwal, B, Abbas S, Chou T-L, Vailyaveettil SM, Kumar A, Quadir S, Ho T-T, Wong DP, Chen L-C, Chen K-H.  2024.  Boosting Thermoelectric Performance in Nanocrystalline Ternary Skutterudite Thin Films through Metallic CoTe2 Integration, 2024. ACS Applied Materials & InterfacesACS Applied Materials & Interfaces. 16(12):14770-14780.: American Chemical Society AbstractWebsite
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Kamal Hussien, M, Sabbah A, Qorbani M, Putikam R, Kholimatussadiah S, Tzou D-LM, Hammad Elsayed M, Lu Y-J, Wang Y-Y, Lee X-H, Lin T-Y, Thang NQ, Wu H-L, Haw S-C, Wu KC-W, Lin M-C, Chen K-H, Chen L-C.  2024.  Constructing B─N─P Bonds in Ultrathin Holey g-C3N4 for Regulating the Local Chemical Environment in Photocatalytic CO2 Reduction to CO, 2024. Small. n/a(n/a):2400724.: John Wiley & Sons, Ltd AbstractWebsite

Abstract The lack of intrinsic active sites for photocatalytic CO2 reduction reaction (CO2RR) and fast recombination rate of charge carriers are the main obstacles to achieving high photocatalytic activity. In this work, a novel phosphorus and boron binary-doped graphitic carbon nitride, highly porous material that exhibits powerful photocatalytic CO2 reduction activity, specifically toward selective CO generation, is disclosed. The coexistence of Lewis-acidic and Lewis-basic sites plays a key role in tuning the electronic structure, promoting charge distribution, extending light-harvesting ability, and promoting dissociation of excitons into active carriers. Porosity and dual dopants create local chemical environments that activate the pyridinic nitrogen atom between the phosphorus and boron atoms on the exposed surface, enabling it to function as an active site for CO2RR. The P?N?B triad is found to lower the activation barrier for reduction of CO2 by stabilizing the COOH reaction intermediate and altering the rate-determining step. As a result, CO yield increased to 22.45 µmol g?1 h?1 under visible light irradiation, which is ≈12 times larger than that of pristine graphitic carbon nitride. This study provides insights into the mechanism of charge carrier dynamics and active site determination, contributing to the understanding of the photocatalytic CO2RR mechanism.

Qorbani, M, Chen K-H, Chen L-C.  2024.  Hybrid and Asymmetric Supercapacitors: Achieving Balanced Stored Charge across Electrode Materials, 2024. Small. n/a(n/a):2400558.: John Wiley & Sons, Ltd AbstractWebsite

Abstract An electrochemical capacitor configuration extends its operational potential window by leveraging diverse charge storage mechanisms on the positive and negative electrodes. Beyond harnessing capacitive, pseudocapacitive, or Faradaic energy storage mechanisms and enhancing electrochemical performance at high rates, achieving a balance of stored charge across electrodes poses a significant challenge over a wide range of charge?discharge currents or sweep rates. Consequently, fabricating hybrid and asymmetric supercapacitors demands precise electrochemical evaluations of electrode materials and the development of a reliable methodology. This work provides an overview of fundamental aspects related to charge-storage mechanisms and electrochemical methods, aiming to discern the contribution of each process. Subsequently, the electrochemical properties, including the working potential windows, rate capability profiles, and stabilities, of various families of electrode materials are explored. It is then demonstrated, how charge balancing between electrodes falters across a broad range of charge?discharge currents or sweep rates. Finally, a methodology for achieving charge balance in hybrid and asymmetric supercapacitors is proposed, outlining multiple conditions dependent on loaded mass and charge?discharge current. Two step-by-step tutorials and model examples for applying this methodology are also provided. The proposed methodology is anticipated to stimulate continued dialogue among researchers, fostering advancements in achieving stable and high-performance supercapacitor devices.

Hammad Elsayed, M, Abdellah M, Alhakemy AZ, Mekhemer IMA, Aboubakr AEA, Chen B-H, Sabbah A, Lin K-H, Chiu W-S, Lin S-J, Chu C-Y, Lu C-H, Yang S-D, Mohamed MG, Kuo S-W, Hung C-H, Chen L-C, Chen K-H, Chou H-H.  2024.  Overcoming small-bandgap charge recombination in visible and NIR-light-driven hydrogen evolution by engineering the polymer photocatalyst structure, 2024. Nature Communications. 15(1):707. AbstractWebsite

Designing an organic polymer photocatalyst for efficient hydrogen evolution with visible and near-infrared (NIR) light activity is still a major challenge. Unlike the common behavior of gradually increasing the charge recombination while shrinking the bandgap, we present here a series of polymer nanoparticles (Pdots) based on ITIC and BTIC units with different π-linkers between the acceptor-donor-acceptor (A-D-A) repeated moieties of the polymer. These polymers act as an efficient single polymer photocatalyst for H2 evolution under both visible and NIR light, without combining or hybridizing with other materials. Importantly, the difluorothiophene (ThF) π-linker facilitates the charge transfer between acceptors of different repeated moieties (A-D-A-(π-Linker)-A-D-A), leading to the enhancement of charge separation between D and A. As a result, the PITIC-ThF Pdots exhibit superior hydrogen evolution rates of 279 µmol/h and 20.5 µmol/h with visible (>420 nm) and NIR (>780 nm) light irradiation, respectively. Furthermore, PITIC-ThF Pdots exhibit a promising apparent quantum yield (AQY) at 700 nm (4.76%).

Krishnamoorthy, V, Sabhapathy P, Raghunath P, Huang C-Y, Sabbah A, Kamal Hussien M, Syum Z, Muthusamy S, Lin M-C, Wu H-L, Chen R-S, Chen K-H, Chen L-C.  2024.  Synergistic Electronic Interaction of Nitrogen Coordinated Fe-Sn Double-Atom Sites: An Efficient Electrocatalyst for Oxygen Reduction Reaction, 2024. Small Methods. n/a(n/a):2301674.: John Wiley & Sons, Ltd AbstractWebsite

Abstract Double-atom site catalysts (DASs) have emerged as a recent trend in the oxygen reduction reaction (ORR), thereby modifying the intermediate adsorption energies and increasing the activity. However, the lack of an efficient dual atom site to improve activity and durability has limited these catalysts from widespread application. Herein, the nitrogen-coordinated iron and tin-based DASs (Fe-Sn-N/C) catalyst are synthesized for ORR. This catalyst has a high activity with ORR half-wave potentials (E1/2) of 0.92 V in alkaline, which is higher than those of the state-of-the-art Pt/C (E1/2 = 0.83 V), Fe-N/C (E1/2 = 0.83 V), and Sn-N/C (E1/2 = 0.77 V). Scanning electron transmission microscopy analysis confirmed the atomically distributed Fe and Sn sites on the N-doped carbon network. X-ray absorption spectroscopy analysis revealed the charge transfer between Fe and Sn. Both experimental and theoretical results indicate that the Sn with Fe-NC (Fe-Sn-N/C) induces charge redistribution, weakening the binding strength of oxygenated intermediates and leading to improved ORR activity. This study provides the synergistic effects of DASs catalysts and addresses the impacts of P-block elements on d-block transition metals in ORR.

Sabhapathy, P, Raghunath P, Sabbah A, Shown I, Bayikadi KS, Xie R-K, Krishnamoorthy V, Lin M-C, Chen K-H, Chen L-C.  2023.  Axial Chlorine Induced Electron Delocalization in Atomically Dispersed FeN4 Electrocatalyst for Oxygen Reduction Reaction with Improved Hydrogen Peroxide Tolerance, 2023. Small. :2303598.: John Wiley & Sons, Ltd AbstractWebsite

Abstract Atomically dispersed iron sites on nitrogen-doped carbon (Fe-NC) are the most active Pt-group-metal-free catalysts for oxygen reduction reaction (ORR). However, due to oxidative corrosion and the Fenton reaction, Fe-NC catalysts are insufficiently active and stable. Herein, w e demonstrated that the axial Cl-modified Fe-NC (Cl-Fe-NC) electrocatalyst is active and stable for the ORR in acidic conditions with high H2O2 tolerance. The Cl-Fe-NC exhibits excellent ORR activity, with a high half-wave potential (E1/2) of 0.82 V versus a reversible hydrogen electrode (RHE), comparable to Pt/C (E1/2 = 0.85 V versus RHE) and better than Fe-NC (E1/2 = 0.79 V versus RHE). X-ray absorption spectroscopy analysis confirms that chlorine is axially integrated into the FeN4. More interestingly, compared to Fe-NC, the Fenton reaction is markedly suppressed in Cl-Fe-NC. In situ electrochemical impedance spectroscopy reveals that Cl-Fe-NC provides efficient electron transfer and faster reaction kinetics than Fe-NC. Density functional theory calculations reveal that incorporating Cl into FeN4 can drive the electron density delocalization of the FeN4 site, leading to a moderate adsorption free energy of OH* (?GOH*), d-band center, and a high onset potential, and promotes the direct four-electron-transfer ORR with weak H2O2 binding ability compared to Cl-free FeN4, indicating superior intrinsic ORR activity.

Syum, Z, Billo T, Sabbah A, kumar Anbalagan A, Quadir S, Hailemariam AG, Sabhapathy P, Lee C-H, Wu H-L, Chen L-C, Chen K-H.  2023.  Enhancing the lithium-ion storage capability of Cu2ZnSnS4 anodes via a nitrogen-doped conductive support, 2023. Chemical Engineering Journal. 465:142786. AbstractWebsite

Achieving lithium-ion batteries with both excellent electrochemical performance and cycling stability is a top priority for their real-world applications. This work reports high-performance and stable Cu2ZnSnS4 (CZTS) anode materials encapsulated by nitrogen-doped carbon (CZTS@N-C) for advanced lithium-ion battery application. Ex-situ X-ray photoelectron spectroscopy and transmission electron microscopy revealed that the nitrogen-doped carbon network features a more conducive solid-electrolyte interphase that enables lower charge-transfer resistance and fast Li+ diffusion kinetics with negligible initial irreversible capacity loss. As a result, the CZTS@N-C electrode delivers a significantly enhanced capacity of 710 mAh g−1 with 73% capacity retention after 220 cycles at a current rate of 0.5 mA g−1 and superior rate performance compared to that of unmodified CZTS. Additionally, the study sheds light on the fast lithiation dynamics chemistry of CZTS@N-C through kinetics analysis, explored by in-situ Raman, ex-situ X-ray absorption, and in-situ electrochemical impedance. This study provides a new approach for fabricating high-performance, durable conductive polymer-encapsulated low-cost transition-metal-sulfide anode materials.

Muthusamy, S, Sabhapathy P, Raghunath P, Sabbah A, Chang Y-C, Krishnamoorthy V, Ho T-T, Chiou J-W, Lin M-C, Chen L-C, Chen K-H.  2023.  Mimicking Metalloenzyme Microenvironments in the Transition Metal-Single Atom Catalysts for Electrochemical Hydrogen Peroxide Synthesis in an Acidic Medium, 2023. Small Methods. :2300234.: John Wiley & Sons, Ltd AbstractWebsite

Abstract Electrochemical reduction of oxygen into hydrogen peroxide in an acidic medium offers an energy-efficient and green H2O2 synthesis as an alternative to the energy-intensive anthraquinone process. Unfortunately, high overpotential, low production rates, and fierce competition from traditional four-electron reduction limit it. In this study, a metalloenzyme-like active structure is mimicked in carbon-based single-atom electrocatalysts for oxygen reduction to H2O2. Using a carbonization strategy, the primary electronic structure of the metal center with nitrogen and oxygen coordination is modulated, followed by epoxy oxygen functionalities close to the metal active sites. In an acidic medium, CoNOC active structures proceed with greater than 98% H2O2 selectivity (2e?/2H+) rather than CoNC active sites that are selective to H2O (4e?/4H+). Among all MNOC (M = Fe, Co, Mn, and Ni) single-atom electrocatalysts, the CoNOC is the most selective (> 98%) for H2O2 production, with a mass activity of 10 A g?1 at 0.60 V vs. RHE. X-ray absorption spectroscopy is used to identify the formation of unsymmetrical MNOC active structures. Experimental results are also compared to density functional theory calculations, which revealed that the structure-activity relationship of the epoxy-surrounded CoNOC active structure reaches optimum (?G*OOH) binding energies for high selectivity.

Muthusamy, S, Sabbah A, Sabhapathy P, Chang Y-C, Billo T, Syum Z, Chen L-C, Chen K-H.  2023.  Modification of Conductive Carbon with N-Coordinated Fe−Co Dual-Metal Sites for Oxygen Reduction Reaction, 2023. ChemElectroChem. n/a(n/a):e202300272.: John Wiley & Sons, Ltd AbstractWebsite

Abstract Earth-abundant commercial conductive carbon materials are ideal electrocatalyst supports but cannot be directly utilized for single-atom catalysts owing to the lack of anchoring sites. Therefore, we employed crosslink polymerization to modify the conductive carbon surface with Fe?Co dual-site electrocatalysts for oxygen reduction reaction (ORR). First, metal-coordinated polyurea (PU) aerogels were prepared using via crosslinked polymerization at ambient temperature. Then, carbon-supported, atomically dispersed Fe?Co dual-atom sites (FeCoNC/BP) were formed by high-temperatures pyrolysis with a nitrogen source. FTIR and 13C NMR measurements showed PU linkages, while 15N NMR revealed metal?nitrogen coordination in the PU gels. Asymmetric, N-coordinated, and isolated Fe?Co active structures were found after pyrolysis using XAS and STEM. In alkaline media, FeCoNC/BP exhibited excellent ORR activity, with a E1/2 of 0.93?V vs. RHE, higher than that of Pt/C (20?%) (0.90?V), FeNC/BP (0.88?V), and CoNC/BP (0.85?V). An accelerated durability test (ADT) on FeCoNC/BP indicated good durability over 35000 cycles. FeCoNC/BP also showed moderate ORR and ADT performance in acidic media. The macro/mesoporous N-doped carbon structures enhanced the mass transport properties of the dual Fe?Co active-sites. Therefore, modifying carbon supports with nonprecious metal catalysts may be a cost-effective-strategy for sustained electrochemical energy conversion.

Kamal Hussien, M, Sabbah A, Qorbani M, Hammad Elsayed M, Quadir S, Raghunath P, Tzou D-LM, Haw S-C, Chou H-H, Thang NQ, Lin M-C, Chen L-C, Chen K-H.  2023.  Numerous defects induced by exfoliation of boron-doped g-C3N4 towards active sites modulation for highly efficient solar-to-fuel conversion, 2023. Materials Today Sustainability. 22:100359. AbstractWebsite

Graphitic carbon nitride (CN) has emerged as a highly promising material in the photocatalysis field. However, its bulk structure suffers from a lack of active sites, limiting its practical application. Herein, a boron-doped CN (BCN) was prepared by a green gas-blowing-assisted thermal polymerization and then subjected to different exfoliation processes in order to delaminate the layered structure and tune the surface-active sites. A thorough comparative study shows that thermal exfoliation creates unsaturated nitrogen sites and induces the formation of interconnected layers that act as an electron diffusion channel for better charge transport. Furthermore, the thermally exfoliated BCN is rich in structural disorders that serve as dissociation defects for photoinduced charge carriers with a low exciton binding energy of 27 meV. Experimental results supported by theoretical calculations show that the nitrogen adjacent to boron is activated by the surrounding surface amino groups and the perforated texture to serve as an active adsorption site towards CO2 and H2O. Consequently, the exfoliated BCN acts as an outstanding bifunctional photocatalyst towards CO2 reduction into CO (40.41 μmol g−1 h−1) and prominent hydrogen evolution (4740 μmol g−1 h−1, 12.2% apparent quantum yield (AQY)).

Qorbani, M, Sabbah A, Lai Y-R, Kholimatussadiah S, Quadir S, Huang C-Y, Shown I, Huang Y-F, Hayashi M, Chen K-H, Chen L-C.  2022.  Atomistic insights into highly active reconstructed edges of monolayer 2H-WSe2 photocatalyst, 2022. Nature Communications. 13(1):1256. AbstractWebsite

Ascertaining the function of in-plane intrinsic defects and edge atoms is necessary for developing efficient low-dimensional photocatalysts. We report the wireless photocatalytic CO2 reduction to CH4 over reconstructed edge atoms of monolayer 2H-WSe2 artificial leaves. Our first-principles calculations demonstrate that reconstructed and imperfect edge configurations enable CO2 binding to form linear and bent molecules. Experimental results show that the solar-to-fuel quantum efficiency is a reciprocal function of the flake size. It also indicates that the consumed electron rate per edge atom is two orders of magnitude larger than the in-plane intrinsic defects. Further, nanoscale redox mapping at the monolayer WSe2–liquid interface confirms that the edge is the most preferred region for charge transfer. Our results pave the way for designing a new class of monolayer transition metal dichalcogenides with reconstructed edges as a non-precious co-catalyst for wired or wireless hydrogen evolution or CO2 reduction reactions.

Sabbah, A, Shown I, Qorbani M, Fu F-Y, Lin T-Y, Wu H-L, Chung P-W, Wu C-I, Santiago SRM, Shen J-L, Chen K-H, Chen L-C.  2022.  Boosting photocatalytic CO2 reduction in a ZnS/ZnIn2S4 heterostructure through strain-induced direct Z-scheme and a mechanistic study of molecular CO2 interaction thereon, 2022. Nano Energy. 93:106809. AbstractWebsite

Employing direct Z-scheme semiconductor heterostructures in photocatalysis offers efficient charge carrier separation and isolation of both redox reactions, thus beneficial to reduce CO2 into solar fuels. Here, a ZnS/ZnIn2S4 heterostructure, comprising cubic ZnS nanocrystals on hexagonal ZnIn2S4 (ZIS) nanosheets, is successfully fabricated in a single-pot hydrothermal approach. The composite ZnS/ZnIn2S4 exhibits microstrain at its interface with an electric field favorable for Z-scheme. At an optimum ratio of Zn:In (~ 1:0.5), an excellent photochemical quantum efficiency of around 0.8% is reached, nearly 200-fold boost compared with pristine ZnS. Electronic levels and band alignments are deduced from ultraviolet photoemission spectroscopy and UV-Vis. Evidence of the direct Z-scheme and carrier dynamics is verified by photo-reduction experiment, along with photoluminescence (PL) and time-resolved PL. Finally, diffuse-reflectance infrared Fourier transformed spectroscopy explores the CO2 and related intermediate species adsorbed on the catalyst during the photocatalytic reaction. This microstrain-induced direct Z-scheme approach opens a new pathway for developing next-generation photocatalysts for CO2 reduction.

Fahimi, Z, Moradlou O, Sabbah A, Chen K-H, Chen L-C, Qorbani M.  2022.  Co3V2O8 hollow spheres with mesoporous walls as high-capacitance electrode for hybrid supercapacitor device, 2022. 436:135225. AbstractWebsite

Bimetal oxides are promising materials in the field of energy storage due to their various oxidation states, synergistic interactions among multiple metal species, and stability. In this work, Co3V2O8 hollow spheres are synthesized by a two-step hydrothermal method: (i) synthesis of V2O5 spheres and (ii) partial replacement of V by Co through the Kirkendall effect. As an electrode, it shows an extrinsic pseudocapacitive charge-storage mechanism due to different oxidation states of V and Co ions. Because of the low crystallinity degree of the mesoporous wall and high accessible surface area of hollow spheres, the optimum Co3V2O8 electrode reaches a high specific capacitance of 2376F g−1 at a current density of 2 A g−1, which is more than two times higher than the top reported values, and a rate capability retention of ∼80% at 20 A g−1. Using Co3V2O8, activated carbon, and KOH as positive, negative electrodes, and electrolyte, respectively, a hybrid supercapacitor device presents maximum energy and power densities of 59.2 Wh kg−1 and 36.6 kW kg−1, respectively. Further, the aqueous supercapacitor device shows superior structural and electrochemical stabilities after 10,000 galvanostatic charge–discharge cycles because of the arrays of voids in the orthorhombic crystal structure of Co3V2O8 that can decrease the volume expansion/shrinkage during the intercalation/deintercalation processes. Our results provide a platform for exploring bimetallic Co and V-based oxides, hydroxides, and sulfides nanostructures as promising energy storage materials in the future.