Kuei-Hsien Chen

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.

An innovative strategy has been developed to activate the basal planes in molybdenum disulfide (MoS2) to improve their electrocatalytic activity by controlling surface electron accumulation (SEA) through aging, annealing, and nitrogen-plasma treatments. The optimal hydrogen evolution reaction (HER) performance was obtained on the surface treated with nitrogen-plasma for 120 s. An overpotential of 0.20 V and a Tafel slope of 120 mV dec−1 were achieved for the optimized condition. The angle-resolved photoemission spectroscopy measurement confirmed the HER efficiency enhanced by the SEA conjugated with the sulfur vacancy active sites in the MoS2 basal planes. This study provides new insight into optimizing MoS2 catalysts for energy applications.

Reduction of CO2 to value-added hydrocarbons through artificial photosynthesis is one of the way to address the energy crisis and climate change issues. It is known that lowering the activation energy of CO2 molecules on the photocatalyst surface and key intermediates is crucial in photocatalytic CO2 reduction. Herein, we present phosphorus-implanted 20-nm SnS2 continuous thin film with sulfur vacancies (i.e., SV-SnS2:P where P substitutes on S sites). The fabrication process involves thermal evaporation, post-sulfurization, and ion implantation. Our gas-phase photocatalytic experiments show an enhanced and selective CO2 photoreduction to CH4 with a yield of 0.13 µmol cm−2 and selectivity of 92 % under solar-light irradiation for 4 h over an optimal ∼4.5 % P and ∼16 % SV. Experimental observations, conducted through X-ray absorption near edge, in situ near ambient pressure X-ray photoelectron, and in situ Fourier transform infrared spectroscopies, along with first-principle density functional theory calculations. Results reveal that P dopant is significantly affected by nearby SV via local charge density transfer from P to the nearest Sn and next-nearest S neighbor atoms, consequently, leads to the stabilization of *COOH and *CHO intermediates, where asterisks stand for P as the active site. Our results demonstrate how active site modulation, without using precious co-catalysts, plays a crucial role in intermediate stabilization in a wireless photocatalysis process.

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%).

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.

Single-atom-supported metal oxides have attracted extensive interest in energy catalysis, offering a promising avenue for mitigating greenhouse gas emissions and environmental pollution. This study presents a facile synthesis of single-atom Fe-modified Bi2WO6 photocatalysts. By carefully tuning the Fe ratios, the 1.5Fe-Bi2WO6 sample demonstrates exceptional photocatalytic efficiency in CO2 to CO reduction (36.78 μmol g−1). Additionally, an outstanding NO removal performance is also achieved through this photocatalyst with an impressively low conversion of toxic NO2 at just 0.37%. The reaction intermediates and mechanisms governing the photocatalytic reduction of CO2 into CO are elucidated using in situ DRIFTS and in situ XAS techniques. Regarding NO removal, the introduction of Fe single-atoms, along with induced oxygen vacancies, plays a pivotal role in facilitating the transformation of NO and NO2 into nitrate by stabilizing NO and NO2 species. Mechanistic insights into photocatalytic NO oxidation are garnered through scavenger trapping and EPR experiments employing DMPO. This study emphasizes single-atom-supported metal oxide's potential in sustainable chemistry and air purification, providing a promising solution for urgent environmental challenges.

High thermoelectric performance is a material challenge associated mainly with the manipulation of lattice dynamics to obtain extrinsic phonon transport routes, which can make the lattice thermal conductivity (κlat) intrinsically low by introducing multiple scattering mechanisms. The present study shows that the lattice-strain-induced phonon scattering resulting from microstructural distortions in GeTe-based compounds can enable ultralow lattice thermal conductivity. The unusual lattice shrinkage, W interstitials, W nanoprecipitates, and heavy elemental mass, in Ge0.85Sb0.1W0.05Te culminate in an ultralow lattice thermal conductivity of ∼0.2 W m−1 K−1 at 825 K. Microstructural distortions in this Sb/W co-doped GeTe are found to be primarily associated with shorter W–Te bonding owing to the anomalous effect of the higher electronegativity of the W atoms. Furthermore, the increased electrical conductivity (σ) resulting from the enhanced vacancy formation caused by W doping and W interstitials synergistically contributes to optimization of the thermoelectric performance (ZT) to ∼2.93 at 825 K. The thermoelectric efficiency (η) as high as ∼17% has been obtained for a single leg in this composition at an operating temperature of 825 K, with an estimated device ZT value of ∼1.38.

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.

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.

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.

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)).

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.

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.

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Tin monosulfide (SnS) is a promising light-harvesting material for solar cell applications, owing to its potential for large-scale production, cost-effectiveness, eco-friendly source materials, and long-term stability. However, SnS crystallizes in an orthorhombic structure, which results in a highly anisotropic charge transport behavior. Tailoring the crystallographic orientation of the SnS absorber layer plays a critical role in the enhancement of the transfer of charge carriers and the power conversion efficiency (PCE). By controlling the substrate tilting angle and temperature ramp rate in vapor transport deposition, the crystal growth orientation was tuned to a preferred direction which significantly suppressed the unfavorable (040) crystallographic plane. Through the combination of these two approaches, the PCE could be increased from 0.11% to 2%. The effect of the tilting angle was numerically simulated to investigate its role in controlling the film uniformity and directing the film growth. In addition, the correlation between the texture coefficient of the (040) plane and the charge transport properties was determined by a combination of analytical methods such as device performance studies, electrochemical impedance spectroscopy, along with transient photovoltage, space-charge-limited current, and dark current measurements. These techniques were blended together to prove that the marked improvement in PCE can be ascribed to a reduced charge recombination (in both SnS bulk and interfaces) and an enhanced hole mobility.

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Multielement alloying is an appealing approach for suppressing thermal conductivity of thermoelectric materials. In this study, we synthesized GeTe-based high-entropy alloys with notable (S, Se) substitution at Te sites and (Ag, Sb) at Ge sites. The Ge0.82Ag0.08Sb0.1S0.5Se0.1Te0.4 exhibits an extremely low thermal conductivity of ∼ 0.66 W/m⋅K and a high Seebeck coefficient (>250 μV/K) over a temperature range of 150 – 400 °C. The influence of lattice distortion on phase transformation and transport properties of Ge0.9-2xAg2xSb0.1S0.5Se0.1Te0.4 (x = 0 – 0.06) was investigated.

Abstract Effects of electronic and atomic structures of V-doped 2D layered SnS2 are studied using X-ray spectroscopy for the development of photocatalytic/photovoltaic applications. Extended X-ray absorption fine structure measurements at V K-edge reveal the presence of VO and VS bonds which form the intercalation of tetrahedral OVS sites in the van der Waals (vdW) gap of SnS2 layers. X-ray absorption near-edge structure (XANES) reveals not only valence state of V dopant in SnS2 is ≈4+ but also the charge transfer (CT) from V to ligands, supported by V Lα,β resonant inelastic X-ray scattering. These results suggest V doping produces extra interlayer covalent interactions and additional conducting channels, which increase the electronic conductivity and CT. This gives rapid transport of photo-excited electrons and effective carrier separation in layered SnS2. Additionally, valence-band photoemission spectra and S K-edge XANES indicate that the density of states near/at valence-band maximum is shifted to lower binding energy in V-doped SnS2 compare to pristine SnS2 and exhibits band gap shrinkage. These findings support first-principles density functional theory calculations of the interstitially tetrahedral OVS site intercalated in the vdW gap, highlighting the CT from V to ligands in V-doped SnS2.

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.

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.

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.

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.

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.

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.