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.

Gas bubble evolution is an important phenomenon in many electrochemical processes and it is highly sensitive to the surface properties. Here we visualize the gas bubble dynamics on the surface of different graphene substrates during hydrogen evolution reaction (HER) using atomic force microscopy combined with scanning electrochemical microscopy. The low overpotential and low surface hydrophobicity of few-layer graphene formed on C-phase SiC causes the uniform distribution of hydrogen nanobubbles, which easily depart from the surface during the reaction. Conversely, the high overpotential and more hydrophobic surface of HOPG induces hydrogen bubbles to linger on the surface for an extended duration, leading to its accumulation and the subsequent formation of microbubbles. This in-situ nanoscale electrochemical mapping of hydrogen bubble dynamics provides new insight into electrocatalytic HER that occurs on non-metal electrodes.

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.

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.

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.

Direct Z-scheme heterojunctions are widely used for photocatalytic water splitting and CO2 reduction due to facilitating well-separated photogenerated charge carriers and spatial isolation of redox reactions. Here, using a facile two-step hydrothermal and ion-exchange method, we uniformly decorate silver orthophosphate (i.e., Ag3PO4) quantum dots with an average characteristic size of ∼10 nm over tin(iv) sulphide (i.e., SnS2) nanosheets to form a 0D/2D heterojunction. The direct Z-scheme mechanism, i.e. charge transport for efficient electron (from SnS2) and hole (from Ag3PO4) recombination, is confirmed by the following experiments: (i) ultraviolet and X-ray photoelectron spectroscopies; (ii) photodeposition of Pt and PbO2 nanoparticles on reduction and oxidation sites, respectively; (iii) in situ X-ray photoelectron spectroscopy; and (iv) electron paramagnetic resonance spectroscopy. Owing to the photoreduction properties of Ag3PO4 with orthophosphate vacancies, Z-scheme charge carrier transfer, and efficient exciton dissociation, an optimized heterojunction shows a high CO2-to-CO reduction yield of 18.3 μmol g−1 h−1 with an illustrious selectivity of ∼95% under light illumination, which is about 3.0 and 47.8 times larger than that of Ag3PO4 and SnS2, respectively. The carbon source for the CO product is verified using a 13CO2 isotopic experiment. Moreover, by tracing the peak at ∼1190 cm−1 in the dark and under light irradiation, in situ diffuse reflectance infrared Fourier transform spectroscopy demonstrates that the CO2 reduction pathway goes through the COOH* intermediate.

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.

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.

AbstractPorous α-Fe2O3 nanoparticles are directly grown on acid treated carbon cloth (ACC) using a simple hydrothermal method (denoted as ACC-α-Fe2O3) for employment as a flexible and wearable electrochemical electrode. The catalytic activity of ACC-α-Fe2O3 allowing the detection of dopamine (DA) is systematically investigated. The results showed that the ACC-α-Fe2O3 electrode exhibits impressive electrochemical sensitivity, stability and selectivity for the detection of DA. The detection limit determined with the amperometric method appears to be around 50nM with a linear range of 0.074–113μM. The impressive DA sensing ability of the as prepared ACC-α-Fe2O3 electrode is due to the good electrochemical behavior and high electroactive surface area (19.96cm2) of α-Fe2O3 nanoparticles anchored on the highly conductive ACC. It is worth noting that such remarkable sensing properties can be maintained even when the electrode is in a folded configuration.