Adsorbed p-Aminothiophenol Molecules on Platinum Nanoparticles Improve Electrocatalytic Hydrogen Evolution.

Electrocatalytic hydrogen evolution is an important approach to produce clean energy, and many electrocatalysts (e.g., platinum) are developed for hydrogen production. However, the electrocatalytic efficiency of commonly used metal catalysts needs to be improved to compensate their high cost. Herein, the electrocatalytic efficiency of platinum nanoparticles (PtNPs) in hydrogen evolution is largely improved via simple surface adsorption of sub-monolayer p-aminothiophenol (PATP) molecules. The overpotential goes down to 86.1 mV, which is 50.2 mV lower than that on naked PtNPs. This catalytic activity is even better than that of 20 wt.% Pt/C, despite the much smaller active surface area of PATP-adsorbed PtNPs than Pt/C. It is theoretically and experimentally confirmed that the improved electrocatalytic activity in hydrogen evolution can be attributed to the change in electronic structure of PtNPs induced by surface adsorption of PATP molecules. More importantly, this strategy can also be used to improve the electrocatalytic activity of palladium, gold, and silver nanoparticles. Therefore, this work provides a simple, convenient, and versatile method for improving the electrocatalytic activity of metal nanocatalysts. This surface adsorption strategy may also be used for improving the efficiency of many other nanocatalysts in many reactions.

Realizing Ultrahigh Transconductance in Organic Electrochemical Transistor by Co-Doping PEDOT:PSS with Ionic Liquid and Dodecylbenzenesulfonate.

Organic electrochemical transistors (OECTs), especially the ones with high transconductance, are highly promising in sensitive detection of chemical and biological species. However, it is still a great challenge to design and fabricate OECTs with very high transconductance. Herein, an OECT with ultrahigh transconductance is reported by introducing ionic liquid and dodecylbenzenesulfonate (DBSA) simultaneously in poly(3,4-ethylenedioxythiophene): polystyrenesulfonate (PEDOT:PSS) as the semiconductive channel. Compared with the OECT based on pristine PEDOT:PSS, the OECT based on co-doped PEDOT:PSS demonstrates a significant enhancement of transconductance from 1.85 to 22.7 mS, because of the increase in volumetric capacitance and conductivity. The enhanced transconductance is attributed to the DBSA-facilitated phase separation between the ionic liquid and PEDOT:PSS, which helps to form conductive domains of ionic liquid in PEDOT:PSS matrix, and the partial dispersion of ionic liquid in the PEDOT:PSS phase. Furthermore, by using the interdigitated electrodes as the source and drain electrodes, an ultrahigh transconductance of 180 mS is obtained, which is superior to that of the state-of-the-art OECTs. Because of the ultrahigh transconductance, the obtained OECT demonstrates sensitive detection of hydrogen peroxide and glucose, making it promising in clinical diagnosis, health monitoring, and environmental surveillance.

Charge Dispersion Strategy for High-Performance and Rain-Proof Triboelectric Nanogenerator.

Triboelectric nanogenerator (TENG) is becoming a sustainable and renewable way of energy harvesting and self-powered sensing because of low cost, simple structure, and high efficiency. However, the output current of existing TENGs is still low. It is proposed that the output current of TENGs can be dramatically improved if the triboelectric charges can distribute inside the triboelectric layers. Herein, a novel single-electrode conductive network-based TENG (CN-TENG) is developed by introducing a conductive network of multiwalled carbon nanotubes in dielectric triboelectric layer of thermoplastic polyurethane (TPU). In this CN-TENG, the contact electrification-induced charges distribute on both the surface and interior of the dielectric TPU layer. Thus, the short-circuit current of CN-TENG improves for 100-fold, compared with that of traditional dielectric TENG. In addition, this CN-TENG, even without packing, can work stably in high-humidity environments and even in the rain, which is another main challenge for conventional TENGs due to charge leakage. Further, this CN-TENG is applied for the first time, to successfully distinguish conductive and dielectric materials. This work provides a new and effective strategy to fabricate TENGs with high output current and humidity-resistivity, greatly expanding their practical applications in energy harvesting, movement sensing, human-machine interaction, and so on.

Selective adsorption of cysteamine molecules on Au/TiO2 boosts visible light-driven photocatalytic hydrogen evolution.

Photocatalytic evolution of hydrogen is becoming a research hotspot because it can help to produce clean energy and reduce environmental pollution. Titanium dioxide (TiO2) and its composites are photocatalysts that are widely used in hydrogen evolution because of their high abundance in nature, low price, and high photo/chemical stability. However, their catalytic performances still need to be further improved, particularly in the visible light spectrum. Herein, visible light-driven photocatalytic evolution of hydrogen on Au/TiO2 nanocomposite is enhanced âˆ¼ 10 folds by selectively functionalizing the nanocomposite with cysteamine molecules. It is revealed that the amine group (-NH2) in cysteamine favors the transfer and separation of photo-generated hot carriers. The rate of hydrogen produced can be further tuned by varying the ionization of the functionalized molecules at different pH values. This work provides a simple, convenient, and effective method that can be used to improve the photocatalytic evolution of hydrogen. This method can also be used for many other nanocatalysts (e.g., Au-MoS2, Au-BiVO4) and catalytic reactions (e.g., carbon dioxide reduction, nitrogen reduction).

High-Performance Organic Electrochemical Transistor Based on Photo-annealed Plasmonic Gold Nanoparticle-Doped PEDOT:PSS.

Organic electrochemical transistors (OECTs), particularly the ones based on PEDOT:PSS, are excellent candidates for chemical and biological sensing because of their unique advantages. Improving the sensitivity and stability of OECTs is crucially important for practical applications. Herein, the transconductance of OECT is improved by 8-fold to 14.9 mS by doping the PEDOT:PSS channel with plasmonic gold nanoparticles (AuNPs) using a solution-based process followed by photo annealing. In addition, the OECT also possesses high flexibility and cyclic stability. It is revealed that the doping of AuNPs increases the conductivity of PEDOT:PSS and the photo annealing improves the crystallinity of the PEDOT:PSS channel and the interaction between AuNPs and PEDOT:PSS. These changes lead to the increase in transconductance and cyclic stability. The prepared OECTs are also demonstrated to be effective in sensitive detection of glucose within a wide concentration range of 10 nM-1 mM. Our OECTs based on photo-annealed plasmonic AuNP-doped PEDOT:PSS may find great applications in chemical and biological sensing, and this strategy may be extended to prepare many other high-performance OECT-based devices.

Strong synergy between gold nanoparticles and cobalt porphyrin induces highly efficient photocatalytic hydrogen evolution.

The reaction efficiency of reactants near plasmonic nanostructures can be enhanced significantly because of plasmonic effects. Herein, we propose that the catalytic activity of molecular catalysts near plasmonic nanostructures may also be enhanced dramatically. Based on this proposal, we develop a highly efficient and stable photocatalytic system for the hydrogen evolution reaction (HER) by compositing a molecular catalyst of cobalt porphyrin together with plasmonic gold nanoparticles, around which plasmonic effects of localized electromagnetic field, local heating, and enhanced hot carrier excitation exist. After optimization, the HER rate and turn-over frequency (TOF) reach 3.21 mol g-1 h-1 and 4650 h-1, respectively. In addition, the catalytic system remains stable after 45-hour catalytic cycles, and the system is catalytically stable after being illuminated for two weeks. The enhanced reaction efficiency is attributed to the excitation of localized surface plasmon resonance, particularly plasmon-generated hot carriers. These findings may pave a new and convenient way for developing plasmon-based photocatalysts with high efficiency and stability.

Selectively Adsorbed p-Aminothiophenol Molecules Improve the Electrocatalytic and Photo-Electrocatalytic Hydrogen Evolution on Au/TiO2.

Electrocatalytic hydrogen evolution reaction (HER) is receiving increasing attention as an effective process to produce clean energy. The commonly used precious metal catalysts can be hybridized with semiconductors to form heterostructures for the improvement of catalytic efficiency and reduction of cost. It will be promising to further improve the efficiency of heterostructure-based nanocatalysts in electrocatalytic and photocatalytic HER using a simple and effective method. Herein, we improve the efficiency of Au/TiO2 in electrocatalytic and photo-electrocatalytic HER by selectively adsorbing p-aminothiophenol (PATP) molecules. The PATP molecules are adsorbed on the gold surface by using a simple solution-based method and favor the charge separation at the Au-TiO2 interface. We also compare the PATP molecules with other thiophenol molecules in the enhancement of electrocatalytic HER. The PATP-induced enhancement in electrocatalysis is then further investigated by density functional theory (DFT) calculations, and this enhancement is attributed to a reduction in Gibbs energy of adsorbed hydrogen after surface adsorption of PATP molecules. This work provides a simple, cost-effective, and highly efficient approach to improve the electrocatalytic and photo-electrocatalytic efficiency of Au/TiO2, and this approach could be easily extended to other heterostructure-based nanocatalysts for performance enhancement and may be used in many other catalytic reactions.

Boosting the Plasmon-Mediated Electrochemical Oxidation of p-Aminothiophenol with p-Hydroxythiophenol as Molecular Cocatalyst.

Plasmon-mediated electrochemistry is an emerging area of interest in which the electrochemical reactions are enhanced by employing metal nanostructures possessing localized surface plasmon resonance (LSPR). However, the reaction efficacy is still far below its theoretical limit due to the ultrafast relaxation of LSPR-generated hot carriers. Herein, we introduce p-hydroxythiophenol (PHTP) as a molecular cocatalyst to significantly improve the reaction efficacy in plasmon-mediated electrochemical oxidation of p-aminothiophenol (PATP) on gold nanoparticles. Using electrochemical techniques, in situ Raman spectroscopy, and theoretical calculations, we elucidate that the presence of PHTP improves the hot hole-mediated electrochemical oxidation of PATP by 2-fold through the trapping of plasmon-mediated hot electrons. In addition, the selectivity of PATP oxidation could also be modulated by the introduction of PHTP cocatalyst. This tactic of employing molecular cocatalyst can be drawn out to endorse various plasmonic electrochemical reactions because of its simple protocol, high efficiency, and high selectivity.

Preparation of Janus nanosheets composed of gold/palladium nanoparticles and reduced graphene oxide for highly efficient emulsion catalysis.

Interface/emulsion catalysis is an effective approach for many organic and inorganic chemical reactions. Positioning catalysts at the interface is essential for highly efficient interface/emulsion catalysis. The sheet-like Janus nanostructures may have great advantages in stabilizing emulsions and improving reaction efficiency. In this work, by using a simple emulsion reaction and photodeposition, we successfully prepare the Janus nanosheets with opposite sides composed of AuNPs/PdNPs and reduced graphene oxide (rGO) respectively, referred to as AuNP-rGO/PdNP-rGO Janus nanosheets. Due to the distinct hydrophilicities on opposite sides, the prepared Janus nanosheets demonstrate high efficiency in emulsion stabilization and emulsion catalysis. By introducing the prepared PdNP-rGO and AuNP-rGO Janus nanosheets in emulsion reactions, highly efficient hydrogenation of p-nitroanisole and photocatalytic degradation of Nile red are demonstrated. This work provides a simple and cost-effective method to prepare Janus nanosheets and realize highly efficient emulsion reactions, and this strategy can be extended to promote many other interface/emulsion reactions.

Molecular Cocatalyst of p-Mercaptophenylboronic Acid Boosts the Plasmon-Mediated Reduction of p-Nitrothiophenol.

Localized surface plasmon resonance (LSPR) has been demonstrated to be highly effective in the initialization or acceleration of chemical reactions because of its unique optical properties. However, because of the ultrashort lifetime (fs to ps) of plasmon-generated hot carriers, the potential of LSPR in photochemical reactions has not been fully exploited. Herein, we demonstrate an acceleration of the plasmon-mediated reduction of p-nitrothiophenol (PNTP) molecules on the surface of silver nanoparticles (AgNPs) with in situ Raman spectroscopy. p-Mercaptophenylboronic acid (PMPBA) molecules coadsorbed on AgNP surfaces act as a molecular cocatalyst in the plasmon-mediated reaction, resulting in a boosting of the PNTP reduction. This boosting is attributed to the improved transfer and separation of the plasmon-generated hot carriers at the interface of the AgNPs and coadsorbed PMPBA molecules. Our finding provides a highly simple, cost-effective, and highly effective strategy to promote plasmonic photochemistry by introducing a molecular cocatalyst, and this strategy can be extended to promote various plasmon-mediated reactions.

Simple, Skin-Attachable, and Multifunctional Colorimetric Sweat Sensor.

In situ analysis of sweat provides a simple, convenient, cost-effective, and noninvasive approach for the early diagnosis of physical illness in humans and is particularly useful in family care. In this study, a flexible and skin-attachable colorimetric sweat sensor for multiplexed analysis is developed using a simple, cost-effective, and convenient method. The obtained sweat sensor can be used to simultaneously detect glucose, lactate, urea, and pH value in sweat, as well as sweat loss and skin temperature. Only 2.5 µL of sweat is enough for the whole test, and the sweat loss and chemical-sensing results can be read out conveniently by naked eyes or a smartphone. In addition, body temperature can also be detected with an additional electrical circuit. Our sweat sensor provides a new, cost-effective, and convenient approach for in vitro diagnosis of multiple components in sweat, and the easy fabrication and cost-effectiveness make our sensor commercializable in the near future.