Graphene Oxide Membrane Reactor for Electrochemical Deuteration Reactions.

The deuteration of organic molecules is considerably important in organic and medicinal chemistry. An electrochemical membrane reactor using proton-conducting graphene oxide (GO) nanosheets was developed to synthesize valuable deuterium-labeled products via an efficient hydrogen-to-deuterium (H/D) exchange under mild conditions at ambient temperature and atmospheric pressure. Deuterons (D+) formed by the anodic oxidation of heavy water (D2O) at the Pt/C anode permeate through the GO membrane to the Pt/C cathode, where organic molecules with functional groups (C≡C and C═O) are deuterated with adsorbed atomic D species. Deuteration occurs in outstanding yields with high levels of D incorporation. We also achieved the electrodeuteration of a drug molecule, ibuprofen, demonstrating the promising feasibility of the GO membrane reactor in the pharmaceutical industry.

Energy Application of Graphene Based Membrane: Hydrogen Separation.

Hydrogen gas (H2 ) is a viable energy carrier that has the potential to replace the traditional fossil fuels and contribute to achieving zero net emissions, making it an attractive option for a hydrogen-based society. However, current H2 purification technologies are often limited by high energy consumption, and as a result, there is a growing demand for alternative techniques that offer higher H2 purity and energy efficiency. Membrane separation has emerged as a promising approach for obtaining high-purity H2 gas with low energy consumption. Nevertheless, despite years of development, commercial polymeric membranes have limited performance, prompting researchers to explore alternative materials. In this context, carbon-based membranes, specifically graphene-based nanomaterials, have gained significant attention as potential membrane materials due to their unique properties. In this review, we provide a comprehensive overview of carbon-based membranes for H2 gas separation, fabrication of the membrane, and its characterization, including their advantages and limitations. We also explore the current technological challenges and suggest insights into future research directions, highlighting potential ways to improve graphene-based membranes performance for H2 separations.

Light-Stimulated Luminescence Control of Lead Halide-Based Perovskite Nanocrystals Coupled with Photochromic Molecules via Electron and Energy Transfer.

Photoswitchable nanomaterials are key materials in the development of advanced imaging techniques, such as super-resolution fluorescence microscopy. The combination of perovskite CsPbBr3 nanocrystals (NCs) with bright photoluminescence (PL) emission and diarylethenes (DAEs) with structural changes in response to ultraviolet (UV) and visible light is a promising candidate system. Herein, CsPbBr3 NCs are coupled with photochromic DAE molecules to control the PL emission from the NCs by light stimulation. The PL emission is successfully switched ON and OFF by alternating UV and visible light irradiation. Time-resolved PL emission studies suggest that Förster resonance energy transfer from CsPbBr3 NCs to the closed-ring form of DAE occurs after UV irradiation, and the PL emission is quenched. Upon visible-light irradiation, DAE is converted to the open-ring isomer, and the PL emission is restored. Femtosecond pump-probe spectroscopy reveals that light stimulation induces not only energy transfer but also photoinduced electron transfer in the NC-DAE pair on the picosecond timescale to form DAE radicals. Thus, it is suggested that the holes residing in the NCs react with the NCs, degrading the PL emission. Stable PL switching is realized using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) as a hole scavenger to avoid the reaction between the holes and NCs.

Study on Sensing Mechanism of Volatile Organic Compounds Using Pt-Loaded ZnO Nanocrystals.

Understanding the surface chemistry of target gases on sensing materials is essential for designing high-performance gas sensors. Here, we report the effect of Pt-loading on the sensing of volatile organic compounds (VOCs) with ZnO gas sensors, demonstrated by diffuse reflection infrared Fourier transform (DRIFT) spectroscopy. Pt-loaded ZnO nanocrystals (NCs) of 13~22 nm are synthesized using the hot soap method. The synthesized powder is deposited on an alumina substrate by screen-printing to form a particulate gas sensing film. The 0.1 wt% Pt-loaded ZnO NC sensor shows the highest sensor response to acetone and ethanol at 350 °C, while the responses to CO and H2 are small and exhibit good selectivity to VOCs. The gas sensing mechanism of ethanol with Pt-ZnO NCs was studied by in situ DRIFT spectroscopy combined with online FT-IR gas analysis. The results show that ethanol reacts with small Pt-loaded ZnO to produce intermediate species such as acetaldehyde, acetate, and carbonate, which generates a high sensor response to ethanol in air.

Electrochemical Detection of Ethanol in Air Using Graphene Oxide Nanosheets Combined with Au-WO3.

Detection, monitoring, and analysis of ethanol are important in various fields such as health care, food industries, and safety control. In this study, we report that a solid electrolyte gas sensor based on a proton-conducting membrane is promising for detecting ethanol in air. We focused on graphene oxide (GO) as a new solid electrolyte because it shows a high proton conductivity at room temperature. GO nanosheets are synthesized by oxidation and exfoliation of expanded graphite via the Tour's method. GO membranes are fabricated by stacking GO nanosheets by vacuum filtration. To detect ethanol, Au-loaded WO3 is used as the sensing electrode due to the excellent activity of gold nanoparticles for the catalysis of organic molecules. Au-WO3 is coupled with rGO (reduced graphene oxide) to facilitate the electron transport in the electrode. Ce ions are intercalated into the GO membrane to facilitate proton transport. The sensor based on the Ce doped-GO membrane combined with Au-WO3/rGO as a sensing electrode shows good electric potential difference (ΔV) responses to ethanol in the air at room temperature. The sensor signal reaches more than 600 mV in response to ethanol at 40 ppm in air, making it possible to detect ethanol at a few ppb (parts per billion) level. The ethanol sensing mechanism was discussed in terms of the mixed-potential theory and catalysis of ethanol on Au-WO3.

Synthesis of Zeolitic Mo-Doped Vanadotungstates and Their Catalytic Activity for Low-Temperature NH3-SCR.

Mo was successfully introduced into a vanadotungstate (VT-1), which is a crystalline microporous zeolitic transition-metal oxide based on cubane clusters [W4O16]8- and VO2+ linkers (MoxW4-x. x: number of Mo in VT-1 unit cell determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES)). It was confirmed that W in the cubane units was substituted by Mo. The resulting materials showed higher microporosity compared with VT-1. The surface area and the micropore volume increased to 296 m2·g-1 and 0.097 cm3·g-1, respectively, for Mo0.6W3.4 compared with the those values for VT-1 (249 m2·g-1 and 0.078 cm3·g-1, respectively). The introduction of Mo changed the acid properties including the acid amount (VT-1: 1.06 mmol g-1, Mo0.6W3.4: 2.18 mmol·g-1) and its strength because of the changes of the chemical bonding in the framework structure. MoxW4-x showed substantial catalytic activity for the selective catalytic reduction of NO with NH3 (NH3-selective catalytic reduction (SCR)) at a temperature as low as 150 °C.

A photoelectrochemical capacitor using polyoxometalates coupled with semiconductor nanocrystals as the photosensitizer.

Solar energy storage technology ensures a sustainable and reliable energy supply. Herein, we show that electrons generated in semiconductor nanocrystals (NCs) of CsPbBr3 by visible light excitation can be stored in polyoxometalates (POMs) of W10O32, and extracted as an electric current using a photoelectrochemical cell.

Single Crystallization of Cs4PbBr6 Perovskite from Supersaturated Organic Solutions Optimized Through Solubility Studies.

We demonstrate the fabrication of millimeter-sized single crystals of 0D-Cs4PbBr6 grown in a supersaturated solution consisting of organic solvents without HBr (aq). One of the precursors, CsBr, was dissolved in ethylene glycol (EG) mixed with dimethyl sulfoxide, which is a good solvent for the other precursor, PbBr2. At a solvent ratio of 20 vol % EG, the solubility of cesium bromide decreased and the title compound, Cs4PbBr6, was selectively formed, whereas, with an EG ratio of 80 vol %, 3D-CsPbBr3 was formed. A phase diagram (solubility curve) of Cs4PbBr6 in the mixed solvent containing 20 vol % EG was obtained by visually observing dissolution and crystal precipitation while changing the temperature. Because the solubility was proportional to the temperature, the solubility curve demonstrated an upper critical solution phenomenon. The solubility near the boiling point of the solution (150 °C) was approximately 0.14 M. A single crystal of Cs4PbBr6 was formed by growing a seed crystal in a supersaturated solution on the low-temperature side of the solubility curve. X-ray analysis established the crystal structure; a fluorescence emission at 520 nm with a full width at half maximum of 20 nm confirms the composition of the single crystal to be Cs4PbBr6.

Selective formation of acetate intermediate prolongs robust ethylene removal at 0 °C for 15 days.

Efficient ethylene (C2H4) removal below room temperatures, especially near 0 °C, is of great importance to suppress that the vegetables and fruits spoil during cold-chain transportation and storage. However, no catalysts have been developed to fulfill the longer-than-2-h C2H4 removal at this low temperature effectively. Here we prepare gold-platinum (Au-Pt) nanoalloy catalysts that show robust C2H4 (of 50 ppm) removal capacity at 0 °C for 15 days (360 h). We find, by virtue of operando Fourier transformed infrared spectroscopy and online temperature-programmed desorption equipped mass spectrometry, that the Au-Pt nanoalloys favor the formation of acetate from selective C2H4 oxidation. And this on-site-formed acetate intermediate would partially cover the catalyst surface at 0 °C, thus exposing active sites to prolong the continuous and effective C2H4 removal. We also demonstrate, by heat treatment, that the performance of the used catalysts will be fully recovered for at least two times.

Selective Detection of CO Using Proton-Conducting Graphene Oxide Membranes with Pt-Doped SnO2 Electrocatalysts: Mechanistic Study by Operando DRIFTS.

To reduce the risk of carbon monoxide (CO) poisoning, there is a strong need for small, compact gas sensors to detect and monitor CO at ppm concentrations. In this study, we focused on detecting CO with electrochemical sensors based on proton-conducting graphene oxide (GO) nanosheets at room temperature. We found that a Ce-doped GO nanosheet membrane fitted with the sensing electrode composed of Pt (10 wt %)-doped SnO2 nanocrystals exhibits an excellent sensor response to CO at 25 °C. Pt doping of SnO2 nanocrystals has made it possible to detect CO more selectively than H2 and ethanol. The CO detection mechanism is analyzed by operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), Fourier transform infrared gas cell measurements, and comprehensive density functional theory-based calculations. The results revealed that adsorption of CO occurs predominantly on Pt sites, and the adsorbed CO is anodically oxidized at the interface between the sensing electrode and proton-conducting membrane, generating the selective sensor response. The strong adsorption of CO was realized with Pt (10 wt %)-doped SnO2 nanocrystals, as revealed by the DRIFTS analysis and temperature-programed desorption technique.

Bulk tungsten-substituted vanadium oxide for low-temperature NOx removal in the presence of water.

NH3-SCR (selective catalytic reduction) is important process for removal of NOx. However, water vapor included in exhaust gases critically inhibits the reaction in a low temperature range. Here, we report bulk W-substituted vanadium oxide catalysts for NH3-SCR at a low temperature (100-150 °C) and in the presence of water (~20 vol%). The 3.5 mol% W-substituted vanadium oxide shows >99% (dry) and ~93% (wet, 5-20 vol% water) NO conversion at 150 °C (250 ppm NO, 250 ppm NH3, 4% O2, SV = 40000 mL h-1 gcat-1). Lewis acid sites of W-substituted vanadium oxide are converted to Brønsted acid sites under a wet condition while the distribution of Brønsted and Lewis acid sites does not change without tungsten. NH4+ species adsorbed on Brønsted acid sites react with NO accompanied by the reduction of V5+ sites at 150 °C. The high redox ability and reactivity of Brønsted acid sites are observed for bulk W-substituted vanadium oxide at a low temperature in the presence of water, and thus the catalytic cycle is less affected by water vapor.