Ball-milled MoS2 with graphene shows enhanced catalytic activity for hydrogen evolution reaction.

The hydrogen evolution reaction (HER) is an important phenomenon in water splitting. Consequently, the development of an active, earth-abundant, and inexpensive HER catalyst is highly desired. MoS2 has drawn considerable interest as an HER catalyst because it is composed of non-precious metal and exhibits high catalytic activity in the nanosheet form. In this study, size-controlled MoS2 particles were synthesized by ball milling. The as-prepared samples exhibited significantly enhanced electrochemical and catalytic properties compared to those of pristine bulk MoS2. Furthermore, the HER activity improved further upon the introduction of graphene into the as-prepared ball-milled samples. In particular, the MoS2 sample ball-milled for 12 h mixed with graphene exhibited optimal performance, showing an overpotential (160 mV at 10 mA cm-2) that was ~ 335 mV lower than that of pristine bulk MoS2. The superior catalytic activity was ascribed to the exposed edge sites, sulfur vacancies, and 1T phase of MoS2, as well as the noteworthy fortifying effect of the electronically conductive flexible material, graphene. The results provide a promising strategy for its application as an efficient and stable HER catalyst.

Li et al. reported MoS₂-based electrocatalysts for the hydrogen evolution reaction. The superior catalytic activity was ascribed to exposed edge sites, sulfur vacancies, 1T phase, and the effect of graphene.

Carbon dioxide adsorption and conversion to methane and ethane on hydrogen boride sheets.

Hydrogen boride (HB) sheets are metal-free two-dimensional materials comprising boron and hydrogen in a 1:1 stoichiometric ratio. In spite of the several advancements, the fundamental interactions between HB sheets and discrete molecules remain unclear. Here, we report the adsorption of CO2 and its conversion to CH4 and C2H6 using hydrogen-deficient HB sheets. Although fresh HB sheets did not adsorb CO2, hydrogen-deficient HB sheets reproducibly physisorbed CO2 at 297 K. The adsorption followed the Langmuir model with a saturation coverage of 2.4 × 10-4 mol g-1 and a heat of adsorption of approximately 20 kJ mol-1, which was supported by density functional theory calculations. When heated in a CO2 atmosphere, hydrogen-deficient HB began reacting with CO2 at 423 K. The detection of CH4 and C2H6 as CO2 reaction products in a moist atmosphere indicated that hydrogen-deficient HB promotes C-C coupling and CO2 conversion reactions. Our findings highlight the application potential of HB sheets as catalysts for CO2 conversion.

Direct Observation of Photoinduced Charge Separation at Transition-Metal Nitride-Semiconductor Interfaces.

Optically excited hot carriers from metallic nanostructures forming metal-semiconductor heterostructures are advantageous for enhancing photoelectric conversion in the sub-band gap photon energy regime. Plasmonic gold has been widely used for hot carrier excitation, but recent works have demonstrated that plasmonic transition-metal nitrides have higher efficiencies in injecting hot electrons to adjacent n-type semiconductors and are more cost-effective. To collect direct evidence of hot carrier excitation from nanostructures, imaging of hot carriers is essential. In this work, photoexcited Kelvin probe force microscopy (KPFM) is used to image hot carriers excited in transition-metal nitride nanostructures forming heterostructures with semiconductors. Among available transition-metal nitrides, we select zirconium nitride (ZrN) for this study. Additionally, both p-type and n-type titanium dioxides (TiO2) are selected to study the transport of hot holes and hot electrons. The KPFM results indicate that for ZrN and p-type TiO2 heterostructures, hot holes are injected into the p-type TiO2 across the Schottky contact. In the case of ZrN and n-type TiO2 heterostructures, hot electrons are injected into the n-type TiO2 across the ohmic contact. Because transition-metal nitrides are known to be more effective than gold at injecting hot carriers into adjacent semiconductors, unambiguously determining the mechanisms of hot carrier transportation of transition-metal nitrides using photoexcited KPFM will facilitate additional studies on hot carrier applications with transition-metal nitrides.

Marimo-Bead-Supported Core-Shell Nanocomposites of Titanium Nitride and Chromium-Doped Titanium Dioxide as a Highly Efficient Water-Floatable Green Photocatalyst.

The release of untreated industrial wastewater creates a hazardous impact on the environment. In this regard, the development of an environmentally friendly catalyst is of paramount importance. Here, we report a highly efficient and reusable core-shell TiN/SiO2/Cr-TiO2 (TSCT) photocatalyst that is composed of SiO2-cladded titanium nitride (TiN) nanoparticles (NPs) decorated with Cr-doped TiO2 NPs for the removal of organic contaminants from water. The TiN NPs serve as the main light absorber component with excellent visible-light absorption along with Cr-TiO2 NPs. The TSCT shows remarkable improvement in the photodecomposition of methylene blue (MB) over Cr-TiO2 and TiO2 NPs. An efficient structural design is proposed by adopting calcium alginate beads (P-Marimo beads) as a transparent scaffold for supporting our TSCT, which floats nature on the water surface and realizes easy handling as well as excellent reusability for multipurpose water purification. Surprisingly, our TSCT is found to keep its catalytic activity even after the illumination is turned off. Our proposed P-Marimo-encapsulated TSCT can be utilized as an excellent green photocatalyst with high photocatalytic performance, good recyclability, and easy handling.

Sub-Band Gap Photodetection from the Titanium Nitride/Germanium Heterostructure.

Photoexcited hot carriers through nonradiative decay offer new opportunities for harnessing longer wavelength light. Here, we have demonstrated a hot-carrier-mediated sub-band gap photodetection in germanium-based planar heterojunction devices. The planar samples that form in situ germanium/titanium nitride (Ge/TiN) interfaces are fabricated by the dc sputtering technique, and the generation of photocurrent by near-infrared (NIR) light illumination is confirmed up to 2600 nm, well exceeding the absorption limit of Ge. The photocurrent obtained with nickel contacts is 3 orders larger than that obtained without metal contacts or with gold contacts in similar structures. The specific detectivity ( D*) value for the TiN/Ge photodetector is obtained to be 6.32 × 105 Jones at the sub-band gap excitation wavelength of 2000 nm without applying any bias. The superior performances of our device are attributed to the broad absorption of the TiN, the plasmonic hot carrier transfer from the TiN to Ge, and built-in potential of the TiN/Ge non-Ohmic junction, which allows efficient separation of photoexcited electron-hole pairs. Our results further support the use of TiN, which is robust and cost-effective, as an alternative to metals for NIR photodetection and photovoltaics when it forms a heterostructure with Ge.

Enhanced Solar Light Absorption and Photoelectrochemical Conversion Using TiN Nanoparticle-Incorporated C3N4-C Dot Sheets.

In this work, a promising strategy to increase the broadband solar light absorption was developed by synthesizing a composite of metal-free carbon nitride-carbon dots (C3N4-C dots) and plasmonic titanium nitride (TiN) nanoparticles (NPs) to improve the photoelectrochemical water-splitting performance under simulated solar radiation. Hot-electron injection from plasmonic TiN NPs to C3N4 played a role in photocatalysis, whereas C dots acted as catalysts for the decomposition of H2O2 to O2. The use of C dots also eliminated the need for a sacrificial reagent and prevented catalytic poisoning. By incorporating the TiN NPs and C dots, a sixfold improvement in the catalytic performance of C3N4 was observed. The proposed approach of combining TiN NPs and C dots with C3N4 proved effective in overcoming low optical absorption and charge recombination losses and also widens the spectral window, leading to improved photocatalytic activity.

Wide-range temperature sensing using highly sensitive green-luminescent ZnO and PMMA-ZnO film as a non-contact optical probe.

The heat is on: A variation of green luminescence intensity of ZnO microcrystals embedded in poly(methyl methacrylate) is observed. This material is used for non-contact thermometer, which has an accuracy of 0.1 K over a temperature range of 83-474 K. Scale bars: 10 µm.