Confined VLS Growth of Single-Layer 2D Tungsten Nitrides.

Two-dimensional (2D) metal nitrides have garnered significant interest due to their potential applications in future electronics and quantum systems. However, the synthesis of such materials with sufficient uniformity and at relevant scales remains an unaddressed challenge. This study demonstrates the potential of confined growth to control and enhance the morphology of 2D metal nitrides. By restricting the reaction volume of vapor-liquid-solid reactions, an enhanced precursor concentration was achieved that reduces the nucleation density, resulting in larger grain sizes and suppression of multilayer growth. Detailed characterization reveals the importance of balancing the energetic and kinetic aspects of tungsten nitride formation toward this ability. The introduction of a promoter enabled the realization of large-scale, single-layer tungsten nitride with a uniform and high interfacial quality. Finally, our advance in morphology control was applied to the production of edge-enriched 2D tungsten nitrides with significantly enhanced hydrogen evolution ability, as indicated by an unprecedented Tafel slope of 55 mV/dec.

Naphthalene Diimide-Based Donor-Acceptor-Donor Small Molecules as Metal-Free Organocatalysts for Photocatalytic CO2 Reaction.

The application of organic small molecules as metal-free photocatalysts for light-driven photoreduction of carbon dioxide (CO2) has seldom been explored. This work developed four naphthalene diimide (NDI)-derived donor-acceptor-donor small molecules with different numbers of thiophene units, namely, NDI-2T, NDI-TT, NDI-4T, and NDI-6T, as metal-free photocatalysts to catalyze the reduction of CO2 under irradiation with an air mass 1.5G solar simulator at one-sun intensity. The structure-property relationship was investigated by exploring the effects of the electron-donating ability of the donor units on the optical properties, redox potential, electron-hole distribution, and exciton lifetime. NDI-6T exhibited the most red-shifted absorption, longest exciton lifetime, and strongest electron-hole separation. However, the large upshift in oxidation potential because of the elevated electron-donating ability of the hexathiophene unit significantly reduced the driving force for catalyst regeneration, leading to poor catalytic performance. Alternatively, NDI-4T possessed proper redox potentials, reduced charge-transfer resistance, and excellent photocurrent intensity; therefore, it effectively converted CO2 to a single product of CO in the presence of water as an electron donor without a sacrificial reagent or cocatalyst with a product yield of 168.6 µmol gcat-1 24 h-1, which was considerably higher than those of NDI-TT (111.9 µmol gcat-1 24 h-1), NDI-2T (88.4 µmol gcat-1 24 h-1), and NDI-6T (40.5 µmol gcat-1 24 h-1). This study provides a practical guideline for the molecular design of conjugated organic molecules as promising photocatalysts for CO2 photoreduction.

Chromatic Fulleropyrrolidine as Long-Lived Metal-Free Catalyst for CO2 Photoreduction Reaction.

Conversion of CO2 into carbonaceous fuels with the aid of solar energy has been an important research subject for decades. Owing to their excellent electron-accepting capacities, fullerene derivatives have been extensively used as n-type semiconductors. This work reports that the fulleropyrrolidine functionalized with 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole, abbreviated as DTBT-C60 , could efficiently catalyze the photoreduction of CO2 to CO. The novel C60 -chromophore dyad structure facilitated better usage of solar light and effective dissociation of excitons. Consequently, the DTBT-C60 exhibited a promising CO yield of 144 µmol gcat -1 under AM1.5G solar illumination for 24 h. Moreover, the isotope experiments demonstrated that water molecules could function as an electron source to reactivate DTBT-C60 . Impressively, DTBT-C60 exhibited an extremely durable catalytic activity for more than one week, facilitating the practical application of photochemical CO2 reaction.

Ag-doped ZnO nanorods embedded reduced graphene oxide nanocomposite for photo-electrochemical applications.

In this paper, the Ag-doped zinc oxide nanorods embedded reduced graphene oxide (ZnO:Ag/rGO) nanocomposite was synthesized for photocatalytic degradation of methyl orange (MO) in the water. The microstructural results confirmed the successful decoration of Ag-doped ZnO nanorods on rGO matrix. The photocatalytic properties, including photocatalytic degradation, charge transfer kinetics and photocurrent generation, are systematically investigated using electrochemical impedance spectroscopy (EIS), photocurrent transient response (PCTR) and open circuit voltage decay (OCVD). The results of photocatalytic dye degradation measurements indicated that ZnO:Ag/rGO nanocomposite is more effective than pristine ZnO to degrade the MO dye, and the degradation rate reached 40.6% in 30 min. The decomposition of MO with ZnO:Ag/rGO nanostructure followed first-order reaction kinetics with a reaction rate constant (K a) of 0.01746 min-1. The EIS, PCTR and OCVD measurements revealed that the Ag doping and incorporation of rGO could suppress the recombination probability in ZnO by the separation of photo-generated electron-hole pairs, which leads to the enhanced photocurrent generation and photocatalytic activity. The photocurrent density of ZnO:Ag/rGO, ZnO/rGO and pristine ZnO are 206, 121.4 and 88.8 nA cm-2, respectively.

Aryl fluoride functionalized graphene oxides for excellent room temperature ammonia sensitivity/selectivity.

Herein, we report the covalent functionalization of graphene oxide (GO) through ''click'' reaction and its applications towards ammonia sensing. This inimitable method of covalent functionalization involves linking GO with azide moiety and click coupling of different derivatives of aryl propargyl ether, which enhances the sensitivity towards ammonia. The functionalized GO were characterized using NMR, XRD, SEM, FT-IR, Raman, UV-Vis, TGA and DSC. Compared to pristine GO, the GO functionalized with Ar samples (GO-Ar) exhibit excellent room temperature ammonia sensing properties with good response/recovery characteristics. It has been observed that 2,3-difluoro and 2,3,4-trifluoro substituted aryl propargyl ether functionalized GO (GO-Ar2 and GO-Ar3) shows superior ammonia sensing with response/recovery of 63%/∼90% and 60%/100%, respectively at 20 ppm. The GO-Ar3 exhibits high sensitivity towards ammonia at 20-100 ppm. Computational studies supports the high sensitivity of GO-Ar towards ammonia due to its high adsorption energy.

Organic semiconductor/graphene oxide composites as a photo-anode for photo-electrochemical applications.

An intimate physical mixture of graphene oxide (GO) and semiconducting organic molecules like bromophenathrene (BrPh) and bromopyrene (BrPy) was prepared by using a ball milling technique. The structural, microstructural, physical and chemical properties of the mixtures (20 wt% of GO) were analyzed by X-ray diffraction, SEM, FT-IR, TGA and TCSPC studies. Furthermore, the electrochemical properties like AC electrical conductivity, transient photocurrent response (PCTR) and open circuit voltage (OCVD) of the samples were analyzed. It has been observed from TCSPC and OCVD measurements that 20 wt% of GO in the semiconductor composite leads to an enhanced life-time of photo-generated charge carriers. The physical mixture composites exhibit a higher photocurrent than pure BrPh and BrPy.