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A catalyst system with dedicated selectivity toward a single hydrocarbon or oxygenate product is essential to enable the industrial application of electrochemical conversion of CO2 to high-value chemicals. Cu is the only known metal catalyst that can convert CO2 to high-order hydrocarbons and oxygenates. However, the Cu-based catalysts suffer from diverse selectivity. Here, we report that the functionalized graphene quantum dots can direct CO2 to CH4 conversion with simultaneous high selectivity and production rate. The electron-donating groups facilitate the yield of CH4 from CO2 electro-reduction while electron-withdrawing groups suppress CO2 electro-reduction. The yield of CH4 on electron-donating group functionalized graphene quantum dots is positively correlated to the electron-donating ability and content of electron-donating group. The graphene quantum dots functionalized by either –OH or –NH2 functional group could achieve Faradaic efficiency of 70.0% for CH4 at −200 mA cm−2 partial current density of CH4. The superior yield of CH4 on electron-donating group- over the electron-withdrawing group-functionalized graphene quantum dots possibly originates from the maintenance of higher charge density of potential active sites (neighboring C or N) and the interaction between the electron-donating group and key intermediates. This work provides insight into the design of active carbon catalysts at the molecular scale for the CO2 electro-reduction. Electrochemical conversion of CO2 to fuels is a promising strategy to reduce the ever-increasing CO2 emission. Here, the authors developed graphene quantum dots (GQDs) catalysts to efficiently convert CO2 to CH4 and revealed the significance of electron-donating functional groups in regulating the reactivity of GQDs. [ABSTRACT FROM AUTHOR]

This article features the importance of nanomaterial–protein interfaces, with a special interest on two-dimensional (2D) nanomaterials, for next generation sensors and electronics. Graphene, the first isolated and studied 2D nanomaterial, is taken as the material of most interest and then focused on its engineering by heteroatom doping. The success of graphene engineering for sensors widened the search for better and efficient biosensor platforms of other layered materials such as boron nitride and transition metal dichalcogenides. But functionalization of 2D backbones with biomolecules often ends up with the disruption of the biological activities due to various reasons. This has to be fundamentally studied and corrected for the clinical implementation of these materials based novel sensing platforms in point-of-care devices and micro-fluidic chips. At the end, importance of various 2D materials–biomolecule interfaces is discussed, and MoS2 based label-free biosensor is highlighted. A method for the modification of MoS2–biomolecule interaction via covalent functionalization of oxygen functionalities in MoS2 is also proposed. [ABSTRACT FROM AUTHOR]

Single-layered molybdenum disulphide with a direct bandgap is a promising two-dimensional material that goes beyond graphene for the next generation of nanoelectronics. Here, we report the controlled vapour phase synthesis of molybdenum disulphide atomic layers and elucidate a fundamental mechanism for the nucleation, growth, and grain boundary formation in its crystalline monolayers. Furthermore, a nucleation-controlled strategy is established to systematically promote the formation of large-area, single- and few-layered films. Using high-resolution electron microscopy imaging, the atomic structure and morphology of the grains and their boundaries in the polycrystalline molybdenum disulphide atomic layers are examined, and the primary mechanisms for grain boundary formation are evaluated. Grain boundaries consisting of 5- and 7- member rings are directly observed with atomic resolution, and their energy landscape is investigated via first-principles calculations. The uniformity in thickness, large grain sizes, and excellent electrical performance signify the high quality and scalable synthesis of the molybdenum disulphide atomic layers. [ABSTRACT FROM AUTHOR]

Graphene and hexagonal boron nitride (h-BN) have similar crystal structures with a lattice constant difference of only 2%. However, graphene is a zero-bandgap semiconductor with remarkably high carrier mobility at room temperature, whereas an atomically thin layer of h-BN is a dielectric with a wide bandgap of ?5.9 eV. Accordingly, if precise two-dimensional domains of graphene and h-BN can be seamlessly stitched together, hybrid atomic layers with interesting electronic applications could be created. Here, we show that planar graphene/h-BN heterostructures can be formed by growing graphene in lithographically patterned h-BN atomic layers. Our approach can create periodic arrangements of domains with size ranging from tens of nanometres to millimetres. The resulting graphene/h-BN atomic layers can be peeled off the growth substrate and transferred to various platforms including flexible substrates. We also show that the technique can be used to fabricate two-dimensional devices, such as a split closed-loop resonator that works as a bandpass filter. [ABSTRACT FROM AUTHOR]

We report that graphene coatings do not significantly disrupt the intrinsic wetting behaviour of surfaces for which surface-water interactions are dominated by van der Waals forces. Our contact angle measurements indicate that a graphene monolayer is wetting-transparent to copper, gold or silicon, but not glass, for which the wettability is dominated by short-range chemical bonding. With increasing number of graphene layers, the contact angle of water on copper gradually transitions towards the bulk graphite value, which is reached for ~6 graphene layers. Molecular dynamics simulations and theoretical predictions confirm our measurements and indicate that graphene's wetting transparency is related to its extreme thinness. We also show a 30-40% increase in condensation heat transfer on copper, as a result of the ability of the graphene coating to suppress copper oxidation without disrupting the intrinsic wettability of the surface. Such an ability to independently tune the properties of surfaces without disrupting their wetting response could have important implications in the design of conducting, conformal and impermeable surface coatings. [ABSTRACT FROM AUTHOR]

Two-dimensional materials, such as graphene and monolayer hexagonal BN (h-BN), are attractive for demonstrating fundamental physics in materials and potential applications in next-generation electronics. Atomic sheets containing hybridized bonds involving elements B, N and C over wide compositional ranges could result in new materials with properties complementary to those of graphene and h-BN, enabling a rich variety of electronic structures, properties and applications. Here we report the synthesis and characterization of large-area atomic layers of h-BNC material, consisting of hybridized, randomly distributed domains of h-BN and C phases with compositions ranging from pure BN to pure graphene. Our studies reveal that their structural features and bandgap are distinct from those of graphene, doped graphene and h-BN. This new form of hybrid h-BNC material enables the development of bandgap-engineered applications in electronics and optics and properties that are distinct from those of graphene and h-BN. [ABSTRACT FROM AUTHOR]

Graphite oxide is one of the main precursors of graphene-based materials, which are highly promising for various technological applications because of their unusual electronic properties. Although epoxy and hydroxyl groups are widely accepted as its main functionalities, the complete structure of graphite oxide has remained elusive. By interpreting spectroscopic data in the context of the major functional groups believed to be present in graphite oxide, we now show evidence for the presence of five- and six-membered-ring lactols. On the basis of this chemical composition, we devised a complete reduction process through chemical conversion by sodium borohydride and sulfuric acid treatment, followed by thermal annealing. Only small amounts of impurities are present in the final product (less than 0.5 wt% of sulfur and nitrogen, compared with about 3 wt% with other chemical reductions). This method is particularly effective in the restoration of the ?-conjugated structure, and leads to highly soluble and conductive graphene materials. [ABSTRACT FROM AUTHOR]

The article discusses how cunning refinements can improve electron transport in polycrystalline graphene by pushing the boundaries and the sizes of the grains. Researchers are facing challenges in the nucleation stage and growth of the material on metal surfaces like copper. Several approaches that affect the creation of large single crystals are also discuss such as using polycrystalline copper, surface energy minimization, and the electronic properties of graphene.

State-of-the-art ultra-sensitive blood glucose-monitoring biosensors, based on glucose oxidase (GOx) covalently linked to a single layer graphene (SLG), will be a valuable next generation diagnostic tool for personal glycemic level management. We report here our observations of sensor matrix structure obtained using a multi-physics approach towards analysis of small-angle neutron scattering (SANS) on graphene-based biosensor functionalized with GOx under different pH conditions for various hierarchical GOx assemblies within SLG. We developed a methodology to separately extract the average shape of GOx molecules within the hierarchical assemblies. The modeling is able to resolve differences in the average GOx dimer structure and shows that treatment under different pH conditions lead to differences within the GOx at the dimer contact region with SLG. The coupling of different analysis methods and modeling approaches we developed in this study provides a universal approach to obtain detailed structural quantifications, for establishing robust structure-property relationships. This is an essential step to obtain an insight into the structure and function of the GOx-SLG interface for optimizing sensor performance. [ABSTRACT FROM AUTHOR]

Reduction of water to hydrogen through electrocatalysis holds great promise for clean energy, but its large-scale application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. Here we report an electrocatalyst for hydrogen generation based on very small amounts of cobalt dispersed as individual atoms on nitrogen-doped graphene. This catalyst is robust and highly active in aqueous media with very low overpotentials (30 mV). A variety of analytical techniques and electrochemical measurements suggest that the catalytically active sites are associated with the metal centres coordinated to nitrogen. This unusual atomic constitution of supported metals is suggestive of a new approach to preparing extremely efficient single-atom catalysts. [ABSTRACT FROM AUTHOR]