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The conversion of photocatalytic methane into methanol in high yield with selectivity remains a huge challenge due to unavoidable overoxidation. Here, the photocatalytic oxidation of CH 4 into CH 3 OH by O 2 is carried out on Ag-decorated facet-dominated TiO 2 . The {001}-dominated TiO 2 shows a durable CH 3 OH yield of 4.8 mmol g −1  h −1 and a selectivity of approximately 80%, which represent much higher values than those reported in recent studies and are better than those obtained for {101}-dominated TiO 2 . Operando Fourier transform infrared spectroscopy, electron spin resonance, and nuclear magnetic resonance techniques are used to comprehensively clarify the underlying mechanism. The straightforward generation of oxygen vacancies on {001} by photoinduced holes plays a key role in avoiding the formation of •CH 3 and •OH, which are the main factors leading to overoxidation and are generally formed on the {101} facet. The generation of oxygen vacancies on {001} results in distinct intermediates and reaction pathways (oxygen vacancy → Ti–O 2 •  → Ti–OO–Ti and Ti–(OO) → Ti–O • pairs), thus achieving high selectivity and yield for CH 4 photooxidation into CH 3 OH. The photocatalytic conversion of CH 4 into CH 3 OH with high activity and selectivity must avoid product overoxidation. Here, authors minimize overoxidation by using a (001)-dominated TiO 2 nanosheet to circumvent CH 4 overoxidation intermediates plus reaction pathways that occur on (101) facets.

HighlightsSynthesis strategies of layered double hydroxides (LDHs) were summarized with classifications of traditional coprecipitation, homogeneous precipitation, and newly developed topochemical oxidation.Diverse approaches of structural modulation and hybridization to enhance the electrocatalytic activity of LDHs were systematically reviewed.Layered double hydroxides (LDHs) have attracted tremendous research interest in widely spreading applications. Most notably, transition-metal-bearing LDHs are expected to serve as highly active electrocatalysts for oxygen evolution reaction (OER) due to their layered structure combined with versatile compositions. Furthermore, reducing the thickness of platelet LDH crystals to nanometer or even molecular scale via cleavage or delamination provides an important clue to enhance the activity. In this review, recent progresses on rational design of LDH nanosheets are reviewed, including direct synthesis via traditional coprecipitation, homogeneous precipitation, and newly developed topochemical oxidation as well as chemical exfoliation of parent LDH crystals. In addition, diverse strategies are introduced to modulate their electrochemical activity by tuning the composition of host metal cations and intercalated counter-anions, and incorporating dopants, cavities, and single atoms. In particular, hybridizing LDHs with conductive components or in situ growing them on conductive substrates to produce freestanding electrodes can further enhance their intrinsic catalytic activity. A brief discussion on future research directions and prospects is also summarized.

Lacking strategies to simultaneously address the intrinsic activity, site density, electrical transport, and stability problems of chalcogels is restricting their application in catalytic hydrogen production. Herein, we resolve these challenges concurrently through chemically activating the molybdenum disulfide (MoS 2 ) surface basal plane by doping with a low content of atomic palladium using a spontaneous interfacial redox technique. Palladium substitution occurs at the molybdenum site, simultaneously introducing sulfur vacancy and converting the 2H into the stabilized 1T structure. Theoretical calculations demonstrate the sulfur atoms next to the palladium sites exhibit low hydrogen adsorption energy at –0.02 eV. The final MoS 2 doped with only 1wt% of palladium demonstrates exchange current density of 805 μA cm −2 and 78 mV overpotential at 10 mA cm −2 , accompanied by a good stability. The combined advantages of our surface activating technique open the possibility of manipulating the catalytic performance of MoS 2 to rival platinum. While water reduction may provide a carbon-neutral means to produce hydrogen gas, there is a scarcity of efficient, earth-abundant electrocatalysts. Here, the authors add palladium into MoS 2 materials to activate and stabilize the conductive basal plane to improve the electrocatalytic activity.

Atomic metal wires have great promise for practical applications in devices due to their unique electronic properties. Unfortunately, such atomic wires are extremely unstable. Here we fabricate stable atomic silver wires (ASWs) with appreciably unoccupied states inside the parallel tunnels of α-MnO 2 nanorods. These unoccupied Ag 4 d orbitals strengthen the Ag–Ag bonds, greatly enhancing the stability of ASWs while the presence of delocalized 5 s electrons makes the ASWs conducting. These stable ASWs form a coherently oriented three-dimensional wire array of over 10 nm in width and up to 1 μm in length allowing us to connect it to nano-electrodes. Current-voltage characteristics of ASWs show a temperature-dependent insulator-to-metal transition, suggesting that the atomic wires could be used as thermal electrical devices. One-dimensional atomic metal wires can exhibit useful properties distinct from their bulk equivalents; however they typically suffer from limited stability. Here, Chen et al create atomic silver wires which are stable and exhibit a temperature dependent metal to insulator transition.

Three-dimensional graphene architectures in the macroworld can in principle maintain all the extraordinary nanoscale properties of individual graphene flakes. However, current 3D graphene products suffer from poor electrical conductivity, low surface area and insufficient mechanical strength/elasticity; the interconnected self-supported reproducible 3D graphenes remain unavailable. Here we report a sugar-blowing approach based on a polymeric predecessor to synthesize a 3D graphene bubble network. The bubble network consists of mono- or few-layered graphitic membranes that are tightly glued, rigidly fixed and spatially scaffolded by micrometre-scale graphitic struts. Such a topological configuration provides intimate structural interconnectivities, freeway for electron/phonon transports, huge accessible surface area, as well as robust mechanical properties. The graphene network thus overcomes the drawbacks of presently available 3D graphene products and opens up a wide horizon for diverse practical usages, for example, high-power high-energy electrochemical capacitors, as highlighted in this work. Three-dimensional graphene offers an ideal sheet-to-sheet connectivity of assembled graphenes, but often suffers from poor electrochemical performance. Wang et al . present a sugar-blowing technique to prepare a 3D graphene, which overcomes such problems and shows potential in supercapacitor applications.

Elastic modulus measured through atomic force microscopy (AFM)-based indentation on single carbon fiber (CF) is found with dependence on lateral applied stress. An in situ indentation experiment inside a high-resolution transmission electron microscope was performed to quantitatively understand this phenomenon by observing microstructure change in the indented area. Change of graphitic basal plane misalignment angle during indentation was linked to a continuous change of modulus with the help of finite element simulation. The established relationship between modulus and indentation force was further used to calculate residual stress distribution in CF imbedded in a CF reinforced polymer composite using the AFM indentation technique. The stress-induced formation of nanoscale defects in the CF and their transformation into fracture were directly characterized.

We present the experimental synthesis of one-dimensional (1D) van der Waals heterostructures, a class of materials where different atomic layers are coaxially stacked. We demonstrate the growth of single-crystal layers of hexagonal boron nitride (BN) and molybdenum disulfide (MoS2) crystals on single-walled carbon nanotubes (SWCNTs). For the latter, larger-diameter nanotubes that overcome strain effect were more readily synthesized. We also report a 5-nanometer–diameter heterostructure consisting of an inner SWCNT, a middle three-layer BN nanotube, and an outer MoS2 nanotube. Electron diffraction verifies that all shells in the heterostructures are single crystals. This work suggests that all of the materials in the current 2D library could be rolled into their 1D counterparts and a plethora of function-designable 1D heterostructures could be realized.

Lacking strategies to simultaneously address the intrinsic activity, site density, electrical transport, and stability problems of chalcogels is restricting their application in catalytic hydrogen production. Herein, we resolve these challenges concurrently through chemically activating the molybdenum disulfide (MoS ) surface basal plane by doping with a low content of atomic palladium using a spontaneous interfacial redox technique. Palladium substitution occurs at the molybdenum site, simultaneously introducing sulfur vacancy and converting the 2H into the stabilized 1T structure. Theoretical calculations demonstrate the sulfur atoms next to the palladium sites exhibit low hydrogen adsorption energy at -0.02 eV. The final MoS doped with only 1wt% of palladium demonstrates exchange current density of 805 μA cm and 78 mV overpotential at 10 mA cm , accompanied by a good stability. The combined advantages of our surface activating technique open the possibility of manipulating the catalytic performance of MoS to rival platinum.

Genome-wide analysis of genomic signatures might reveal novel mechanisms for gastric cancer (GC) tumorigenesis. Here, we analysis structural variations (SVs) and mutational signatures via whole-genome sequencing of 168 GCs. Our data demonstrates diverse models of complex SVs operative in GC, which lead to high-level amplification of oncogenes. We find varying proportion of tandem-duplications (TDs) among individuals and identify 24 TD hotspots involving well-established cancer genes such as CCND1, ERBB2 and MYC . Specifically, we nominate a novel hotspot involving the super-enhancer of ZFP36L2 presents in approximately 10% GCs from different cohorts, the oncogenic role of which is further confirmed by experimental data. In addition, our data reveal a mutational signature, specifically occurring in noncoding region, significantly enriched in tumors with cadherin 1 mutations, and associated with poor prognoses. Collectively, our data suggest that TDs might serve as an important mechanism for cancer gene activation and provide a novel signature for stratification. Structural variations in gastric cancer impact progression. Here, the authors perform whole-genome sequencing on 168 gastric cancer patients and identified tandem-duplications of super-enhancer ZFP36L2 in 10% of gastric cancer, and mutational signatures in tumors with cadherin 1 mutations that associated with poor prognoses.