The concept of using single molecules as key building blocks for logic gates, diodes and transistors to perform basic functions of digital electronic devices at the molecular scale has been explored over the past decades. However, in addition to mimicking the basic functions of current silicon devices, molecules often possess unique properties that have no parallel in conventional materials and promise new hybrid devices with novel functions that cannot be achieved with equivalent solid-state devices. The most appealing example is the molecular switch. Over the past decade, molecular switches on surfaces have been intensely investigated. A variety of external stimuli such as light, electric field, temperature, tunneling electrons and even chemical stimulus have been used to activate these molecular switches between bistable or even multiple states by manipulating molecular conformations, dipole orientations, spin states, charge states and even chemical bond formation. The switching event can occur either on surfaces or in break junctions. The aim of this review is to highlight recent advances in molecular switches triggered by various external stimuli, as investigated by low-temperature scanning tunneling microscopy (LT-STM) and the break junction technique. We begin by presenting the molecular switches triggered by various external stimuli that do not provide single molecule selectivity, referred to as non-selective switching. Special focus is then given to selective single molecule switching realized using the LT-STM tip on surfaces. Single molecule switches operated by different mechanisms are reviewed and discussed. Finally, molecular switches embedded in self-assembled monolayers (SAMs) and single molecule junctions are addressed.

Controlling the Dirac point of graphene is essential for complementary circuits. Here, we describe the use of 2-(2-methoxyphenyl)-1,3-dimethyl-2,3-dihydro-1H-benzoimidazole (o-MeO-DMBI) as a strong n-type dopant for chemical-vapor-deposition (CVD) grown graphene. The Dirac point of graphene can be tuned significantly by spin-coating o-MeO-DMBI solutions on the graphene sheets at different concentrations. The transport of graphene can be changed from p-type to ambipolar and finally n-type. The electron transfer between o-MeO-DMBI and graphene was additionally confirmed by Raman imaging and photoemission spectroscopy (PES) measurements. Finally, we fabricated a complementary inverter via inkjet printing patterning of o-MeO-DMBI solutions on graphene to demonstrate the potential of o-MeO-DMBI n-type doping on graphene for future applications in electrical devices.

Although Cu/ZnO-based catalysts have been long used for the hydrogenation of CO2 to methanol, open questions still remain regarding the role and the dynamic nature of the active sites formed at the metal-oxide interface. Here, we apply high-pressure operando spectroscopy methods to well-defined Cu and Cu0.7Zn0.3 nanoparticles supported on ZnO/Al2O3, γ-Al2O3 and SiO2 to correlate their structure, composition and catalytic performance. We obtain similar activity and methanol selectivity for Cu/ZnO/Al2O3 and CuZn/SiO2, but the methanol yield decreases with time on stream for the latter sample. Operando X-ray absorption spectroscopy data reveal the formation of reduced Zn species coexisting with ZnO on CuZn/SiO2. Near-ambient pressure X-ray photoelectron spectroscopy shows Zn surface segregation and the formation of a ZnO-rich shell on CuZn/SiO2. In this work we demonstrate the beneficial effect of Zn, even in diluted form, and highlight the influence of the oxide support and the Cu-Zn interface in the reactivity.

Charge redistribution at heterogeneous interfaces is a fundamental aspect of surface chemistry. Manipulating the amount of charges and the magnitude of dipole moments at the interface in a controlled way has attracted tremendous attention for its potential to modify the activity of heterogeneous catalysts in catalyst design. Two-dimensional ultrathin silica films with well-defined atomic structures have been recently synthesized and proposed as model systems for heterogeneous catalysts studies. R. Wlodarczyk et al. (Phys. Rev. B, 85, 085403 (2012)) have demonstrated that the electronic structure of silica/ Ru(0001) can be reversibly tuned by changing the amount of interfacial chemisorbed oxygen. Here we carried out systematic investigations to understand the underlying mechanism through which the electronic structure at the silica/Ru(0001) interface can be tuned. As corroborated by both in situ X-ray photoelectron spectroscopy and density functional theory calculations, the observed interface energy level alignments strongly depend on the surface and interfacial charge transfer induced dipoles at the silica/ Ru(0001) heterojunction. These observations may help to understand variations in catalytic performance of the model system from the viewpoint of the electronic properties at the confined space between the silica bilayer and the Ru(0001) surface. The same behavior is observed for the aluminosilicate bilayer, which has been previously proposed as a model system for zeolites.Jian-Qiang Zhong and Mengen Wang contributed equally to this work.

The dual-emissive N, S co-doped carbon dots (N, S-CDs) with a long emission wavelength were synthesized via solvothermal method. The N, S-CDs possess relatively high photoluminescence (PL) quantum yield (QY) (35.7%) towards near-infrared fluorescent peak up to 648 nm. With the advanced characterization techniques including X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), etc. It is found that the doped N, S elements play an important role in the formation of high QY CDs. The N, S-CDs exist distinct pH-sensitive feature with reversible fluorescence in a good linear relationship with pH values in the range of 1.0-13.0. What is more, N, S-CDs can be used as an ultrasensitive Ag + probe sensor with the resolution up to 0.4 μM. This finding will expand the application of as prepared N, S-CDs in sensing and environmental fields.