Hydrogen (H) generation by electrochemical water splitting is a key technique for sustainable energy applications. Two-dimensional (2D) transition-metal dichalcogenide (MoS) and silver phosphate (AgPO) possess excellent electrochemical hydrogen evolution reaction (HER) properties when they are combined together as a composite rather than individuals. Reports examining the HER activity by using AgPO, especially, in combination with the 2D layered MoS are limited in literature.
View Article and Find Full Text PDFLangmuir
December 2023
The current study highlights the successful integration of an in silico design with experimental validation to create a highly effective corrosion inhibitor for copper (Cu) surfaces. The synthesized sulfonated zinc phthalocyanine (Zn-Pc) is electrochemically characterized and demonstrates an impressive 97% inhibition efficiency, comparable to the widely used industrial corrosion inhibitor, BTA, for Cu surfaces. The corrosion inhibition is comprehensively analyzed through potentiodynamic polarization and impedance spectroscopy techniques, supported by their respective equivalent circuits.
View Article and Find Full Text PDFThe difference in resistive switching characteristics by modifying the device configuration provides a unique operating principle, which is essential for both fundamental studies and the development of future memory devices. Here, we demonstrate the poly(methyl methacrylate) (PMMA)-based resistive switching characteristics using four different combinations of electrode/electrolyte arrangement in the device geometry. From the current-voltage () measurements, all the PMMA-based devices revealed nonvolatile memory behavior with a higher ON/OFF resistance ratio (∼10-10).
View Article and Find Full Text PDFThe detailed understanding and control of ionic transport pathways in the electrode/electrolyte interface is vital for realizing micro-scale energy storage devices and formulating adequate design principles. A planar device geometry with nanostructured thin solid polymer electrolyte (SPE) and potassium hydroxide (KOH) incorporated poly(-vinyl imidazole) (PVI) is demonstrated for micro-supercapacitors (MSCs). The adsorption/desorption kinetics of ionic charges in the interfacial regime of ITO/PVI-KOH has been investigated for electrical double layer capacitance (EDLC) characteristics.
View Article and Find Full Text PDFInterfacial modification of the photoanode|electrolyte interface using oleic acid (OA) is thoroughly investigated in this present study. The overall photoconversion efficiency of 11.8% was achieved under the illumination of 100 mW cm with an optical filter of AM 1.
View Article and Find Full Text PDFWe report a low-temperature scanning tunneling microscopy investigation of the in-situ growth of gadolinium phthalocyaninato complexes by combined deposition of free-base phthalocyanines and gadolinium atoms on a smooth Ag(111) substrate. A careful control of the stoichiometry allows the expression of a multilevel structurecomposed of irregularly distributed Gd (Pc) complexes, x=2-5, thus paving new avenues for surface-confined columnar growth.
View Article and Find Full Text PDFSelf-assembled organic molecules can potentially be an excellent source of charge and spin for two-dimensional (2D) atomic-layer superconductors. Here we investigate 2D heterostructures based on In atomic layers epitaxially grown on Si and highly ordered metal-phthalocyanine (MPc, M = Mn, Cu) through a variety of techniques: scanning tunneling microscopy, electron transport measurements, angle-resolved photoemission spectroscopy, X-ray magnetic circular dichroism, and ab initio calculations. We demonstrate that the superconducting transition temperature (T) of the heterostructures can be modified in a controllable manner.
View Article and Find Full Text PDFSelectivity in chemical reactions is a major objective in industrial processes to minimize spurious byproducts and to save scarce resources. In homogeneous catalysis the most important factor which determines selectivity is structural symmetry. However, a transfer of the symmetry concept to heterogeneous catalysis still requires a detailed comprehension of the underlying processes.
View Article and Find Full Text PDFSurface-supported molecular motors are nanomechanical devices of particular interest in terms of future nanoscale applications. However, the molecular motors realized so far consist of covalently bonded groups that cannot be reconfigured without undergoing a chemical reaction. Here we demonstrate that a platinum-porphyrin-based supramolecularly assembled dimer supported on a Au(111) surface can be rotated with high directionality using the tunneling current of a scanning tunneling microscope (STM).
View Article and Find Full Text PDFWe report on the construction of well-defined surface quantum well arrangements by combining self-assembly protocols and molecular manipulation procedures. After the controlled removal of individual porphyrin molecules from dense-packed arrays on Ag(111), the surface state electrons are confined at the bare silver patches. These act as quantum wells that show well-defined unoccupied bound surface states.
View Article and Find Full Text PDFThe formation of 2D surface-confined supramolecular porous networks is scientifically and technologically appealing, notably for hosting guest species and confinement phenomena. In this study, we report a scanning tunneling microscopy (STM) study of the self-assembly of a tripod molecule specifically equipped with pyridyl functional groups to steer a simultaneous expression of lateral pyridyl-pyridyl interactions and Cu-pyridyl coordination bonds. The assembly protocols yield a new class of porous open assemblies, the formation of which is driven by multiple interactions.
View Article and Find Full Text PDFThe fabrication and control of coordination compounds or architectures at well-defined interfaces is a thriving research domain with promise for various research areas, including single-site catalysis, molecular magnetism, light-harvesting, and molecular rotors and machines. To date, such systems have been realized either by grafting or depositing prefabricated metal-organic complexes or by protocols combining molecular linkers and single metal atoms at the interface. Here we report a different pathway employing metal-organic chemical vapor deposition, as exemplified by the reaction of meso-tetraphenylporphyrin derivatives on atomistically clean Ag(111) with a metal carbonyl precursor (Ru3(CO)12) under vacuum conditions.
View Article and Find Full Text PDFThe tessellation of the Euclidean plane by regular polygons has been contemplated since ancient times and presents intriguing aspects embracing mathematics, art, and crystallography. Significant efforts were devoted to engineer specific 2D interfacial tessellations at the molecular level, but periodic patterns with distinct five-vertex motifs remained elusive. Here, we report a direct scanning tunneling microscopy investigation on the cerium-directed assembly of linear polyphenyl molecular linkers with terminal carbonitrile groups on a smooth Ag(111) noble-metal surface.
View Article and Find Full Text PDFWe investigated the surface bonding and ordering of free-base porphine (2H-P), the parent compound of all porphyrins, on a smooth noble metal support. Our multitechnique investigation reveals a surprisingly rich and complex behavior, including intramolecular proton switching, repulsive intermolecular interactions, and density-driven phase transformations. For small concentrations, molecular-level observations using low-temperature scanning tunneling microscopy clearly show the operation of repulsive interactions between 2H-P molecules in direct contact with the employed Ag(111) surface, preventing the formation of islands.
View Article and Find Full Text PDFUltrathin films of boron nitride (BN) have recently attracted considerable interest given their successful incorporation in graphene nanodevices and their use as spacer layers to electronically decouple and order functional adsorbates. Here, we introduce a BN monolayer grown by chemical vapor deposition of borazine on a single crystal Cu support, representing a model system for an electronically patterned but topographically smooth substrate. Scanning tunneling microscopy and spectroscopy experiments evidence a weak bonding of the single BN sheet to Cu, preserving the insulating character of bulk hexagonal boron nitride, combined with a periodic lateral variation of the local work function and the surface potential.
View Article and Find Full Text PDFRepulsive interactions: a staging of supramolecular aggregation from (0D) clusters to (1D) chains and (2D) assemblies as a function of molecular coverage of dipolar porphyrins adsorbed on the Ag(111) surface is described. It displays a complex interplay of both attractive and repulsive molecule-molecule interactions, the emergence of chirality, and the registry of the substrate.
View Article and Find Full Text PDFThe control of organic molecules, supramolecular complexes and donor-acceptor systems at interfaces is a key issue in the development of novel hybrid architectures for regulation of charge-carrier transport pathways in nanoelectronics or organic photovoltaics. However, at present little is known regarding the intricate features of stacked molecular nanostructures stabilized by noncovalent interactions. Here we explore at the single molecule level the geometry and electronic properties of model donor-acceptor dyads stabilized by van der Waals interactions on a single crystal Ag(111) support.
View Article and Find Full Text PDFStudies of complex condensed matter systems have led to the discovery of materials of unexpected spatial organization as glasses, glassy crystals, quasicrystals, and protein and virus crystals. Here, we present two-dimensional (2D) short-range disordered molecular crystalline networks, which, regarding spatial organization, can be considered as surface analogues of 3D glassy crystals. In particular, the deposition of a flexible molecular module on Cu(111) gives rise to distinct phases whose characteristics have been examined in real space by scanning tunneling microscopy: a 2D short-range distortional disordered crystalline network and a 2D short-range orientational disordered crystalline network, respectively.
View Article and Find Full Text PDFThe development of a variety of nanoscale applications requires the fabrication and control of atomic or molecular switches that can be reversibly operated by light, a short-range force, electric current or other external stimuli. For such molecules to be used as electronic components, they should be directly coupled to a metallic support and the switching unit should be easily connected to other molecular species without suppressing switching performance. Here, we show that a free-base tetraphenyl-porphyrin molecule, which is anchored to a silver surface, can function as a molecular conductance switch.
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