Synthesis and Characterization of Dendritic Pt Nanoparticles by Using Cationic Surfactant

Platinum (Pt) is known as one of the most promising electrocatalysts, and nanostructured Pt materials have enhanced its activity due to their abundant catalytically active sites derived from their high surface area. Herein, we synthesize fascinating dendritic Pt nanoparticles (DPNs) by a softtemplating method using hexadecyltrimethylammonium chloride (CTAC) as a pore-forming agent. The dissolved negatively charged Pt precursor (PtCl4 2¹) effectively interact with the surfactant. The particle size of the obtained DPNs is around 20 nm, and the pore walls are composed of Pt nanocrystals. The obtained DPNs show good electrocatalytic activity towards methanol oxidation reaction (MOR) compared to commercial Pt black (PtB), and its stability is also higher than that of Pt

Electrochemical supermolecular templating of mesoporous Rh films

Making mesoporous rhodium (Rh) with traditional soft-templating methods is challenging because Rh has a high surface energy compared to other metals. Here, we report a synthetic concept to generate mesoporous Rh films (MRFs) by electrochemical co-deposition of Rh precursors and block copolymer micelles. We investigate the effect of deposition potentials and pH on the resulting mesoporous structures. Controlled electrodeposition enables us to conformally coat the entire surface of the electrode with a homogeneous mesoporous Rh film with any arbitrary thickness up to ∼840 nm. The average pore size of the MRF is ∼14 nm, with an average wall thickness of ∼9.5 nm. Since the MRFs are directly deposited on conducting substrates, they can be used as porous electrodes for various important electrocatalytic reactions. We examine the performance of these MRFs for the electrochemical methanol oxidation reaction (MOR) and find that they have a mass-normalized peak current density ∼4 times higher than a commercial Rh black (RhB) catalyst

Electrochemical supermolecular templating of mesoporous Rh films

Making mesoporous rhodium (Rh) with traditional soft-templating methods is challenging because Rh has a high surface energy compared to other metals. Here, we report a synthetic concept to generate mesoporous Rh films (MRFs) by electrochemical co-deposition of Rh precursors and block copolymer micelles. We investigate the effect of deposition potentials and pH on the resulting mesoporous structures. Controlled electrodeposition enables us to conformally coat the entire surface of the electrode with a homogeneous mesoporous Rh film with any arbitrary thickness up to ∼840 nm. The average pore size of the MRF is ∼14 nm, with an average wall thickness of ∼9.5 nm. Since the MRFs are directly deposited on conducting substrates, they can be used as porous electrodes for various important electrocatalytic reactions. We examine the performance of these MRFs for the electrochemical methanol oxidation reaction (MOR) and find that they have a mass-normalized peak current density ∼4 times higher than a commercial Rh black (RhB) catalyst

Novel porous metal phosphonates as efficient electrocatalysts for the oxygen evolution reaction

Recently, metal-doped organic-inorganic hybrid nanomaterials have attracted substantial attention for their high catalytic activity in the electrochemical oxygen evolution reaction (OER). Here, we report three novel porous metal phosphonates, cobalt phosphonate (CoPIm), nickel phosphonate (NiPIm), and nickel-cobalt phosphonate (NiCoPIm), using iminodi(methylphosphonic acid) as an organophosphorous precursor via a hydrothermal nontemplated synthetic route. All three materials have been explored as electrocatalysts for the OER. Notably, the CoPIm material exhibits excellent electrocatalytic behavior among all of the as-prepared catalysts. The high surface area and the formation of active CoOOH species on the catalyst surface during the OER process are the main driving force for a superior electrochemical OER. The CoPIm catalyst requires a very small overpotential (334 mV) to reach the current density of 10 mA cm in 1.0 M KOH solution with a Tafel slope of 58.6 mV dec as compared to NiPIm, NiCoPIm, and commercial IrO. Additionally, the prepared CoPIm catalyst shows excellent stability up to 25 h, suggesting its potential in electrochemical water splitting

Retrospect and Prospect: Nanoarchitectonics of Platinum-Group-Metal-Based Materials

Nanoarchitectonics, a concept encompassing nanoscale microstructures and atomic arrangements in materials, enables the precise modification of materials for desired applications by controlling their physical and chemical properties, as well as surface charge or energy. Particularly in metal materials, where surface reactions play a critical role, nanoarchitecture becomes the most influential factor affecting activity, selectivity, and stability. Focusing on platinum-group metals (PGMs) due to their inherently high efficiency in energy and environmental applications, this article provides a comprehensive review of synthetic methods for the morphological control of metal nanomaterials. The morphological control is classified into atomic arrangements in 0D, 1D, and 2D nanocrystals, as well as nanoporous structures, and the mechanisms of major reactions are covered in detail. Each chapter is supplemented with a table featuring several examples, facilitating the reader\u27s understanding of the structural controls of PGMs. Finally, the article outlines future challenges in achieving novel metal nanoarchitecture. The hope is that this review provides valuable insights into the synthesis of PGM-based nanomaterials and serves as a guide for designing and synthesizing innovative metal nanostructures for diverse applications

Designed Patterning of Mesoporous Metal Films Based on Electrochemical Micelle Assembly Combined with Lithographical Techniques

Mesoporous noble metals and their patterning techniques for obtaining unique patterned structures are highly attractive for electrocatalysis, photocatalysis, and optoelectronics device applications owing to their expedient properties such as high level of exposed active locations, cascade electrocatalytic sites, and large surface area. However, patterning techniques for mesoporous substrates are still limited to metal oxide and silica films, although there is growing demand for developing techniques related to patterning mesoporous metals. In this study, the first demonstration of mesoporous metal films on patterned gold (Au) substrates, prefabricated using photolithographic techniques, is reported. First, different growth rates of mesoporous Au metal films on patterned Au substrates are demonstrated by varying deposition times and voltages. In addition, mesoporous Au films are also fabricated on various patterns of Au substrates including stripe and mesh lines. An alternative fabrication method using a photoresist insulating mask also yields growth of mesoporous Au within the patterning. Moreover, patterned mesoporous films of palladium (Pd) and palladium–copper alloy (PdCu) are demonstrated on the same types of substrates to show versatility of this method. Patterned mesoporous Au films (PMGF) shows higher electrochemically-active surface area (ECSA) and higher sensitivity toward glucose oxidation than nonpatterned mesoporous Au films (NMGF)

Mesoporous metallic iridium nanosheets

Two-dimensional (2D) metals are an emerging class of nanostructures that have attracted enormous research interest due to their unusual electronic and thermal transport properties. Adding mesopores in the plane of ultrathin 2D metals is the next big step in manipulating these structures because increasing their surface area improves the utilization of the material and the availability of active sites. Here, we report a novel synthetic strategy to prepare an unprecedented type of 2D mesoporous metallic iridium (Ir) nanosheet. Mesoporous Ir nanosheets can be synthesized with close-packed assemblies of diblock copolymer (poly-(ethylene oxide)-b-polystyrene, PEO-b-PS) micelles aligned in the 2D plane of the nanosheets. This novel synthetic route opens a new dimension of control in the synthesis of 2D metals, enabling new kinds of mesoporous architectures with abundant catalytically active sites. Because of their unique structural features, the mesoporous metallic Ir nanosheets exhibit a high electrocatalytic activity toward the oxygen evolution reaction (OER) in acidic solution as compared to commercially available catalysts

Erratum: Highly Selective Reduction of Carbon Dioxide to Methane on Novel Mesoporous Rh Catalysts (ACS Appl. Mater. Interfaces (2018) 10:30 (24963-24968) DOI: 10.1021/acsami.8b06977)

In Table S1 (Supporting Information), some values were misordered. The following Table S1 is the revised one. [Table presented here]

Electrochemical preparation system for unique mesoporous hemisphere gold nanoparticles using block copolymer micelles

Gold nanoparticles (AuNPs) are widely used in various applications, such as biological delivery, catalysis, and others. In this report, we present a novel synthetic method to prepare mesoporous hemisphere gold nanoparticles (MHAuNPs) via electrochemical reduction reaction with the aid of polymeric micelle assembly as a pore-directing agent

A mesoporous non-precious metal boride system: synthesis of mesoporous cobalt boride by strictly controlled chemical reduction

Generating high surface area mesoporous transition metal boride is interesting because the incorporation of boron atoms generates lattice distortions that lead to the formation of amorphous metal boride with unique properties in catalysis. Here we report the first synthesis of mesoporous cobalt boron amorphous alloy colloidal particles using a soft template-directed assembly approach. Dual reducing agents are used to precisely control the chemical reduction process of mesoporous cobalt boron nanospheres. The Earth-abundance of cobalt boride combined with the high surface area and mesoporous nanoarchitecture enables solar-energy efficient photothermal conversion of CO into CO compared to non-porous cobalt boron alloys and commercial cobalt catalysts