Bo Jiang

Nanoarchitectures for Mesoporous Metals.

The field of mesoporous metal nanoarchitectonics offers several advantages which cannot be found elsewhere. These materials have been showcasing impressive enhancements of their electrochemical properties for further implementation, compared to their micro- and macroporous counterparts. Since the last few decades, various methods have been developed to achieve narrow pore size distribution with a tunable porosity and particle morphology. While hard templates offer a reliable and intuitive approach to synthesize mesoporous metals, the complexity of the technique and the use of harmful chemicals pushed several research groups to focus in other directions. For example, soft templates (e.g., lyotropic crystals, micelles assemblies) and solution phase methods (requiring to control reduction reactions) offer more and more possibilities in terms of available compositions and morphologies. Indeed, various metal (Pt, Pd, Au, Ru, etc.) can now be synthesized as dendritic, core@shell, hollow or polyhedral nanoparticles, with single- or multicomponents, alloyed or not, with unprecedented electrochemical activity.

Tunable‐Sized Polymeric Micelles and Their Assembly for the Preparation of Large Mesoporous Platinum Nanoparticles

Platinum nanoparticles with continuously tunable mesoporous structures were prepared by a simple, one-step polymeric approach. By virtue of their large pore size, these structures have a high surface area that is accessible to reagents. In the synthetic method, variation of the solvent composition plays an essential role in the systematic control of pore size and particle shape. The mesoporous Pt catalyst exhibited superior electrocatalytic activity for the methanol oxidation reaction compared to commercially available Pt catalysts. This polymeric-micelle approach provides an additional design concept for the creation of next generation of metallic catalysts.

Self-Construction from 2D to 3D: One-Pot Layer-by-Layer Assembly of Graphene Oxide Sheets Held Together by Coordination Polymers.

Deposition of Ni-based cyanide bridged coordination polymer (NiCNNi) flakes onto the surfaces of graphene oxide (GO) sheets, which allows precise control of the resulting lamellar nanoarchitecture by in situ crystallization, is reported. GO sheets are utilized as nucleation sites that promote the optimized crystal growth of NiCNNi flakes. The NiCNNi-coated GO sheets then self-assemble and are stabilized as ordered lamellar nanomaterials. Regulated thermal treatment under nitrogen results in a Ni3 C-GO composite with a similar morphology to the starting material, and the Ni3 C-GO composite exhibits outstanding electrocatalytic activity and excellent durability for the oxygen reduction reaction.

Multimetallic Mesoporous Spheres Through Surfactant-Directed Synthesis

Multimetallic mesoporous spheres are successfully synthesized with ultra‐large mesopores with the assistance of nonionic triblock copolymer (F127) as a structural directing agent. The kinetically controlled reduction rate of metal species and the concentration of F127 are critical to the formation of the large mesopores.

Surfactant-Directed Synthesis of Mesoporous Pd Films with Perpendicular Mesochannels as Efficient Electrocatalysts

Palladium (Pd) films with perpendicularly aligned mesochannels are expected to provide fascinating electrocatalytic properties due to their low diffusion resistance and the full utilization of their large surface area. There have been no studies on such mesoporous metal films, because of the difficulties in controlling both the vertical alignment of the molecular template and the crystal growth in the metallic pore walls. Here we report an effective approach for the synthesis of mesoporous Pd films with mesochannels perpendicularly aligned to the substrate by an elaborated electrochemical deposition. The films show a superior electrocatalytic activity by taking full advantage of the perpendicularly aligned mesochannels.

Mesoporous palladium–copper bimetallic electrodes for selective electrocatalytic reduction of aqueous CO2 to CO

Finding a highly efficient, selective and economic approach for electrochemical reduction of aqueous carbon dioxide is a great challenge in realizing an artificial system for a sustainable carbon cycle. Novel mesoporous palladium–copper bimetallic electrocatalysts with superior activity and high faradaic efficiencies (FEs) are reported for the first time. The mesoporous nanostructure provides a roughened surface which is abundant in active sites and promotes selective conversion of CO2 to CO. First-principles calculations exhibit that Pd atoms on the catalyst surface serve as reactive centers and highly selective CO formation is attributed to the geometric and electronic effects within the palladium–copper bimetallic alloys. The CO2 and COOH* intermediate adsorption ability and the CO desorption ability on Pd atoms are effectively enhanced in the presence of Cu. Our results provide wide ranging implications for further improving the design and preparation of CO2 reduction electrocatalysts.

Synthesis of ternary PtPdCu spheres with three-dimensional nanoporous architectures toward superior electrocatalysts

We report a simple method for the preparation of ternary PtPdCu spheres with a three-dimensional (3D) nanoporous structure in a solution phase. The structure, composition, and electronic states of the obtained material are characterized and studied by various physical techniques. By varying the amount of Cu precursor involved in the reaction, the composition of the spheres can be adjusted without affecting the morphology. Due to the nanoporous structure and the multimetallic synergetic effect, our ternary nanoporous PtPdCu spheres exhibited 1.7, 2.8, and 4.9 times higher activity than that of binary nanoporous PtPd spheres, dendritic Pt, and commercial Pt black catalysts, respectively.

Mesoporous metallic rhodium nanoparticles

Mesoporous noble metals are an emerging class of cutting-edge nanostructured catalysts due to their abundant exposed active sites and highly accessible surfaces. Although various noble metal (e.g. Pt, Pd and Au) structures have been synthesized by hard- and soft-templating methods, mesoporous rhodium (Rh) nanoparticles have never been generated via chemical reduction, in part due to the relatively high surface energy of rhodium (Rh) metal. Here we describe a simple, scalable route to generate mesoporous Rh by chemical reduction on polymeric micelle templates [poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA)]. The mesoporous Rh nanoparticles exhibited a ∼2.6 times enhancement for the electrocatalytic oxidation of methanol compared to commercially available Rh catalyst. Surprisingly, the high surface area mesoporous structure of the Rh catalyst was thermally stable up to 400 °C. The combination of high surface area and thermal stability also enables superior catalytic activity for the remediation of nitric oxide (NO) in lean-burn exhaust containing high concentrations of O2.

First Synthesis of Continuous Mesoporous Copper Films with Uniformly Sized Pores by Electrochemical Soft Templating

Although mesoporous metals have been synthesized by electrochemical methods, the possible compositions have been limited to noble metals (e.g., palladium, platinum, gold) and their alloys. Herein we describe the first fabrication of continuously mesoporous Cu films using polymeric micelles as soft templates to control the growth of Cu under sophisticated electrochemical conditions. Uniformly sized mesopores are evenly distributed over the entire film, and the pore walls are composed of highly crystalized Cu.

Morphosynthesis of nanoporous pseudo Pd@Pt bimetallic particles with controlled electrocatalytic activity

Nanoporous pseudo Pd@Pt bimetallic particles were prepared using a facile one-step synthetic approach. The morphologies of the resultant particles are changed from spheres to cubes by increasing the molar ratio of the Pd/Pt precursor solution. Compared to commercially available Pt black and Pt/C-20%, the nanoporous pseudo Pd@Pt bimetallic particles were up to 7 times and 2.1 times more active for the methanol oxidation reaction on the basis of equivalent Pt, respectively. This excellent electrocatalytic activity is caused by a combination of the high surface area of the nanoporous architecture in addition to the bimetallic synergetic effect. Through this work, we demonstrate a general approach for the creation of nanoporous bimetallic Pt-based particles with controlled shape, composition and size for enhanced catalytic activity.