Copper‐Halide Polymer Nanowires as Versatile Supports for Single‐Atom Catalysts

Abstract

Single‐atom catalysts are heterogeneous catalysts with atomistically dispersed atoms acting as a catalytically active center, and have recently attracted much attention owing to the minimal use of noble metals. However, a scalable and inexpensive support that can stably anchor isolated atoms remains a challenge due to high surface energy. Here, copper‐halide polymer nanowires with sub‐nanometer pores are proposed as a versatile support for single‐atom catalysts. The synthesis of the nanowires is straightforward and completed in a few minutes. Well‐defined sub‐nanometer pores and a large free volume of the nanowires are advantageous over any other support material. The nanowires can anchor various atomistically dispersed metal atoms into the sub‐nanometer pores up to ≈3 at% via a simple solution process, and this value is at least twice as big as previously reported data. The hydrogen evolution reaction activity of −18.0 A mgPt−1 at −0.2 V overpotential shows its potential for single‐atom catalysts support.

Surface Coordination Chemistry of Atomically Dispersed Metal Catalysts

“…In addition to the phosphorus-based ligands, other coordinating groups, such as the bipyridyl and cationic imidazole moieties, can be introduced into the polymer framework for incorporating metal species through coordination and/or electrostatic interactions for the construction of ADCs. 790,791 The stability of the water-sensitive metal complex catalysts can be dramatically enhanced by coordinating them onto superhydrophobic polymers. A nice example of such polymers is the polymer made from the monomer of tris(2-tert-butyl-4vinylphenyl)phosphite under solvothermal condition (Figure 50e).…”

“…While the Rh-COPL-3bp&10P exhibited the highest TOF, the Rh-COPL-3.75bp&10P showed the highest ratio of linear to branched aldehydes. In addition to the phosphorus-based ligands, other coordinating groups, such as the bipyridyl and cationic imidazole moieties, can be introduced into the polymer framework for incorporating metal species through coordination and/or electrostatic interactions for the construction of ADCs. , …”

A Simple Mechanical Method to Modulate the Electrochemical Electrosorption Processes at Metal Surfaces

“…The electrocatalytic activity of electrode materials is certainly important in the field of energy-related issues. More and more strategies have been developed to extremely enhance the activity, e.g., novel microstructures, single atom materials, and composition effects [1,2,3,4,5,6,7,8]. Recently, the coupling of surface mechanics and the electrochemical process has been considered an interesting topic and offers a new understanding in the field of electrochemistry [9,10,11,12,13,14].…”

Electrochemical Nitrogen Reduction Kinetics on a Copper Sulfide Catalyst for NH3Synthesis at Low Temperature and Atmospheric Pressure

“…The representative TEM and SEM images of the as-synthesized Fe–CuS/C catalysts are shown in Figure . Wires composed of copper and sulfur were formed with thicknesses in the range of 100–200 nm with a varying length more than a few micrometers . Upon the addition of 0.5 atom % Fe to the CuS nanorods, Fe nanoparticles of approximately 30 nm diameter were formed on the CuS wires, as shown in the elemental mapping image (Figure b).…”

“…Wires composed of copper and sulfur were formed with thicknesses in the range of 100−200 nm with a varying length more than a few micrometers. 30 Upon the addition of 0.5 atom % Fe to the CuS nanorods, Fe nanoparticles of approximately 30 nm diameter were formed on the CuS wires, as shown in the elemental mapping image (Figure 1b). The catalyst mixed with carbon was also synthesized by adding conductive carbon into the precursor solution.…”