Simple Bottom-Up Synthesis of Bismuthene Nanostructures with a Suitable Morphology for Competitive Performance in the Electrocatalytic Nitrogen Reduction Reaction

Abstract

Nitrogen reduction to ammonia under ambient conditions has received important attention, in which high-performing catalysts are sought. A new, facile, and seedless solvothermal method based on a high-temperature reduction route has been developed in this work for the production of bismuthene nanostructures with excellent performance in the electrocatalytic nitrogen reduction reaction (NRR). Different reaction conditions were tested, such as the type of solvent, surfactant, reducing agent, reaction temperature, and time, as well as bismuth precursor source, resulting in distinct particle morphologies. Two-dimensional sheet-like structures and small particles displayed very high electrocatalytic activity, attributed to the abundance of tips, edges, and high surface area. NRR experiments resulted in an ammonia yield of 571 ± 0.1 μg h −1 cm −2 with a respective Faradaic efficiency of 7.94 ± 0.2% vs Ag/AgCl. The easy implementation of the synthetic reaction to produce Bi nanostructures facilitates its potential scale up to larger production yields.

Bismuth‐Noble Metal Alloy Nanostructures Prepared by Colloidal Chemical Routes for Use in Hydrogen Evolution and Oxygen Reduction Electrocatalysis: Bi‐Pt Versus Bi‐Pd

“…Hexagonal nanoplates with length mostly in the range 700–900 nm and a thickness of around 10 nm were observed, as shown previously. [ 35 ]…”

“…Since one of the goals of the current work was to compare the electrocatalytic efficiency of our bimetallic nanostructures with monometallic ones, in sample Sa‐4 we synthesized pure Bi nanostructures; the synthesis of this sample is described in our recent work on monoelemental bismuth nanosheets. [ 35 ] DEG was the solvent also in this sample while branched PEI was employed as surfactant and growth modifier, with bismuth nitrate as precursor and a synthesis temperature of 240 °C. Hexagonal nanoplates with length mostly in the range 700–900 nm and a thickness of around 10 nm were observed, as shown previously.…”

“…Sample Sa‐4 was synthesized as reported in our recent work on monometallic Bi. [ 35 ] Briefly, 860 mg PEI were added in 30 ml DEG in a sealed beaker in an autoclave under stirring. 1 g hydrazine was then introduced in the reaction mixture followed by the addition of 485 mg of Bi‐nitrate pentahydrate (Fluka).…”

“…Hexagonal nanoplates with length mostly in the range 700-900 nm and a thickness of around 10 nm were observed, as shown previously. [35] Taking into account that the sample Sa-1 was relatively rich in Pt, we wanted to produce a sample close to the PtBi 2 composition. For this reason, in Sa-5 DMF (dimethylformamide) was employed as a solvent instead of water.…”

Emerging p-Block-Element-Based Electrocatalysts for Sustainable Nitrogen Conversion

“…100 After the reduction process, the edge sites, sulfur dopant, or bismuth vacancies can be obtained on the surface of Bi to serve as active sites for boosting NH 3 synthesis. In addition to the topotactic transformation strategy, direct solvothermal, hydrothermal, and electrodeposition methods were also developed to prepare Bi nanocubes, 32 multiyolk− shell Bi@porous carbon, 101 bismuthene nanostructures, 102 a porous Bi electrode, 103 and a Bi nanosheet array. 104 In 2019, Yan et al reported that potassium cations (K + ) could promote the electrocatalytic reduction of N 2 to ammonia on Bi nanocubes.…”