Selective Electrooxidation of Glycerol to Formic Acid over Carbon Supported Ni_1–xM_x(M = Bi, Pd, and Au) Nanocatalysts and Coelectrolysis of CO₂

Abstract

The composition effect of carbon supported Ni x M 1−x (M = Bi, Pd, and Au) nanomaterials toward glycerol electrooxidation (GEOR) was evaluated in alkaline media. Ni-rich catalysts with different atomic ratios (M atomic ratio ≤20%) were synthesized by the heatless coreduction method and characterized by various physicochemical and electrochemical techniques. All structures of the Ni x M 1−x /C catalysts were composed of a rich phase of Ni(OH) 2 , as evidenced by TDA-TGA and XPS. Among the different nanomaterials, the Ni 0.9 Au 0.1 /C catalyst provided the lowest onset potential (+0.12 V vs Hg/HgO) and the highest peak current density. In situ infrared spectroscopy experiments combined with electrochemical measurements exhibited the formation of formate for all catalysts, thus indicating the breakage of C− C bonds of glycerol. GEOR led to 100% selectivity for formate after 1 h electrolysis and 100% conversion of glycerol after 24 h at +1.55 V. Furthermore, when these inexpensive catalysts were tested in tandem with cathodic CO 2 electroreduction, the anodic Ni 0.9 Au 0.1 /C catalyst displayed the highest partial current density for CO and the lowest onset potential.

MnO2 Electrocatalysts Coordinating Alcohol Oxidation for Ultra‐Durable Hydrogen and Chemical Productions in Acidic Solutions

“…[16] Thea bsorption bands at % 1240, and % 1364 and % 1385 cm À1 are considered to belong to COOH. [17] Besides,t he asymmeteic (O-C-O) Angewandte Chemie streching of COO À *(% 1541 and % 1519 cm À1 )i sv isible in this spectrum. [18] According to analysis of in situ FTIR and ex situ NMR results,apossible pathway of glycerol oxidation catalyzed by MnO 2 /CP under acid condition is proposed.…”

Recent Advances on Electrolysis for Simultaneous Generation of Valuable Chemicals at both Anode and Cathode

“…Valuable chemicals can be obtained from the electro-oxidation of various alcohols, accompanied by H 2 generation at the counter electrode. For example, formate/ formic acid from methanol [48][49][50][51][52] or glycerol, [53,54] acetate [55][56][57][58][59] or ethyl acetate [60] from ethanol, acetone [36] from isopropanol, lactate or pyruvate [11] from 1,2-propanediol, acrylate [61] from 1,3-propandiol, tartronate or mesoxalate [62] from glycerol, etc.…”

“…test was conducted after neutralizing with HCl and lyophilizing of obtained electrolyte. [54] In addition, CO 2 RR integrated with wastewater treatment with a tin cathode and a boron-doped diamond anode by Sabatino et al, where CO 2 RR was reduced to formic acid and a sort of azoic dye Acid Orange 7 (AO7) was oxidized to reach wastewater purification. The gas was evaluated by GC with TCD, and liquid formic acid was identified and quantified by HPLC.…”

MnO2 Electrocatalysts Coordinating Alcohol Oxidation for Ultra‐Durable Hydrogen and Chemical Productions in Acidic Solutions

“…[16] Thea bsorption bands at % 1240, and % 1364 and % 1385 cm À1 are considered to belong to COOH. [17] Besides,t he asymmeteic (O-C-O) Angewandte Chemie Forschungsartikel 21638 www.angewandte.de streching of COO À *(% 1541 and % 1519 cm À1 )i sv isible in this spectrum. [18] According to analysis of in situ FTIR and ex situ NMR results,apossible pathway of glycerol oxidation catalyzed by MnO 2 /CP under acid condition is proposed.…”