CHEMICAL ENGINEERING TRANSACTIONS
VOL. 73, 2019
A publication of
The Italian Association
of Chemical Engineering
Online at www.aidic.it/cet
Guest Editors: Andrea D’Anna, Paolo Ciambelli, Carmelo Sunseri
Copyright © 2019, AIDIC Servizi S.r.l.
I SBN 978-88-95608-70-9; I SSN 2283-9216
Catalytic Activity of Cu and Cu/Sn Electrodes during CO
2
Reduction from Aqueous Media
Laura Mais
a,
*, Simonetta Palmas
a
, Annalisa Vacca
a
, Michele Mascia
a
, Francesca
Ferrara
b
, Alberto Pettinau
b
a
Dipartimento di Ingegneria Meccanica, Chimica e dei Materiali, Università degli Studi di Cagliari,
via Marengo 2, 09123 Cagliari, Italy
b
Sotacarbo S.p.A., c/o Grande Miniera di Serbariu, 09013 Carbonia, Italy
l.mais@dimcm.unica.it
In this work, we investigated the catalytic activity of copper-based electrodes during CO
2
reduction from
KHCO
3
aqueous solutions. Copper electrodes, synthetized by the electrochemical reduction of thermally
formed copper oxide (CuRE), or by decorating of CuRE with tin (CuRE/Sn) were tested. Moreover,
commercial copper or tin foils have been used for comparison. Different electrochemical techniques such as
cyclic voltammeteries and linear sweep voltammetries were adopted in order to derive information on the
reductive processes and to characterise the behaviour of the electrodes. Higher cathodic currents were
obtained using CuRE and CuRE/Sn with respect to commercial foils. Depending on the applied potential,
lower faradic efficiency (FE) is obtained at CuRE/Sn rather than at CuRE, and a very high loading of Sn
seems to be required to increase the FE by some percentage points. Interestingly, at the lowest investigated
potential (-0.8 V), the presence of Sn, even at low amount, was able to catalyse the formic acid formation, with
a FE of 14%.
1. Introduction
Carbon dioxide increases continuously in the atmosphere, due to the growth of anthropogenic emissions, and
this has made it an issue of global concern, as CO
2
is considered one of the main greenhouse gases
responsible for global warming. In recent years, considerable attention has been paid to the control of CO
2
emissions, and their conversion, in order to mitigate the negative impact of this gas on the atmosphere.
Currently, the emission of CO
2
into the atmosphere can be reduced by several technologies, such as CO
2
capture and storage (Hossain and De Lasa, 2008). A better approach is to convert carbon dioxide into useful
liquid fuels and value-added chemicals, such as formic acid, methanol, methane, etc. (Kortlever et al., 2015).
Several techniques have been investigated in recent years, such as photochemistry, thermochemistry and
electrochemistry, to reduce catalytically CO
2
to fuels and chemicals (Centi et al., 2013; Lim et al., 2014).
Among these, the electrochemical approach has become attractive because it has several advantages, such
as easy control and scale-up of the process, mild conditions for the electroreduction of CO
2
.
The main drawbacks of the electrochemical reduction of CO
2
under ambient conditions include the very
negative potential required and the difficulty in controlling the selectivity of the reaction; in fact, the reduction of
CO
2
can occur via 2, 6, 8 and 12 electrons, resulting in a variety of products, such as carbon monoxide, formic
acid, methanol, formaldehyde, methane and acetic acid. (Hori et al., 2002; Wang et al., 2015; Chen et al.,
2015; Merino-Garcia et al., 2017). Among them, formic acid is one of the most interesting due to its highest
value-added with respect to the other possible products from CO
2
reduction. Moreover, formic acid is the
simplest naturally existing carboxylic acid, and its demand is dramatically expanding, year by year, due to its
various applications. For example, a significant proportion of formic acid is used in agriculture as a
preservative, due to its natural antibacterial properties. In industry, formic acid is commonly used in the
production of leather, the manufacture of rubber and dyeing of textiles, since, unlike mineral acids, it
evaporates without leaving any residues. Furthermore, formic acid has been proposed as a feed for fuel cells
(Yu and Pickup, 2008).
97
DOI: 10.3303/CET1973017
Paper Received: 15 March 2018; Revised: 28 August 2018; Accepted: 07 January 2019
Please cite this article as: Mais L., Palmas S., Vacca A., Mascia M., Ferrara F., Pettinau A., 2019, Catalytic Activity of Cu and Cu/sn Electrodes
During CO2 Reduction from Aqueous Media , Chemical Engineering Transactions, 73, 97-102 DOI:10.3303/CET1973017