Electrochemical reduction of carbon dioxide

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The electrochemical reduction of carbon dioxide, also known as CO2RR, is the conversion of carbon dioxide (CO2) to more reduced chemical species using electrical energy. It represents one potential step in the broad scheme of carbon capture and utilization. [1]

Contents

CO2RR can produce diverse compounds including formate (HCOO-), carbon monoxide (CO), methane (CH4), ethylene (C2H4), and ethanol (C2H5OH). [2] The main challenges are the relatively high cost of electricity (vs petroleum) and that CO2 is often contaminated with O2 and must be purified before reduction.

The first examples of CO2RR are from the 19th century, when carbon dioxide was reduced to carbon monoxide using a zinc cathode. Research in this field intensified in the 1980s following the oil embargoes of the 1970s. As of 2021, pilot-scale carbon dioxide electrochemical reduction is being developed by several companies, including Siemens, [3] Dioxide Materials, [4] [5] Twelve and GIGKarasek. The techno-economic analysis was recently conducted to assess the key technical gaps and commercial potentials of the carbon dioxide electrolysis technology at near ambient conditions. [6] [7]

Chemicals from carbon dioxide

In carbon fixation, plants convert carbon dioxide into sugars, from which many biosynthetic pathways originate. The catalyst responsible for this conversion, RuBisCO, is the most common protein. Some anaerobic organisms employ enzymes to convert CO2 to carbon monoxide, from which fatty acids can be made. [8]

In industry, a few products are made from CO2, including urea, salicylic acid, methanol, and certain inorganic and organic carbonates. [9] In the laboratory, carbon dioxide is sometimes used to prepare carboxylic acids in a process known as carboxylation. An electrochemical CO2 electrolyzer that operates at room temperature has not yet been commercialized. Elevated temperature solid oxide electrolyzer cells (SOECs) for CO2 reduction to CO are commercially available. For example, Haldor Topsoe offers SOECs for CO2 reduction with a reported 6-8 kWh per Nm3 [note 1] CO produced and purity up to 99.999% CO. [10]

Electrocatalysis

The electrochemical reduction of carbon dioxide to various products is usually described as:

ReactionReduction potential Eo (V) at pH = 7 vs SHE [11]
CO2 + 2 H+ + 2 e− → CO + H2O−0.52
CO2 + 2 H+ + 2 e− → HCOOH −0.61
CO2 + 8 H+ + 8 e− → CH4 + 2 H2O−0.24
2 CO2 + 12 H+ + 12 e− → C2H4 + 4 H2O−0.34

The redox potentials for these reactions are similar to that for hydrogen evolution in aqueous electrolytes, thus electrochemical reduction of CO2 is usually competitive with hydrogen evolution reaction. [2]

Electrochemical methods have gained significant attention:

  1. at ambient pressure and room temperature;
  2. in connection with renewable energy sources (see also solar fuel)
  3. competitive controllability, modularity and scale-up are relatively simple. [12]

The electrochemical reduction or electrocatalytic conversion of CO2 can produce value-added chemicals such methane, ethylene, ethanol, etc., and the products are mainly dependent on the selected catalysts and operating potentials (applying reduction voltage). A variety of homogeneous and heterogeneous catalysts [13] have been evaluated. [14] [2]

Many such processes are assumed to operate via the intermediacy of metal carbon dioxide complexes. [15] Many processes suffer from high overpotential, low current efficiency, low selectivity, slow kinetics, and/or poor catalyst stability. [16]

The composition of the electrolyte can be decisive. [17] [18] [19] Gas-diffusion electrodes are beneficial. [20] [21] [22]

Catalysts

Catalysts can be grouped by their primary products. [14] [23] [24] Several metal are unfit for CO2RR because they promote to perform hydrogen evolution instead. [25] Electrocatalysts selective for one particular organic compound include tin or bismuth for formate and silver or gold for carbon monoxide. Copper produces multiple reduced products such as methane, ethylene or ethanol, while methanol, propanol and 1-butanol have also been produced in minute quantities. [26]

Three common products are carbon monoxide, formate, or higher order carbon products (two or more carbons). [27]

Carbon monoxide-producing

Carbon monoxide can be produced from CO2RR over various precious metal catalysts. [28] Steel has proven to be one such catalyst., [29] or hydrogen. [30]

Mechanistically, carbon monoxide arises from the metal bonded to the carbon of CO2 (see metallacarboxylic acid). Oxygen is lost as water. [31]

Formate/formic acid-producing

Formic acid is produced as a primary product from CO2RR over diverse catalysts. [32]

Catalysts that promote Formic Acid production from CO2 operate by strongly binding to both oxygen atoms of CO2, allowing protons to attack the central carbon. After attacking the central carbon, one proton attaching to an oxygen results in the creation of formate. [31] Indium catalysts promote formate production because the Indium-Oxygen binding energy is stronger than the Indium-Carbon binding energy. [33] This promotes the production of formate instead of Carbon Monoxide.

C>1-producing catalysts

Copper electrocatalysts produce multicarbon compounds from CO2. These include C2 products (ethylene, ethanol, acetate, etc.) and even C3 products (propanol, acetone, etc.) [34] These products are more valuable than C1 products, but the current efficiencies are low. [35]

See also

Notes

  1. ↑ Normal Cubic Meter - the quantity of gas that occupies one cubic meter at standard temperature and pressure.

Related Research Articles

<span class="mw-page-title-main">Carbon monoxide</span> Colourless, odourless, tasteless and toxic gas

Carbon monoxide is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simplest carbon oxide. In coordination complexes, the carbon monoxide ligand is called carbonyl. It is a key ingredient in many processes in industrial chemistry.

<span class="mw-page-title-main">Electrolysis</span> Technique in chemistry and manufacturing

In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity".

<span class="mw-page-title-main">Formic acid</span> Simplest carboxylic acid (HCOOH)

Formic acid, systematically named methanoic acid, is the simplest carboxylic acid, and has the chemical formula HCOOH and structure H−C(=O)−O−H. It is an important intermediate in chemical synthesis and occurs naturally, most notably in some ants. Esters, salts and the anion derived from formic acid are called formates. Industrially, formic acid is produced from methanol.

<span class="mw-page-title-main">Sabatier reaction</span> Methanation process of carbon dioxide with hydrogen

The Sabatier reaction or Sabatier process produces methane and water from a reaction of hydrogen with carbon dioxide at elevated temperatures and pressures in the presence of a nickel catalyst. It was discovered by the French chemists Paul Sabatier and Jean-Baptiste Senderens in 1897. Optionally, ruthenium on alumina makes a more efficient catalyst. It is described by the following exothermic reaction:

Artificial photosynthesis is a chemical process that biomimics the natural process of photosynthesis. The term artificial photosynthesis is used loosely, refer to any scheme for capturing and storing energy from sunlight by producing a fuel, specifically a solar fuel. An advantage of artificial photosynthesis is that the solar energy can be immediately converted and stored. By contrast, using photovoltaic cells, sunlight is converted into electricity and then converted again into chemical energy for storage, with some necessary losses of energy associated with the second conversion. The byproducts of these reactions are environmentally friendly. Artificially photosynthesized fuel would be a carbon-neutral source of energy, which could be used for transportation or homes. The economics of artificial photosynthesis are not competitive.

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<span class="mw-page-title-main">Electrocatalyst</span> Catalyst participating in electrochemical reactions

An electrocatalyst is a catalyst that participates in electrochemical reactions. Electrocatalysts are a specific form of catalysts that function at electrode surfaces or, most commonly, may be the electrode surface itself. An electrocatalyst can be heterogeneous such as a platinized electrode. Homogeneous electrocatalysts, which are soluble, assist in transferring electrons between the electrode and reactants, and/or facilitate an intermediate chemical transformation described by an overall half reaction. Major challenges in electrocatalysts focus on fuel cells.

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<span class="mw-page-title-main">C1 chemistry</span> One-carbon molecule chemical processes

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<span class="mw-page-title-main">Carbon capture and utilization</span>

Carbon capture and utilization (CCU) is the process of capturing carbon dioxide (CO2) from industrial processes and transporting it via pipelines to where one intends to use it in industrial processes.

Hydrogen evolution reaction (HER) is a chemical reaction that yields H2. The conversion of protons to H2 requires reducing equivalents and usually a catalyst. In nature, HER is catalyzed by hydrogenase enzymes. Commercial electrolyzers typically employ platinum supported as the catalyst at the anode of the electrolyzer. HER is useful for producing hydrogen gas, providing a clean-burning fuel. HER, however, can also be an unwelcome side reaction that competes with other reductions such as nitrogen fixation, or electrochemical reduction of carbon dioxide or chrome plating.

Solar reforming is the sunlight-driven conversion of diverse carbon waste resources into sustainable fuels and value-added chemicals. It encompasses a set of technologies operating under ambient and aqueous conditions, utilizing solar spectrum to generate maximum value. Solar reforming offers an attractive and unifying solution to address the contemporary challenges of climate change and environmental pollution by creating a sustainable circular network of waste upcycling, clean fuel generation and the consequent mitigation of greenhouse emissions.

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