Вы находитесь на странице: 1из 29

1.

Introduction

CO2 Hazardous:
A rapidly growing population and industrialization has caused the
world’s natural resources difficulty in keeping up with demands. Today,
fossil fuels such as coal, oil or natural gas (i.e., hydrocarbons) are burned in
power plants to produce energy. As we’ve becomes more dependent on
carbon-based fuels. We’ve seen a rapid increase in the atmospheric
concentration of CO2; from around 280 parts per million (ppm) before the
industrial revolution, to 370 ppm today. If current trends of fossil fuel use
continue the concentration of CO2 is likely to exceed 700 ppm by the end of
this century. According to experts, this could lead to global warming of
between1.4 and 5.80C, which may results in more frequent severe weather
conditions and damage to many natural ecosystems. Many believe that it is
realistic to promote actions that ensure stabilization of atmospheric CO2
concentrations at around 500-550 ppm. This is a considerable challenge,
given that global energy demand is expected to double between 2000 and
2050.

Carbon dioxide is one of the primary greenhouse gases causing


Earth’s global warming effect. Carbon dioxide trap heat, helping warm the
globe. The surge in carbon dioxide levels due to human activity since the
Industrial Revolution is now causing an overall warming of the planet that
is having impacts around the globe. And the burning of fuel generates not
only carbon dioxide, but also air pollutants that are harmful to human
health.

1
Why Reduction is Necessary?

We know CO2 is a greenhouse gas and if the concentration level of CO2


increases then gradually the earth becomes warmer. This is the main
reason why CO2 reduction is necessary.

CO2 emission from the trucks, cars, factories and electricity plants
that power the world’s economies are a chief reason global temperature
rises nearly 10C from pre industrial times. To maintain the level of
temperature we must reduce the concentration of CO2 level in atmosphere.

CO2 Reduction Pathway

In the past century, researchers have focused on investigating


different pathways to convert carbon dioxide to valuable products such as
hydrocarbons and alcohols. Hydrogenation of carbon dioxide has been
intensively studied and has shown promising results in pilot plants;
however, high temperature and high pressure conditions, in addition to
high consumption of hydrogen, make this process less efficient. The
conversion of carbon dioxide at room temperature and atmospheric
pressure using solar light or electrical energy are more attractive routes.
Photo catalysis uses semiconductor to promote reactions in the presence of
light radiation. Formic acid, methane, methanol, and ethanol are common
products of the photo electrochemical reduction of carbon dioxide at
metal/oxide electrodes; however, the quantum efficiency and production
rate are very low. A recent innovation in conversion of carbon dioxide has
been developed via aqueous electro catalytic reduction (Hori, 2008).

2
Photo electrochemical Reduction of CO2

Photo electrochemical reduction of carbon dioxide or photo catalysis


generally uses semiconductors to promote reaction in the presence of sun
light. The semiconductor is used as a catalyst to absorb solar energy and
generate electrons and protons needed for the reduction of carbon dioxide.
While hydrogenation of carbon dioxide requires high temperature and high
pressure conditions ((400-800 K, 2-12 MPa) (Chinches et al., 1987; Joo et
al., 1999; Wu et al., 2001; Saito et al., 2004), photo catalysis occurs under
relatively mild conditions with advantageous energy input – sun light – a
continuous and readily available source. Photocatalytic 12 method not only
can reduce carbon dioxide emissions, but also can produce very useful
chemicals such as formic acid, formaldehyde, methanol, methane, etc.
Figure 2.3 shows a model of the CO2 photocatalytic reduction mechanism
on Cu/TiO2. With the assistant of light radiation, an electron hole pair (eand
h+) is generated per absorbed photon. While OH radicals and O2 are formed
from the scavenging holes on titania (TiO2), CO2 and H2O molecules interact
with the trapped electrons on the Cu clusters to produce methanol.

In 1978, a photo electrode consisting of a single crystal p-gallium


phosphide was used for the photo electrochemical reaction (Halmann,
1978). Unlike the reduction of carbon dioxide on metal cathodes which
stops essentially after two electron transfer because of the high over
potential for formic acid reduction, the photo-electrolysis on p-gallium
phosphide proceeds further to yield formaldehyde and methanol. After 90
hours of irradiation, product concentration was as follows: formic acid
5x10-2 M, formaldehyde 2.8x10-4 M, and methanol 8.1x10-4 M.

One of the most challenging tasks for photo electrochemical


reduction of carbon dioxide to methanol is enhancement efficiencies. From

3
a thermodynamic perspective, converting one mole of carbon dioxide to
methanol requires 228 kJ of energy. Six electrons are required to reduce C+4
of CO2 to C-2 of CH3OH as discussed from equation 1.6. The reaction
mechanism in the photo reduction of carbon dioxide involves two main
radicals H• and •CO2ˉ. These radicals 15 are produced by electron transfer
from the valence band to the conducting band in the semiconductor by
photon absorption having an energy equal to or greater than the band gap
of the semiconductor. With a band gap of 3.2 eV, TiO2 is ideal to promote
the carbon dioxide reduction using UV illumination. Several researchers
have investigated the efficiency and selectivity of the processes by
modifying the photo catalyst surface with metal. In 1992, photocatalytic
reduction of carbon dioxide in an aqueous TiO2 suspension mixed with
copper powder was introduced (Hirano et al., 1992); however, TiO2 by
itself is an inefficient catalyst for the photochemical reduction of carbon
dioxide because of low product yields. The presence of copper particles on
the TiO2 surface not only offers reaction sites for carbon dioxide with an
excited electron but also helps the reducing species react with positive
holes on the semiconductor site

By adding potassium bicarbonate (0.01 M KHCO3) into the CO2


saturated aqueous solution containing TiO2 suspension mixed with copper
powder, methanol yield was doubled as compared with the bicarbonate-
free solution (Hirano et al., 1992). Tseng et al. used titania and titania
supported copper catalysts prepared by an improved sol-gel, a
homogeneous hydrolysis technique, to improve the photo electrochemical
reduction efficiency (Tseng et al., 2002). Concentration of catalyst and
copper loading were also investigated. Energy Dispersive X-ray
Spectroscopy (EDX) and X-ray Photoelectron Spectroscopy (XPS) analyses
revealed that Cu2p3/2 is 933.4 eV, which indicated primary Cu2O species on
the TiO2 supports and most copper clusters were on the TiO2 surface.
The electron positive hole recombination leading to limited product
formation on the catalyst surface lowers the photo catalysis process’s

4
efficiencies. Product efficiency and selectivity depend primarily on the type
of catalyst. Even though copper based titanium oxide has been known to be
the best catalyst for methanol production in the photo electrochemical
process, in order to upgrade to an industrial scale, methanol yields need to
be improved significantly. In addition, with an extremely low light
intensity, a large surface area would be needed to provide enough energy
for the reaction to occur efficiently (Wu et al., 2005). Therefore, another
alternative solution for carbon dioxide reduction is necessary.
Electrochemical Reduction of CO2

The foundations of electrochemistry in the late 18th century were


marked by the investigation of Galvani and Volta. They established the
relationship between chemical reactions and electricity. Electrochemistry
studies chemical reactions occurring at the interface of an electron
conductor (the working electrode) and an ionic conductor (the electrolyte).
Electrons are transferred between the electrode and the electrolyte in the
solution. It is called an electrochemical reaction when an external voltage
drives the reaction or a voltage is created by a chemical reaction. Since
electrons are transferred between molecules, this reaction is also called an
oxidation - reduction (redox) reaction. An electrochemical reaction
mechanism is a step by step sequence of electron transfer. An electro
catalytic process involves oxidation and reduction through direct transfer
of electrons. Researches and applications in this area have attracted many
scientists from all over the world during the past century.

One of the most practical recent electro catalytic applications is the


electrochemical reduction of carbon dioxide to hydrocarbons and alcohols.
This method uses electricity produced from renewable energy source
including hydro, solar, wind, geothermal, wave and tides for generation of
electrons. The direct electrochemical reduction of CO2 to CH3OH presents
an attractive method to produce liquid fuels such as dimethyl ether (DME),

5
synthetic gasoline, and feedstock for several organic compounds (Lee et al.,
1995; Jayamurthy et al., 1996). Although CH3OH is typically produced in
hydrogenation reactions using syngas and CO2 feeds (400-800 K, 2-12 MPa)
(Chinchen et al., 1986; Chinchen et al., 1987; Joo et al., 1999; Wu et al.,
2001; Saito et al., 2004), the aqueous electrochemical process operates at
room temperature and offers a convenient means for storing electrical
energy without increasing CO2 emissions.

Synthetic catalysts for the electro catalytic reduction of CO2, which


could facilitate such an artificial CO2 neutral redox cycle, have been studied
for many decades1–4. A main challenge in electrochemical CO2 reduction is
to develop catalysts that are capable of reducing CO2 beyond the two-
electron products carbon monoxide (CO), formic acid (HCOOH), and oxalate
(C2O4 2- ). Unfortunately, the formation of reduction products requiring four
or more electrons is invariably associated with considerable over
potentials due to the multiple intermediates involved in the reaction
mechanisms5 (although more reduced products often have higher stability
and correspondingly more positive equilibrium potentials). Metallic copper
is unique in producing significant amounts of high-energy multi-electron
transfer products such as methane, ethylene and ethanol3,6,7. Molecular
catalysts that are capable of reducing CO2 to a product different from one of
the above-mentioned two-electron products are much less common and
typically involve a strong interaction with the working electrode8. A
second important challenge in CO2 electro catalysis concerns the
suppression of the concomitant evolution of hydrogen, which is a dominant
side reaction for CO2 reduction from aqueous electrolytes. Strategies for
suppressing hydrogen evolution typically involve working with high(er)
CO2 to proton ratios, such as high CO2 pressures or solvents with a higher
CO2 solubility.
6
Product obtained during Electrochemical Reduction of CO2

There are so many product such as Hydrocarbons and fuels are


produced during electrochemical reduction of CO2 depending upon the
catalyst use, electrode used and also the physical condition such as Temp.
and Pressure. The products are Methanol, Ethanol, Propanol, Formic Acid,
Aldehyde, Ethylene, Propylene, Carbon monoxide (CO)[2];

Catalyst Required for Electrochemical Reduction of CO2

We know in a reaction catalyst plays a major role for the formation of


product by increasing the reaction rate. In electrochemical reduction
catalyst plays similar role for the reduction reaction. Here for the
electrochemical Reduction of CO2 we use different type of catalyst for
reduction. But out of these only few of them gives better efficiency for
production. The catalysts are copper porphyrin complex used as a
heterogeneous catalyst, using copper oxide catalyst, reduction at Cu/ZnO
surface, Molybdenum disulphide edges, Renewable and metal free carbon
nanofiber catalysts, cobalt oxide on Graphene, using Graphene
oxide/carbon nanotube electrode in ionic liquid/acetonitrile system.

Why Graphene/Reduced Graphene is used for Preparation of


catalyst?

Graphene is considered as one of the most promising materials in a


wide range of applications because of its outstanding electronic, optical,
thermal, and mechanical properties. Given its large specific surface area,
two-dimensional structure, facile decoration, and high adsorption capacity,
numerous graphene-based nanomaterials with unprecedented
characteristics have been designed, prepared, and applied in catalysis. In

7
this article, we first reviewed common synthetic methods to prepare
graphene-based catalysts followed by critical comments and possible
solutions. We then briefly summarized the characterization techniques that
were relevant to catalysis applications and their applications in energy
conversion, environmental protection, and several other typical fields.
Finally, we discussed the challenges and opportunities for the future
development of graphene-based nanomaterials in sustainable catalysis.

Graphene

Graphene is, a single atomic layer of graphite; which is an allotrope of


carbon that is made up of very tightly bonded carbon atoms organized into
a hexagonal lattice. What makes graphene so special is its sp2 hybridization
and very thin atomic thickness (of 0.345Nm). These properties are what
enable graphene to break so many records in terms of strength, electricity
and heat conduction (as well as many others). Now, let’s explore just what
makes graphene so special, what are its intrinsic properties that separate it
from other forms of carbon, and other 2D crystalline compounds?

Before monolayer graphene was isolated in 2004, it was theoretically


believed that two dimensional compounds could not exist due to thermal
instability when separated. However, once graphene was isolated, it was
clear that it was actually possible, and it took scientists some time to find
out exactly how. After suspended graphene sheets were studied by
transmission electron microscopy, scientists believed that they found the
reason to be due to slight rippling in the graphene, modifying the structure
of the material. However, later research suggests that it is actually due to
the fact that the carbon to carbon bonds in graphene are so small and
strong that they prevent thermal fluctuations from destabilizing it.

8
Properties of Graphene:

Electronic Properties: One of the major useful properties of graphene is


that it is a zero-overlap semimetal (with both holes and electrons as charge
carriers) with very high electrical conductivity

Mechanical Strength: Another of graphene’s stand-out properties is its


inherent strength. Due to the strength of its 0.142 Nm-long carbon bonds,
graphene is the strongest material ever discovered, with an ultimate tensile
strength of 130,000,000,000 Pascals.
9
Optical Properties: Graphene’s ability to absorb a rather large 2.3% of
white light is also an interestingly unique property, despite being only one
atom thick. This is due to its aforementioned electronic properties.

Why polyaniline coated electrode is used?

We know in Electrochemical Reduction of CO2 Product distribution


in CO2 reduction mainly depends on the electrode material and the
supporting electrolyte. The processes have been studied on various metal
electrodes by several authors. However, most of these methods are not
convenient for technical applications due to the high over potentials up to
−6 V (SCE) on metal electrodes and low current densities obtained during
the electrolysis. If water is used as a proton source, hydrogen evolution,
which accompanies the reduction of CO2, decreases current efficiency
significantly. Another disadvantage of water is the low solubility of
CO2 (0.033 mol dm−3 at 25 °C, 1 atm) in this solvent, which generally limits
the yield of the reduction products. The solubility of CO2 can be increased
by high pressure e.g. 1.7 mol dm−3 solubility has been obtained at 60 atm
CO2 pressure. Several authors [10];[11];[12];[13]; have reported that the
partial current density for CO2reduction increases when the reaction is
carried out under high pressure by using Co, Fe, Pt, Pd, Ni, In and Pb gas
diffusion electrodes (GDE) in aqueous solutions.

Furthermore, all these metals need highly negative over potentials


even lower than −1.4 V (SCE) in both protic and aprotic solutions. In order
to decrease the over potential, new electrode materials should be tested.

It has also been reported that aprotic electrolytes such as dimethyl


sulfoxide (DMSO), N,N-dimethyl form amide (DMF), propylene carbonate

10
(PC) and acetonitrile (AN) supply oxalic acid as the main product while
carbon monoxide, methanol and formic acid are the minor products [1].

Because of their specific properties and simple preparation,


conducting polymers such as polyaniline (PAn), polypyrrole and
polythiophene have gained importance in electro catalysis. The growth of
electrodeposited PAn films on Pt electrodes is easy under potentiodynamic
conditions in acidic aqueous solutions. Prussian blue (PB) laminated PAn
has been used by Ogura et al. [15];[16]; in a complicated electrode for CO2
reduction under high pressure. In order to overcome the high over
potentials, the authors have developed a mediated electrode system, in
which two films consisting of an inorganic conductor as the inner layer and
a conducting polymer (outer layer) are laminated on a Pt electrode. The
reaction products were lactic acid, acetic acid, formic acid, methanol and
ethanol. By using this modified electrode, CO2 was reduced at −0.8 V
(Ag | AgCl).

11
(Structure of Polyaniline)

In this study, methanol has been used as the mediums in solubility


of CO2 in this solvent is approximately five times higher than in
water [1];[2];[3]. Electro reduction of CO2 has been investigated at the
lowest possible over potential of −0.4 V (SCE) on a simple bulk PAn
electrode under ambient conditions and under high pressure in
methanol+LiClO4 as the supporting electrolyte. As far as we know, this is
the first study of electro reduction of CO2 under these conditions.

12
CHAPTER-2

LITERATURE SURVEY

13
Literature Review

This part describes graphene and graphene coated catalyst which are
used for reduction of CO2 and also the characterization of the catalyst
nanoparticles which are reported on various literatures which help us to
execute the present investigation. Several studies relating graphene and
graphene based nanoparticles for carbon dioxide reduction are performed
across the world for the last few years.

The main products are methanol, formic acid, formaldehyde, methane and
syngas [2]. The different product formation is mainly depends on the
selection of catalyst. As the major work have been done on metal catalyst.
The selection of electrolyte is also very important parameter for
electrochemical reduction of carbon dioxide [3]. Most of the work has been
done by using aqueous electrolyte. Very few researchers used non aqueous
electrolyte for the conversion of Carbon dioxide. Many of researchers found
that lower temperatures suppress hydrogen evolution and increase
efficiency for CO2 reduction. For getting higher faradaic efficiency the
solubility of carbon dioxide should high. High hydrogen overvoltage
electrodes with negligible CO adsorption (such as Hg, Cd, Pb, Tl, In and Sn)
can reduce CO2 with a high current efficiency. Researchers showed interest
in metal alloy also, they got good faradaic efficiency by using Copper metal
alloys. However, Copper and its alloys tend to give a mix of products,
including hydrogen. After using metal and metal alloy electrodes the
researchers turns to gas diffusion electrodes which shows good current
efficiency towards electrochemical reduction of Carbon dioxide.

14
CATALYST METHODS REFERENCE
NAME &PRODUCTS

pure cobalt metal Partially oxidized 10.1038/nature 16455


and partially atomic cobalt layers for
Vol 529, 7 January 2016
oxidised cobalt carbon dioxide electro
metal reduction to liquid fuel

Molybdenum Robust carbon dioxide Nature 5470,30 jul 2014


disulphide edges reduction on moly-
bednum disulphide
edges

Copper oxide(I) Selective ACS PP,2814-2821 March


Electrochemical
catalysts 31 2015
Reduction of Carbon
Dioxide to Ethylene and
Ethanol on Copper(I)
Oxide Catalysts
Metal free carbon Renewable and metal- Ncomms/3819,
nanofibre free carbon nanofiber
2 Dec 2013
catalysts for carbon
dioxide reduction to
form carbon monoxide

Immobilized Electrocatalytic M.S. Inorganic Chem.


cobalt reduction of carbon 2010,49, 3557-3566
protoporphyrin dioxide to CO and CH4

15
Cobalt phthalocyanine Highly selective and 1038/ncomms14675
carbon nanotube active CO2 reduction to 8 March 2017
hybrid structures produce Methane

Nanostructured Tin Electrochemical 10.1021/ja4113885,


Catalysts Reduction of Carbon 1734−1737,Dec 2014
Dioxide to Formic Acid

Metal Electrodes Reduction of CO2 to Bull Chem. Soc


Carbon monoxide and Japan,63,
Methanol
2459-2462(1990)

16
CHAPTER-3

OBJECTIVES

17
3.1 Objectives of the Thesis are

 Synthesis of Graphene Oxide and characteristic study of it.


 Synthesis of Reduced Graphene Oxide and characteristic study of it.
 Preparation of Graphene based catalyst.

 Electrochemical Reduction of CO2 to methanol by using the prepared
catalyst.
 Characterisation of Electrochemical Reduction of CO2.

18
CHAPTER-4

EXPERIMENTAL

19
4.1 Preparation of Graphene Oxide (GO)

Materials Required

1. Graphite flakes – (Luba Cheme, extra pure 99.5 %, 50 µm avg sizes,


bulk density 20-30 gm/100 ml).
2. Sulphuric Acid( H2SO4 )-(MERCK,98% concentration, density 1.84
Kg/Lit)
3. Phosphoric Acid (H3PO4)- (MERCK,88% concentration ,density-1.75
Kg/lit)
4. Potassium Permanganate (KMnO4)-(MERCK,99% purity)
5. Hydrochloric Acid(HCl)-(MERCK-35% concentration, density 1.18
Kg/lit)
6. Ethanol(C2H5OH)-(MERCK,99.9% purity, density .79 Kg/lit)
7. Distilled water

Methods:
Graphite Oxide can be prepared from different methods like –

Improved Hummer’s Method


Among these three methods the last one i.e. Improved Hummer’s Method is
the ideal as we can get best quality Graphite Oxide.

Improved Hummer’s Method:


This is the fastest common method of producing Graphite Oxide
maintaining the high C/O ratio.

The steps involved in this method are—

20
1. In a 1 lit biker H2SO4 (98%) 360 ml and H3PO4 (88%) 40 ml were
taken, in the ratio 9:1.
2. After that, Graphite powder was added into the acid mixture and
stirred it for 15 minutes with the help of a Hot plate (RPM=600-650).
3. After that KMnO4 =18 gm was added very slowly (took 5minutes to
add) to the above mixture by stirring. This reaction exothermic in
nature so the temperature was seen to increase abruptly to 60oC .So
addition of KMnO4 was done very cautiously.
4. After addition, the mixture was stirred for 15 min and temperature
was noted. When temperature decreased to 50oC, a hot plate was
used to maintain the mixture temperature 55 - 600C for 7-8 hrs.
5. Temperature should be maintained throughout the reaction, after
completion of reaction 400ml cold water (10-15oc) was added into
the mixture.
6. Then 6 ml H2O2 was added and the mixture was kept on ice bath
overnight.
7. Next day yellowish coloured GO precipitated. The above clear solvent
was discarded slowly by siphon.
8. Then to wash the GO slurry 400 ml HCl solution (3:1:1 vol ratio)
added and kept the mixture for GO precipitate.
9. After 3 hrs when GO precipitated, the liquid above was separated by
siphon.
10. After successive stages of washing, 200 ml of ether [THF] was
added to the material for the coagulation of the material.
11. After 4 hr. again the clear liquid above was separated and thick GO n
slurry was taken.
12. Then filtration was done by filter paper.

21
13. Lastly the wet GO was scraped from filter paper and kept in
Vacuum Oven at 90oc for 4 hours for drying.
14. Thus the dried GO was cooled and kept in sample bottle.

4.2 Preparation of Reduced Graphene Oxide (rGO)


Materials Required
 10gm of Graphene Oxide(GO)
 1L of distilled water
 NaOH solution
 20 ml Hydrazine mono hydrate (N2H4, 64-65%)
 Filtration paper

Working Procedure for Preparation


 10 gm of GO was stirred into 1L of distilled water. This
dispersion was stirred until it became a clear solution with no
visible particulate material.
 After that pH of the solution was increased to 10 by adding
NaOH solution and 20 ml hydrazine monohydrate was added to
the solution at 950C and stirrer for 4 hr and subsequently the
reaction was completed.
 The reduced GO was collected by filtration as a Black powder.
 The obtained powder was washed with distilled water several
times until pH is nearly 7 and until to remove the excess
hydrazine.
 Final product was dried in a vacuum oven at 1000C for 24 hr.

22
CHAPTER-5

FUTURE PLANNING

23
5.1 Future planning of my Thesis are

 Synthesis of Graphene based Electrocatalyst


 Characterisation of catalyst
 Electrochemical reduction of CO2
 Synthesis and Characterisation of the product obtained after
reduction

24
CHAPTER 6
REFERNCES

25
References:
1. Hori, Y. in Modern Aspects of Electrochemistry (eds Vayenas, C. G.,
White, R. E. & Gamboa-Aldeco, M. E.) 89–189 (Springer, 2008).
2. Kuhl, K. P. et al. Electrocatalytic conversion of carbon dioxide to
methane and methanol on transition metal surfaces. J. Am. Chem. Soc.
136, 14107–14113 (2014).
3. Appel, A. M. et al. Frontiers, opportunities, and challenges in
biochemical and chemical catalysis of CO2 fixation. Chem. Rev. 113,
6621–6658 (2013).
4. Torelli, D. A. et al. Nickel-gallium-catalyzed electrochemical
reduction of CO2 to highly reduced products at low overpotentials.
ACS Catal 6, 2100–2104 (2016).
5. Reske, R. et al. Controlling catalytic selectivities during CO2
electroreduction on thin Cu metal overlayers. J. Phys. Chem. Lett. 4,
2410–2413 (2013).
6. Spichiger-Ulmann, M. & Augustynski, J. Electrochemical reduction
of bicarbonate ions at a bright palladium cathode. J. Chem. Soc.
Faraday Trans. 1 81, 713–716 (1985).
7. Chen, Y., Lewis, N. & Xiang, C. Operational constraints and
strategies for systems to effect the sustainable, solar-driven
reduction of atmospheric CO2. Energy Environ. Sci. 8, 3663–3674
(2015).
8. Lieber, C. M. & Lewis, N. S. Catalytic reduction of carbon dioxide at
carbon electrodes modified with cobalt phthalocyanine. J. Am. Chem.
Soc. 106, 5033–5034 (1984).
9. Lin, S. et al. Covalent organic frameworks comprising cobalt
porphyrins for catalytic CO2 reduction in water. Science 349, 1208–
1213 (2015).

26
10. Asadi, M. et al. Nanostructured transition metal dichalcogenide
electrocatalysts for CO2 reduction in ionic liquid. Science 353, 467–
470 (2016).
11. Maurin, A. & Robert, M. Noncovalent immobilization of a
molecular ironbased electrocatalyst on carbon electrodes for
selective, efficient CO2-to-CO conversion in water. J. Am. Chem. Soc.
138, 2492–2495 (2016).
12. Li, C. W. & Kanan, M. W. CO2 reduction at low overpotential on Cu
electrodes resulting from the reduction of thick Cu2O films. J. Am.
Chem. Soc. 134, 7231–7234 (2012).
13. Rosen, J. et al. Electrodeposited Zn dendrites with enhanced CO
selectivity for electrocatalytic CO2 reduction. ACS Catal. 5, 4586–
4591 (2015).
14. Gao,D. et al. Size-dependent electrocatalytic reduction of CO2
over Pd nanoparticles. J. Am. Chem. Soc. 137, 4288–4291 (2015).
15. Nielsen, I. M. B. & Leung, K. Cobalt porphyrin catalyzed
electrochemical reduction of carbon dioxide in water. 1. a density
functional study of intermediates. J. Phys. Chem. A 114, 10166–10173
(2010).
16. Koper, M. T. M. Theory of the transition from sequential to
concerted electrochemical proton-electron transfer. Phys. Chem.
Chem. Phys. 15, 1399–1407 (2013).
17. Koper, M. T. M. Theory of multiple proton-electron transfer
reactions and its implications for electrocatalysis. Chem. Sci. 4, 2710–
2723 (2013).
18. Nørskov, J. K. et al. Origin of the overpotential for oxygen
reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892
(2004).

27
19. Koper, M. M. Analysis of electrocatalytic reaction schemes:
distinction between rate-determining and potential-determining
steps. J. Solid State Electrochem. 17, 339–344 (2013).
20. Kang, P., Chen, Z., Nayak, A., Zhang, S. & Meyer, T. J. Single catalyst
electrocatalytic reduction of CO2 in water to H2 þ CO syngas
mixtures with water oxidation to O2. Energ. Environ. Sci. 7, 4007–
4012 (2014).
21. Jo¨decke, M., Pe´rez-Salado Kamps, A´. & Maurer, G. An
experimental investigation of the solubility of CO2 in (N,N-
dimethylmethanamide þ water). J. Chem. Eng. Data 57, 1249–1266
(2012).
22. Kwon, Y. & Koper, M. T. M. Combining voltammetry with HPLC:
application to electro-oxidation of glycerol. Anal. Chem. 82, 5420–
5424 (2010).
23. Pardew, J., Burke, K. & Wang, Y. Generalized gradient
approximation for the exchange-correlation hole of a many-electron
system. Phys. Rev. B 54, 16533–16539 (1996).
24. Troullier, N. & Martins, J. Efficient pseudopotentials for plane-
wave calculations. II. Operators for fast iterative diagonalization.
Phys. Rev. B 43, 8861–8869 (1991).
25. Ufimtsev, I. S. & Martinez, T. J. Quantum chemistry on graphical
processing units. analytical energy gradients, geometry optimization,
and first principles molecular dynamics. J. Chem. Theory Comput. 5,
2619–2628 (2009).
26. Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and
accurate ab initio parametrization of density functional dispersion
correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132,
154104 (2010).

28
27. Grimme, S., Ehrlich, S.& Goerigk, L. Effect of the damping function
in dispersion corrected density functional theory. J. Comput. Chem.
32, 1456–1465 (2011).
28. Gewirth, A. A.; Thorum, M. S. Inorg. Chem. 2010, 49, 3557− 3566.
29. Armand, M.; Tarascon, J. M. Nature 2008, 451, 652−657.
30. Stamenkovic,V.;Mun, B. S.; Mayrhofer, K. J. J.; Ross, P. N.; Markovic,
N. M.; Rossmeisl, J.; Greeley, J.;Norskov, J. K. Angew. Chem., Int. Ed.
2006, 45, 2897−2901

29