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. 2021 Oct 5;6(41):27045–27051. doi: 10.1021/acsomega.1c03599

Conversion of CO2 into Formic Acid on Transition Metal-Porphyrin-like Graphene: First Principles Calculations

Seunghan Lee †, Hyeonhu Bae †, Amit Singh ‡,§, Tanveer Hussain ∥, Thanayut Kaewmaraya ⊥,#, Hoonkyung Lee †,*
PMCID: PMC8529598  PMID: 34693124

Abstract

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Recently, transition metal (TM)-porphyrin-like graphene has been predicted to be a promising material for CO2 capturing under favorable conditions. Such materials can capture CO2 at 300 K and release it at 450 K. However, the captured CO2 gas is mostly stored in oceans. With the aid of first principles calculations, we herein propose a method in which the captured CO2 is converted into an environmentally friendly product, formic acid. Addition of H2 to CO2 molecules adsorbed on Sc- and Ti-porphyrin-like graphene was found to catalyze this conversion. We also performed nudged elastic band calculations and thermodynamic analysis using the first-order Polanyi–Wigner equation and equilibrium statistical mechanics to investigate the chemical reactions involved in this conversion. In addition, we performed Bader charge analysis to obtain insights into the mechanism of charge transfer and adsorption throughout the conversion. Our study presents a novel method in which the captured CO2 is treated by converting it into an environmentally friendly product. Since this method does not require CO2 storage, it is expected to be an effective strategy to manage the rising CO2 level in the environment.

1. Introduction

Carbon dioxide (CO2), a greenhouse gas, is the main cause of global warming.1−4 The global surface temperature has increased significantly in recent years because of the drastic increase in CO2 emissions, and the combustion of fossil fuels contributes significantly to this. As an essential step toward mitigating the climate change, considerable efforts have been made to develop technologies for collecting CO2 from flue gases.1 The conventional methods for capturing CO2 from flue gases rely heavily on the use of aqueous ammonia.5−7 However, this approach suffers from poor solvent regeneration and corrosion due to the toxic nature of the amine solution.8−10

Recently, nanostructures or porous materials such as graphene, zeolites, and metal–organic frameworks have gained significant attention as CO2 capturing materials because of the high regeneration of CO2 gas through its physisorption on the material surface11−21 and the high capacity of the materials due to their large surface area (e.g., ∼2600 m2/g for graphene).22 However, their capture capacity significantly reduces under ambient conditions such as room temperature and atmospheric CO2 pressure because of the low binding energy of CO2 (approximately few tens of meV per CO2 molecule) to these materials. Moreover, the selectivity of CO2 from flue gases toward these materials is poor,20−23 and this largely hinders their use in CO2 capture from flue gases.23

More recently, through computational high-throughput screening based on first principles thermodynamics,24−26 metal-porphyrin-like graphene and Ca-decorated nanoribbons were shown to capture CO2 from flue gases under ambient conditions.24−26 They could selectively capture CO2 from other ambient gases such as H2, N2, and CH4, with a CO2 capture capacity of ∼3 mmol/g.24−26 The Ca atoms and d orbitals of transition metals (TMs) have a predominant contribution to the binding of CO2 during its capture.27−31 Meanwhile, transition metal-porphyrin-like graphene is synthesized in experiments.32 Therefore, metal-porphyrin-like graphene materials can serve as a promising reversible CO2 capture material. However, storage of CO2 in oceans and ground is still a matter of concern because of the high cost of CO2 storage after its release on Sc- and Ti-porphyrin-like graphene.

Herein, we present a first principles study of a novel method for treating CO2 following its capture. The proposed method converts CO2 on metal-porphyrin-like graphene to formic acid (HCOOH) by adding H2 as shown in Figure 1, which is slightly acidic and harmless; that is, it is environmentally friendly.33−37 CO2 storage in oceans and ground can thus be avoided, resulting in easier management of the captured CO2. Our results show that the addition of H2 molecules to the CO2 molecule adsorbed on the TM atom led to the formation of formic acid. The d orbitals of the TM atoms play a role in catalyzing the reaction between CO2 and H2 to form formic acid. This provides a novel framework for converting CO2 into environmentally friendly products, without the need for a CO2 storage process. Furthermore, formic acid has different uses in the form of food preservation additives, preservatives, and antibacterial agents and in dyeing and processing of leather and rubber. The conversion of CO2 into formic acid and its derivatives33 or CO2 conversion for fuel cells and hydrogen storage has already been studied.34−37

Figure 1.

Figure 1

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Schematic for the consecutive reaction of CO2 adsorbed on TM-porphyrin-like graphene to produce HCOOH upon addition of H2. (a) The H2 molecule approaches the CO2 molecule adsorbed on the TM-porphyrin-like graphene. (b) H2 is dissociatively adsorbed on the TM atom. (c) The product of the reaction between H2 with CO2 on the TM atom is HCOOH. (d) Release of the HCOOH molecule adsorbed on TM-porphyrin-like graphene.

2. Results and Discussion

To investigate the possibility of conversion of CO2 into formic acid on TM-porphyrin-like graphene, we performed the first principles calculations of CO2 adsorption on Sc- and Ti-porphyrin-like graphene. CO2 adsorption on TM results in the formation of the η2 – CO2 structure through Dewar interaction.27 The TM-promoted reaction pathway of CO2 and H2 to form formic acid was obtained using the NEB method.38−42 The process by which the Sc and Ti atoms participate in this reaction can be divided into four stages involving four intermediate states. Each step was investigated with various trial coordinates. Here, we assume that the real process occurs in an energy surface, which corresponds to the minimum energy path for reaction. Thus, the minimum energy path of CO2 conversion that we presented in our paper is the most probable process in experiments.

When CO2 is adsorbed on the TM atom, it may adopt three configurations depending on the number of bonds. Based on hapticity, these three configurations can be classified as η1, η2, and η3 as shown in Figure 2a–c. In the case of the Sc atom, CO2 has the strongest binding in the η2 mode formed using two bonds, with a binding energy of 0.75 eV. Meanwhile, in the case of the Ti atom, the largest binding energy of 1.09 eV was observed in the η2 mode. This suggests that CO2 binds to Sc- and Ti-porphyrin-like graphene by adopting the η1 configuration.

Figure 2.

Figure 2

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(a–c) Optimized atomic structures of CO2 binding to TM-porphyrin-like graphene with η1, η2, and η3 configurations, respectively. (d) Calculated reaction energy of H2 dissociation on CO2 on Sc-porphyrin-like graphene to afford HCOOH obtained using the NEB method. Four transition states and five metastable states exist in the reaction pathway for the conversion of H2 and CO2 to HCOOH on Sc-porphyrin-like graphene.

We added H2 molecules to the CO2-adsorbed Sc-porphyrin-like graphene to obtain the optimized geometry upon adsorption. The distance between the Sc atom and H2 molecule was 3.41 Å, and the bond length was 0.75 Å. Moreover, formic acid could be generated from this configuration (Figure 1a). We performed the NEB calculations to investigate the energy barrier for the conversion of CO2 and H2 to formic acid on the Sc atom. Four transition states (TS1, TS2, TS3, and TS4) and five metastable states were found for this conversion (Figure 2d). The energy barriers corresponding to TS1, TS2, TS3, and TS4 were 13.5, 1.1, 10.5, and 9.0 kcal/mol, respectively. There were four intermediates (IM1, IM2, IM3, and IM4) corresponding to these transition states. For TS1, the H2 molecule is dissociated to HCOOH@Sc, in which the distance between the H atoms is 2.12 Å. Formic acid was generated with a net energy barrier of 33.7 kcal/mol, via the formation of four transition states and five intermediates (Figure 2d).

In Sc-porphyrin-like graphene, first, the H2 molecule dissociates into two hydrogen atoms that bind to a carbon atom and an extra oxygen atom that is not involved in TM binding. The bound CO2 combines with a H2 molecule to adopt the η1 – CO2 configuration, eventually driving the binding reaction to generate formic acid via several stages. The NEB calculations confirmed that there were five steps in this reaction (Figure 2d). The H2 molecule adjacent to CO2 binds to the C and O atoms that do not participate in the η2 bond formation. The energy barrier of this reaction is ∼13.5 kcal/mol according to the NEB calculations. The step with the highest activation energy barrier according to the Arrhenius equation is the rate-determining step of the overall reaction; the other steps do not contribute to the overall rate of the reaction.

We next investigated the conversion of CO2 into formic acid on Ti-porphyrin-like graphene. CO2 was adsorbed on the Ti atom with a binding energy of 1.09 eV, and the distance between CO2 and the Ti atom was 2.06 Å. We performed NEB calculations to identify the TS and IM states between CO2@Ti (initial state) and HCOOH + Ti (final state). Four TS and five IM states were also found between the initial and final states (Figure 3). The dissociation of CO2 is similar to that on Sc-porphyrin-like graphene.

Figure 3.

Figure 3

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Calculated reaction energy of H2 dissociation on CO2 on Ti-porphyrin-like graphene to afford HCOOH obtained using the NEB method. Four transition states and five metastable states exist in the reaction pathway for the conversion of H2 and CO2 to HCOOH on Ti-porphyrin-like graphene.

Now, we calculated the escape time from the initial state (IM0) to the first intermediate state (IM1) to investigate the practical conditions of the conversion because the step with the highest activation energy barrier is the rate-determining step of the overall reaction (Figure 4a), while the other steps do not contribute to the overall rate of the reaction. Using the first-order Polanyi–Wigner equation,43 adsorption coverages (θ) between the two states in time t are expressed as

2. 1
2. 2

where i and k indicate the index for representing the states (i = 1 for the initial state and i = 2 for the first intermediate state) and reaction rate constant, i.e., the frequency of collisions resulting in a reaction, respectively. The rate is expressed as follows by the Arrhenius equation

2. 3

where ν, kB, and T denote the trial frequency, Boltzmann constant, and temperature, respectively.

2. 4
2. 5

where θ0 indicates the initial value of the coverage at the initial state.

Figure 4.

Figure 4

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(a) Schematic of the reaction energy of conversion of CO2 on Sc-porphyrin-like graphene with H2 to HCOOH, where the value of the activation barrier corresponds to 13.5 kcal/mol (TS1) between the initial state (IM0) and the first intermediate state (IM1) from the NEB calculations (Figure 3). (b) Calculated adsorption coverages as a function of time at 300, 400, and 500 K using eq 5.

The calculated coverage for given temperatures is shown in Figure 4b, where the trial frequency is chosen to be 0.5 THz. The characteristic time for escape is from a few seconds to a few microseconds. From this result, we suggest that a suitable experiment condition for the conversion is ∼300 to 500 K.

To achieve the conversion of CO2 to HCOOH, HCOOH attached to Sc or Ti should be released. Here, we carried out the evaluation of the desorption of HCOOH in equilibrium between the HCOOH molecule attached to Sc or Ti and HCOOH gas using the grand partition function. The fractional occupancy for the adsorption site, f(P, T), is expressed by the formula24

2. 6

where P, μ(P, T), and Eads indicate the pressure of a gas, chemical potential of a gas at a given P and T, and adsorption energy, respectively. The chemical potential of HCOOH gas was parameterized by the following formula

2. 7

where μideal(P, T) denotes the chemical potential of the ideal gas model and constants A and B in a linearized excess part are 0.09350 eV and −1.09233 meV/K for HCOOH with R2 = 0.999 in the range from 1 atm to 1 natm and 200 to 700 K, respectively. A pressure-dependent term in an excess part is negligible in this range. HCOOH molecules are released on Sc- and Ti-porphyrin-like graphene at ∼500 K and ∼10–6 bar as shown in Figure 5. In addition, we have already shown that the reaction for the conversion of CO2 to HCOOH gas occurs at easily achievable conditions (Figure 4). Therefore, the activity for the conversion of CO2 on Sc- and Ti-porphyrin-like graphene can be controlled by varying the temperature.

Figure 5.

Figure 5

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Calculated fractional occupancy of HCOOH on (a) Sc- and (b) Ti-porphyrin-like graphene as a function of temperature at the isobaric process.

We also studied the binding mechanism of formic acid on a TM-porphyrin-like graphene. It was found that the π states of CO2 and formic acid were significantly involved in hybridization with the d states of Sc and Ti (Figure 6a–d). The charge density in the occupied states and charge density difference are shown in Figure 6e–h. This indicates that the presence of chemical bonding between the CO2 molecule and Sc and Ti atoms can be explained using the Dewar–Chatt–Duncanson model, which describes TM–organic complexes in terms of electron donation (hybridization of empty TM d states with filled π states) and back donation (hybridization of filled TM d states with empty π states).27,28

Figure 6.

Figure 6

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Density of states of Sc- and Ti-porphyrin-like graphene, charge density difference, and charge density at the Fermi level. (a) Projected density of states (PDOS) of CO2, H2, and Sc of Sc-porphyrin-like graphene. (b) PDOS of HCOOH and Sc of Sc-porphyrin-like graphene. (c) PDOS of CO2, H2, and Ti of Ti-porphyrin-like graphene. (d) PDOS of HCOOH and Ti of Ti-porphyrin-like graphene. (e) Charge density difference between Sc-porphyrin-like graphene and HCOOH; red and blue colors indicate depletion and accumulation of electrons, respectively. (f) Charge density at the Fermi level of Sc-porphyrin-like graphene with HCOOH; the value of the isosurface is 0.002764 e/Å3. (g) Planar averaged charge density difference along the z direction of Sc-porphyrin-like graphene with HCOOH. (h) Planar averaged charge density at the Fermi level along the z direction of Ti-porphyrin-like graphene with HCOOH. The red and blue dashed lines indicate the position of the graphene and TM atom, respectively. The gray zone indicates the position of HCOOH.

We also performed the Bader charge analysis44−47 to better understand the charge transfer mechanism throughout the conversion. The positive value indicates that the charge is transferred from the surroundings to the atoms, while a negative value indicates the opposite phenomenon. In the case of Sc-porphyrin-like graphene, CO2 adsorption results in a charge transfer of −2.33, −3.44, 1.97, and 2.25 electrons for the Sc, C, O1, and O2 atoms, respectively (Figure 7a), while the adsorption of HCOOH results in the charge transfer of −2.34, −2.58, 1.93, 1.99, −0.13, and −1.00 electrons for the Sc, C, O1, O2, H1, and H2 atoms, respectively (Figure 7b). In the case of Ti-porphyrin-like graphene, adsorption of CO2 results in charge transfer of −2.35, −2.32, 1.53, and 1.87 electrons for the Ti, C, O1, and O2 atoms, respectively (Figure 7c), while the adsorption of HCOOH results in charge transfer of −2.27, −2.45, 1.93, 1.95, −0.14, and −1.00 electrons for the Ti, C, O1, O2, H1, and H2 atoms, respectively (Figure 7d). For both Sc- and Ti-porphyrin-like graphene, the Bader charge transfer analysis suggested that CO2 was strongly chemisorbed. Further addition of H2 resulted in the formation of formic acid, which was weakly adsorbed relative to CO2, and therefore, the release of formic acid was practically feasible.

Figure 7.

Figure 7

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Bader charge analysis for (a) Sc-porphyrin-like graphene with adsorbed CO2, (b) Sc-porphyrin-like graphene with adsorbed HCOOH, (c) Ti-porphyrin-like graphene with adsorbed CO2, and (d) Ti-porphyrin-like graphene with adsorbed HCOOH. The values mentioned near the atoms indicate transferred charges, e indicates the elementary charge (1.602 × 10–19 C), and + and – signs indicate accumulation and depletion of the electrons, respectively.

3. Conclusions

We investigated the feasibility of the TM-porphyrin-like graphene-mediated conversion of CO2 to formic acid using first principles calculations. There were three significant findings in this study: (1) TM atoms aid the conversion of CO2 into formic acid, (2) the d orbitals play an important role in this conversion, and (3) there are three TS and four IM states in this reaction pathway. Our results show that TM-porphyrin-like graphene can be used for the conversion of CO2 into formic acid upon addition of H2. When exposed to H2 gas, TM-porphyrin-like graphene can capture CO2 and convert and release it in the form of formic acid. The Bader analysis reveals that CO2 was strongly chemisorbed, and the addition of H2 resulted in the formation of formic acid, which was relatively weakly adsorbed, thereby assisting the release of formic acid at a feasible temperature. Thus, we conclude that TM-porphyrin-like graphene can selectively capture CO2 and transform it into formic acid, which is an environmentally friendly compound.

4. Computational Methods

We performed first principles density functional theory48 calculations using the Vienna Ab Initio Simulation Package (VASP) with the projector augmented wave (PAW) method49,50 for conversion of CO2 on TM-porphyrin-like graphene adsorption, our model for the TM-porphyrin-like graphene comprised a 4 × 4 hexagonal supercell (Figure 8), and the composition of the supercell was C26N4TM1, where C, N, and TM denote carbon, nitrogen, and transition metal atoms, respectively. The kinetic energy cutoff was set at 600 eV to ensure accurate calculations. The structure was geometrically optimized till the Hellmann–Feynman force acting on each atom was less than 0.01 eV/Å. We used 4 × 4 × 1 k-point sampling for each case, and the Brillouin zone integration was performed using the Monkhorst–Pack scheme.51 There is no dependence of the lattice constant as to the type of TM. Since the strength of the interaction between CO2 and TM is ∼1 eV, which is much greater than that of a few meV, we did not consider the van der Waals interaction for the conversion process of CO2. The nudged elastic band (NEB) calculations52,53 were performed to obtain the transient states between a particular configuration of CO2 + H2 and formic acid.

Figure 8.

Figure 8

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Periodic calculation model for the 4 × 4 TM-porphyrin-like-graphene. The dotted line indicates the supercell for our calculations with a lattice constant of 9.88 Å.

Acknowledgments

The authors gratefully acknowledge financial support from the Basic Science Research Program (NRF-2018R1D1A1B07046751) through the National Research Foundation (NRF) of Korea, funded by the Ministry of Science, ICT and Future Planning and by the National Research Foundation (NRF) of Korea grant funded by the Korean government (MSIT; NRF-2021R1A5A103299611).

Author Contributions

All authors have given approval to the final version of the manuscript.

The authors declare no competing financial interest.

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