Copolymers of bipyridinium and metal (Zn & Ni) porphyrin derivatives; theoretical insights and electrochemical activity towards CO2

This study reports the electropolymerization of novel keto functionalized octaethyl metal porphyrins (Zn2+ and Ni2+) in the presence of 4,4′-bipyridine (4,4′-bpy) as a bridging nucleophile. The polymer films were characterized by electrochemical, spectroscopic (UV-Vis, XPS, FT-IR and Raman spectroscopy) and imaging (AFM and SEM) techniques. The absorption and electronic spectra confirm the presence of both porphyrin and 4,4′-bipyridine units in the film. The surface morphology reveals homogeneous film deposition with average roughness values of approx. 8 nm. The theoretical studies performed offered insights into the interplay of different metal centres (Zn2+ and Ni2+) and the keto functionality of the porphyrin unit in the formation of copolymer films. The electrochemical interaction of polymer films with CO2 suggests a reversible trap and release of CO2 with low energy barriers for both the polymers.


Introduction
Remarkable development has been seen over the past few decades for compounds containing transition metal complexes due to their versatile conjugated p electron molecular structures and variable catalytic and electronic properties. [1][2][3] Catalysts based on metal-nitrogen-carbon (M-N-C) extended structures bear the perceptible advantage of well-dened, efficient and robust molecular structures, allowing functionalization and customization at the atomic level to improve the overall catalytic performance and ease for mechanistic study. 4,5 Arguably, nature is the best source of inspiration for modern technology. Combining the best features of bioinspired and manmade transition metal complexes those including porphyrins, phthalocyanines, cyclam and their analogues pave a new route towards efficient catalyst for a broad range of reactions. 3,6,7 Porphyrin a N4 macrocycles are an excellent electronic mediator and are widely studied as they display interesting activity in homogeneous media and conned to electrode surface when used as electro catalyst. 8 Their properties are also modulated by varying the metal in the ring centre. Metalloporphyrins offer rich and reversible redox properties when conned to electrode surface and tends to improve utilization of active sites and promote electron transport reactions. 9 In addition to these attributes, the functionalized porphyrin has been recognized to offer drastically altered chemical, molecular and physical properties. 10 The functionalized porphyrins in the form of metal-organic framework and covalent polymer attracts great attention in material science due to high surface area, an important property in gas storage and capture. 11 The functional groups are introduced either at the peripheral or the core of the macrocycles, thereby changing aromaticity and degeneracy of the electronic structure. 12 To date, methods such as covalent self-assembly, spin coating, drop-casting, electropolymerization, electrospray and electrostatic self-assembly are employed to immobilize different porphyrins on electrode surfaces. 13,14 Among them, electropolymerization allows the formation of polymer lms with enhanced stability and high surface area; moreover, compact layers with control over thickness can be produced. 15,16 Different strategies have been demonstrated to electropolymerize porphyrin lms with high density on the electrode surface. 10,[17][18][19][20] Ruhlmann and coworkers reported an easy and simple method to electropolymerize porphyrins without electroactive substituents in presence of Lewis bases with at least two active sites as bridging nucleophiles. 21,22 The key step was attributed to the nucleophilic reaction between the Lewis bases and the generated dication of the octaethylporphyrins. Also, polymer properties like conductance through the extended conjugation can be varied by changing bridging nucleophile or functionalizing the porphyrins, keeping at least two accessible meso positions. 10,[23][24][25] Metalloporphyrins immobilized electrodes are extensively studied for their profound usage in diverse application. In this work, we demonstrate the electropolymerization of b-keto functionalized metal porphyrins (NiOEPK and ZnOEPK) in the presence of a bridging ligand 4,4 0 -bpy (4,4 0 -bipyridine) on the FTO surface. In the search of earth abundant and non-precious metal based system the studies of the two particular porphyrin units i.e. ZnOEPK and NiOEPK are interesting as Ni porphyrins are ring oxidized along with the central metal, unlike Zn porphyrin with two ring oxidation steps with unreacted central metal. 21 Bipyridine complexes are also mostly studied molecular catalysts. 4,4 0 -bpy functioning as bridging nucleophile and also as a peripheral substituent is crucial, as it has overall inuence on the electronic structure of the system, which it turn dictates its electrochemical activity. 26-28 UV-Vis, FTIR, Raman and X-ray photoelectron spectroscopy along with AFM, SEM and EDX establishes the graing of 4,4 0 -bpy with the porphyrin to form polymer lms on the electrode surface. DFT calculations were performed to investigate the electropolymerization process of bketo functionalized porphyrin (ZnOEPK and NiOEPK) with 4,4 0bpy and understand the effect of the central metal atom and keto functionalization on polymer formation. We also looked into the electrochemical interaction of deposited polymer lms with N 2 and CO 2 . Metalloprophyrins are known to possess favorable properties regarding CO 2 electrocatalysis. However, with this type of polymer there are also other not so well-known electrochemical interactions with CO 2 . Addition of CO 2 proceeds via carbamate formation involving the 4,4 0 -bpy substituents. This process proceeds with reversible trap and release of CO 2 with low energy barriers.

Materials
All chemical reagents and solvents used were analytical grades or higher. Zinc octaethyl porphyrin ketone (ZnOEPK) and nickel octaethyl porphyrin ketone (NiOEPK) were synthesized according to the previous report. 12

Electrochemical measurements
Cyclic voltammetry was performed using a conventional three electrodes system and an Autolab PGSTAT101 potentiostat.
One-sided uorinated indium tin oxide (FTO) [Pilkington] with a sheet resistance of 8.1 U sq À1 , was used as a working electrode. Before use, it was cleaned by ultrasonication in acetone, ethanol and water for 10 min followed by plasma cleaning for 3 min. A coiled platinum wire was used as a counter electrode. All potentials are reported vs. a silver chloride coated silver wire (Ag/AgCl) pseudo reference electrode prepared galvanostatically in saturated KCl(aq) and calibrated against ferrocene/ ferrocenium couple, E ref ¼ 0.45 V in 0.1 M TBAPF 6 in acetonitrile.

Electropolymerization
All the polymer lms were formed by 25 iterative potentiodynamic cycles in 5 Â 10 À4 M porphyrin (NiOEPK and ZnOEPK) and 5 Â 10 À4 M 4,4 0 -bpy solution in 0.1 M TBAPF 6 in (4 : 1) DCE : ACN. The potential range was in between À0.6 to 1.6 V vs. Ag/AgCl at a scan rate of 200 mV s À1 . Electropolymerization of porphyrin in the presence of an appropriate bridging nucleophile leads to the growth of a polymer lm. 21,22 The obtained polymer lms were rinsed with ACN followed by quartz-distilled water to remove traces of unreacted starting material on the electrode surfaces and preserved in a desiccator for further use.

Interaction with CO 2
To understand the interaction of carbon dioxide with the ketofunctionalized porphyrin polymer lms cyclic voltammetry (CV) measurements were performed in three-electrode customized airtight single compartment cell. The polymer lms of ZnOEPK and NiOEPK on/or blank FTO was used as a working electrode, Pt wire as a counter electrode and Ag/AgCl as a quasi-reference electrode. The studies were performed in deaerated and dry 0.1 M TBAPF 6 in ACN solution pre-saturated with either N 2 , CO 2 or Ar for 30 min at a scan rate of 100 mV s À1 in the potential range of 0 to À1.35 V vs. Ag/AgCl.

Spectroscopic measurements
UV-Vis absorption spectra of the monomer dissolved in DCM and polymer lm on the electrode surface were recorded by an Agilent Cary 60 UV-Vis spectrophotometer with blank FTO as a reference for background correction.
FTIR spectra of the polymer lms were measured by a Bruker Vertex 70 FTIR spectrometer with MCT detector cooled with liquid nitrogen. Each spectrum was recorded at 55 incidence angle relative to a surface normal using a Harrick Seagull accessory, compiling 248 scans at 4 cm À1 spectral resolution.
Raman spectra were obtained by Renishaw inVia confocal Raman microscope equipped with a CCD detector and a Leica microscope. Spectra were recorded with 50Â objective, 1200 l mm À1 grating and using a 532 nm diode laser as the excitation source with 10 mW laser power and accumulation of 1.
XPS measurements of porphyrin lm on the FTO substrates were recorded by PerkinElmer PHI 5400 spectrometer using Mg Ka radiation (1253.6 eV). All the binding energies were calibrated to the peak position of the main C 1s signal at 284.6 eV of the porphyrins. All the XPS spectra were tted using and Voigt line shape (convolution of Gaussian and Lorentzian) aer subtraction of Shirley background tting was performed using the Igor Pro SPANCF curve tting macro package. Broad energy range survey scans were performed to determine the atomic concentration and to check possible impurities with a pass energy of 89.45 eV. Higher-resolution spectra were also collected for selected core-levels. For those, pass energy of 37.75 eV was used.

Morphology of the lms
AFM studies were conducted by Veeco diCaliber on the modi-ed electrode surface using silicon tipped cantilever operating in the tapping mode. The image processing and analysis have been carried out using the WSxM 4.0 soware. Surface morphology was evaluated by Thermo Scientic Apreo S (FE-SEM) with Oxford Instrument Ultim Max 100 EDS spectrometer.

Theoretical studies
To understand the polymerization of keto functionalized octaethyl porphyrin with 4,4 0 -bpy, the most favourable position for the nucleophilic interaction of rst 4,4 0 -bpy was determined by optimizing all four different meso positions. The most stable structure among these four structures was then optimized for the second 4,4 0 -bpy to understand the variation in polymerization due to change in the central atom. All the calculations were carried out within the Kohn-Sham formulation of DFT. Projector augmented wave potential 30,31 was used, with Perdew-Burke-Ernzerhof (PBE) 32 approximation for the exchangecorrelation and generalized gradient approximation, 33 as implemented in-plane wave pseudopotential based code, VASP. [34][35][36] Cubic simulation cell, with images separated by at least 15 A of vacuum in all three directions, was used. The porphyrin structure was created using Quantumwise-VNL-2017.1. 37 For each SCF cycle, energy convergence criteria of 10 À4 eV were implemented. For structural optimization, force cutoff of 0.01 eV A À1 was used. The M-N distances of the crystallographically characterized ZnOEP and NiOEP is 2.05 A and 1.96 A respectively which matches exactly with the previously reported results. 38,39 HOMO and LUMO of the systems were plotted with isosurface value of one-tenth of its maxima.

Electropolymerization
The consecutive voltammetric scans recorded during electropolymerization of metal octaethyl porphyrin ketones (M ¼ Zn 2+ [ZnOEPK À0.6 to 1.6 V vs. Ag/AgCl] and Ni 2+ [NiOEPK À0.55 to 1.55 V vs. Ag/AgCl]) in the presence 4,4 0 -bpy acting as bridging nucleophile at a scan rate of 200 mV s À1 starting from 0 V going in the anodic direction are presented in Fig. 1 and 2. The potential window is optimized for obtaining homogeneous reproducible production of stable polymer lms.
During the rst cycle, NiOEPK showed one oxidation peak at 0.71 V and an increasing current starting at 1.2 V and on the reverse scan one reduction peak at 0.31 V. From the second cycle on three oxidation peaks can be seen at 0.69, 1.05 and 1.38 V. The rst two peaks originate from the cation and dication formation of the metal porphyrin. 22,40,41 The porphyrin dication being strong electrophile undergoes nucleophilic attack by 4,4 0 -bpy to form isoporphyrin cation 42 as depicted in Scheme 1. The third peak is attributed to the reversible oxidation of an isoporphyrin. All these peaks shi towards more positive potential due to the progress of electrode coating, these peaks merge later into one broad peak at 1.41 V. On the reverse scan, the reductive peaks at 0.31, À0.05 and À0.18 V are seen together with an increase in current close to the switching potential, which originates from the second reduction of the 4,4 0 -bpy. The two later ones are from the reduction of isoporphyrin and bipyridinium respectively and are merging into a major cathodic peak À0.18 V. The peak developed at 0.31 V is the reduction of the oxidized porphyrin in the solution. In ZnOEPK (Fig. 2), three successive one electron oxidation peaks were observed at 0.42, 1.02, and 1.3 V. The rst two peaks originate from the cation and dication formation of the porphyrin and the third peak is attributed to the reversible oxidation of an isoporphyrin. 22 On further iterative scans, the rst peak diminishes aer a few cycles and the latter two peaks merge into one broad peak that is shied to a higher potential. In the cathodic direction, the reduction peaks at À0.04 and À0.22 V for ZnOEPK are associated with the reduction of isoporphyrin and bipyridinium, respectively. Upon continuous scans, these peaks merge into a major cathodic peak similar to NiEOPK. In both cases, there is an increasing current starting from À0.4 V which is assigned to the beginning of the second one electron reduction of bipyridium unit. The progressive increase in the peak current with every cycle clearly shows the continues growth and deposition of the polymer lm on the electrode surface. 23,43 Theoretical studies The mechanism for electropolymerization of akin porphyrin species is well established. It occurs via nucleophilic attack of the bridging nucleophile at the active meso position leading to the formation of polymers. To understand the effect of keto functionalization and metal centres (M ¼ Zn and Ni) on the obtained polymer geometry, DFT studies were performed. First, we will compare the inuence of central atom Zn and Ni on the resulting ZnOEPK and NiOEPK structures respectively. The effect of completely and partially lled valance orbitals (as in case of Zn and Ni) reects in the respective porphyrins structures. Despite Zn having smaller ionic radii than Ni, Zn-N bond length in ZnOEPK ranges from 2.21 to 2.32 A. Whereas, the bond length of Ni-N in NiOEPK showed hardly any variation (1.97 A to 1.98 A). Also, it accounts for the blue shi in the spectra. Further, all M-N bond lengths are almost equal in NiOEPK, unlike that of ZnOEPK (Fig. 3).
The signicant contribution of the central atom in NiOEPK and ZnOEPK is witnessed from the spatial distribution of HOMO-LUMO in both the systems (Fig. 4). The differences in the HOMO and LUMO explain the variation observed in the preferred meso position for the nucleophilic addition of the rst 4,4 0 -bpy nucleophile. The HOMO in ZnOEPK is mostly around the central Zn atom and nearby N and C atoms, whereas in NiOEPK it is more delocalized and spread over most of the porphyrin but categorically excluding N atoms. However, LUMO in ZnOEPK is comparatively more delocalized and prominent around the keto group, while LUMO in NiOEPK is mostly localized near the central metal atom (Fig. 4). DFT studies validate that the rst 4,4 0 -bpy prefers meso position near to the keto group for ZnOEPK. Whereas in NiOEPK, energetically most favourable meso position is farthest from the keto group (Fig. S5 †). This interesting consequences due to the inuence of different metal species is understood based on the subtle differences observed in the spatial distribution of HOMO-LUMO of NiOEPK and ZnOEPK (Fig. 4).
The LUMO of NiOEPK and ZnOEPK with the rst 4,4 0 -bpy nucleophile were further analyzed to investigate the nucleophilic addition of the second 4,4 0 -bpy nucleophile. As shown in Fig. 5, LUMO in both NiOEPK and ZnOEPK are identical. It is interesting to note that LUMO are distributed over the meso position opposite to the rst 4,4 0 -bpy which facilitates linear polymerization in both the porphyrins (structure of linear polymerization is shown in Fig. S6 †). It should be noticed, that second 4,4 0 -bpy prefers the opposite position concerning rst bpy nucleophile attached to the porphyrins. It turns out to be the farthest meso position from keto group in ZnOEPK and the nearest in case of NiOEPK. Further, both 4,4 0 -bpy units prefer parallel orientation to each other and perpendicular to the plane of the porphyrin unit while proceeding linearly.

Spectroscopic analysis
The UV-Vis spectra in Fig. 6A and S1A † of the polymer lms on FTO and their monomers dissolved in DCM exhibit typical porphyrin traits with a strong Soret band and weaker Q band/s arising due to transition between HOMOs and LUMOs in the metal centre and the substituents. [45][46][47] The number of Q bands in the monomer with the introduction of a keto group on the porphyrin backbone is attributed to a decrease in the symmetry of the molecule. The blue shi observed in Ni complex as compared to Zn is due to decreased electron density arising from p bond delocalization with increase energy available for electron transition. 48 However, the absorption spectra of the  polymer lms exhibit broader Soret band and one detectable Q band with reduced intensity and red-shied (Table 1). This effect due to polymerization is well documented by extension in conjugation with the increased number of electron withdrawing pyridinium spacers. 49 This reects the change in symmetry with graing of 4,4 0 -bpy on the porphyrin along with the integrity of the porphyrin unit in the polymer lms. 50,51 FTIR spectra of NiOEPK monomer and polymer (Fig. 6B) and ZnOEPK monomer and polymer (Fig. S1B †) reveals characteristic modes of vibration from the porphyrin framework. However, the spectrum of the polymer lm is much broader with reduced intensity. The intense band at 1722 cm À1 is assigned to C]O stretching on the 5 members strained ring. The downshi is attributed to elongated conjugation. The characteristic C]N stretching vibration from the pyridinium ring at 1627 cm À1 manifests the presence of 4,4 0 -bpy in the polymer skeleton. 52 The weak peaks around 1015, 1213 and 1448 cm À1 correspond to C-H rocking vibration, C-N vibration and skeletal vibration from the pyrrole ring, respectively. 52,53 The peak at 852 cm À1 is associated with meso C-H out of plane bending vibration. 54 The formation of a polymer lm with porphyrin character on the electrode surface was further shown by Raman spectroscopy. Fig. 7A and S2 † demonstrating some characteristic   Paper RSC Advances bands around 1400-1670 cm À1 range, mainly from the porphyrin skeleton i.e. C]C and C]N stretching modes. 46 For the monomer samples, the inuence of M-N bond strength on the C]C and C]N stretching vibrations are evident. 55 A slight shi in these stretching modes due to polymerization can be observed. In the case of the polymers, there are considerable coupling with stretching vibration arising from the 4,4 0 -bpy linker. The strong intensity around 1300 cm À1 in the polymer lms indicates incorporation of 4,4 0 -bpy in the porphyrin network. The retention of the optical and electronic properties of the monomer unit in the polymer lm suggests the P-conjugated system remain intact on the electrode surface. The elemental composition and chemical state of the polymeric lms were further examined by XPS analysis. The deconvoluted XPS spectra into component peaks are shown in Fig. 8 and S3. † The C 1s XPS spectra are unfolded into three components. The peaks at $284.6 and $285.9 eV are attributed to the carbon backbone (C-C/C]C and C]N) of the porphyrin lms and the one at $288.2 eV is characteristic for the C-N and C]O moiety residing on the porphyrin. 47,56 The photoelectron N 1s spectra also exhibit three distinct signals.
Mainly the peak arising at $398.6 eV (lower binding energy [BE]) is characteristic of the four nitrogens in the metalloporphyrin (Zn 2+ and Ni 2+ ) framework. 47,57 The peaks at $399.9 and $401.9 eV are approximated to the spacer used for interconnecting the porphyrin and to the electropositive pyridine (bpy + ) nitrogen atom, respectively. 58 The O 1s spectra manifest the most intense signal to oxygen bound carbon (O]C) on the porphyrin at $531.4 eV. 56 An additional peak recorded at 533.4 eV is due to absorbed oxygen impurities on the lm surface. 59 The XPS spectrum also shows the presence of F 1s and P 2p attributed to the counter ion PF 6 À . 59 These metalloporphyrin lms exhibit characteristic BE of the 2p core levels of M(II) species. In poly ZnOEPK the presence of Zn(II) centred porphyrin is conrmed by the BE of Zn 2P 3/2 and Zn 2P 1/2 at 1021.9 and 1045.1 eV, respectively. 60 In the case of poly NiOEPK, the presence of Ni(II) is evidenced by the appearance of 2P 3/2 and 2P 1/2 core levels at 854.4 and 873.2 eV, respectively. 45 The spectrum also incorporates two structureless and very weak shakeup satellites at 862.6 and 881.8 eV ubiquitous in Ni(II) porphyrin due to relaxation effect. 45,47,57 The weakness of these signals is in agreement with the diamagnetic nature of Ni(II) in poly NiOEPK. 45,57 The similarity  in the nature of poly NiOEPK and poly ZnOEPK, except for the central metal species, clearly reects from the N 1s, C 1s and O 1s spectra.

Morphology
The AFM and SEM images of the polymer lms aer 25 cycles (Fig. 7B, 9 and S4 †) demonstrates a tightly packed distorted sphere containing rough surface, depicting heterogeneous polymerization of keto functionalized porphyrin across the FTO electrode surface. From AFM the roughness estimated by the root mean squared (RMS) was around 8 nm for the polymer lms. Also, the EDX mapping revealed uniform distribution of Ni, N, C and O in the polymer lms.

Interaction between CO 2 and polymer lm
To understand the potential as a catalyst, electrochemical interaction between the CO 2 and the polymer were investigated in the absence (N 2 ) and the presence of CO 2 . The measurement including nitrogen-saturated solution showed two distinct reduction peaks (Fig. 10). The rst, located at near À0.2 V is attributed to the formation of radical cation of the bpy linker and the second reduction peak observed at approximately À0.6 V is attributed to the second reduction of the bpy linker. The shape and position of the peaks are well in line with similar polymers described in the literature. 22,23,61 However, there is a minor additional reduction process observable at À1.05 V which is more clearly seen in the case of ZnOEPK. Aer saturation of the electrolyte with CO 2 , the reduction processes of the bpy linker take place roughly at the same potentials as earlier.
Some peak voltage variation is observed because of the possible activity of CO 2 on the redox active species in the lm. However, the most noticeable feature induced by CO 2 is the apparent activation of the À1.05 V reduction process. The presence of CO 2 induces one additional reversible redox process in the lm.
The reversibility and overall shape of the reduction peak, however, does not support the idea of electrocatalytic reduction of CO 2 by the metal centre of the porphyrin. Further investigation of reversible processes in the negative voltage range is difficult because the lm becomes increasingly labile at voltages more negative than À1.3 V. When proceeding beyond this point  the reverse oxidation scan does not produce reliable information anymore. In Fig. 10 the CO 2 induced current growth can be observed in the peak at À1.05 V. It is found that the addition of CO 2 in bipyridine containing material increases the reduction current of bipyridine 62 and some bipyridyl derivatives. 63,64 The Lewis basicity of the unsubstituted pyridyl or bipyridyl nitrogen has shown to support the formation of stable carbamates aer reduction to radical form in presence of CO 2 (Scheme 2). 62,63 CO 2 interaction with the polymer lm especially the activation of À1.05 V process could be attributed to intermediate carbamate formation in the monosubstituted bipyridines (Scheme 2). The exact structure of the polymer is under discussion but there are possibilities of having bipyridinium functionalities at the end of the chain as well as a side chain. The potential of the carbamate formation has been observed to shi with the bipyridine substitution. [62][63][64] Unsubstituted bipyridine has the highest negative formation potential for carbamate formation 62 while the propyl-substituted bipyridine has formation potential close to the values observed here. 63 The presence of electroactive bipyridyl substituents was previously detected by Schaming et al. form an additional reduction wave observed at 0.3 V more negative than rst bipyridine spacer reduction. 22 In our data, however, the same cannot be clearly detected. That might be due to different structure i.e. the keto functionalization of the porphyrin monomer. There are also previous papers concerning the redox properties of pyridinium and bipyridinium substituents. A porphyrin monomer substituted with four pyridiniums 65 or bipyridiniums 66 leads into four separate reduction waves at a considerably high negative voltage, which is an indication of interaction between the substituents. However, in a porphyrin pentamer having only viologen linkers and no side groups, all the rst and second reductions of the linkers take place at the same time at considerably lower voltages, 66 which is an indication of independent nature of the linkers.

Conclusion
We have demonstrated a controlled and reproducible electrosynthesis of a novel keto functionalized porphyrin and 4,4 0 -bpy copolymer. The spectroscopic data of the polymer lms resemble those of the monomer unit except for slight shis and broadening of bands in the polymer lm, indicating that porphyrin molecules are preserved and remain intact in the lm. The polymer lms exhibit similar topographical characteristics. Theoretical studies provide insight into the effect of the central metal atom and the keto functional group on the mode of polymerization. The nucleophilic addition of 4,4 0 -bpy in ZnOEPK occurs at 20 th meso position close to the keto group whereas in NiOEPK it is attaching at 10 th meso position opposite to the keto group. However, with the introduction of a second 4,4 0 -bpy unit coupling occurs perpendicular to the plane of porphyrin, opposite to the rst unit leading to polymers with linear orientation considering theoretical studies were performed for the initial two 4,4 0 -bpy units.
The polymer lms were investigated by cyclic voltammetry to understand the electrochemical interaction with CO 2 in ACN. The lm response to CO 2 in comparison to N 2 infers the immediate interaction of CO 2 . The interaction is seen as an activation process at À1.05 V and could be associated with the formation of intermediate carbamate. The interaction can also be utilized as an activation route towards CO 2 reduction or as controlled electrochemical trapping and release of CO 2 .

Conflicts of interest
There are no conicts to declare.