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Tuning Electronic Structures of Covalent Co Porphyrin Polymers for Electrocatalytic CO 2 Reduction in Aqueous Solutions

2022; Chinese Chemical Society; Volume: 4; Issue: 9 Linguagem: Inglês

10.31635/ccschem.022.202101706

2096-5745

Yabo Wang, Xuepeng Zhang, Haitao Lei, Kai Guo, Gelun Xu, Lisi Xie, Xialiang Li, Wei Zhang, Ulf‐Peter Apfel, Rui Cao,

Electrocatalysts for Energy Conversion

Open AccessCCS ChemistryCOMMUNICATION5 Sep 2022Tuning Electronic Structures of Covalent Co Porphyrin Polymers for Electrocatalytic CO2 Reduction in Aqueous Solutions Yabo Wang†, Xue-Peng Zhang†, Haitao Lei, Kai Guo, Gelun Xu, Lisi Xie, Xialiang Li, Wei Zhang, Ulf-Peter Apfel and Rui Cao Yabo Wang† Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119 †Y. Wang and X.-P. Zhang contributed equally to this work.Google Scholar More articles by this author , Xue-Peng Zhang† Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119 †Y. Wang and X.-P. Zhang contributed equally to this work.Google Scholar More articles by this author , Haitao Lei Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119 Google Scholar More articles by this author , Kai Guo Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119 Google Scholar More articles by this author , Gelun Xu Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119 Google Scholar More articles by this author , Lisi Xie Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119 Google Scholar More articles by this author , Xialiang Li Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119 Google Scholar More articles by this author , Wei Zhang Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119 Google Scholar More articles by this author , Ulf-Peter Apfel Fakultät für Chemie und Biochemie, Ruhr-Universität Bochum, 44801 Bochum Fraunhofer UMSICHT, 46047 Oberhausen Google Scholar More articles by this author and Rui Cao *Corresponding author: E-mail Address: [email protected] Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119 Google Scholar More articles by this author https://doi.org/10.31635/ccschem.022.202101706 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Improving the selectivity of the electrocatalytic CO2 reduction reaction (CO2RR) over hydrogen evolution in aqueous solutions is required but challenging because the two reactions occur at close thermodynamic potentials and compete with each other. Herein, we report on the selective CO2RR in aqueous solutions utilizing covalent Co porphyrin polymers with fine-tuned electronic structures. Co[email protected], [email protected], and [email protected], synthesized by Hay-coupling Co porphyrin monomers on carbon nanotubes, showed higher activity and durability than the respective monomers for CO2RR. By tuning the electronic structures, the CO2RR selectivity of [email protected] (FECO > 95%) and [email protected] (FECO > 80%) was significantly improved compared with [email protected] (FECO < 20%). Remarkably, [email protected] catalyzed CO2RR with FECO > 95% in aqueous solutions in a wide overpotential range of 460–760 mV. Theoretical studies suggest that the electron-rich CoI centers of CoP and CoP-Ph can favorably bind CO2, leading to improved CO2RR selectivity. Download figure Download PowerPoint Introduction The electrocatalytic CO2 reduction reaction (CO2RR) using CO2 as sustainable feedstock is an attractive choice for making fuels and value-added chemicals.1–3 Protons are required for the C–O bond cleavage.4,5 Consequently, CO2RR in aqueous solutions is desirable since water is abundant and green and can provide sufficient protons.6,7 However, electrocatalytic reduction of water itself to hydrogen [E° = 0 V versus reversible hydrogen electrode (RHE)] and CO2RR (E° = –0.11 V versus RHE for the CO2-to-CO conversion) occur at very close thermodynamic potentials, and thus they compete with each other.8,9 More seriously, the hydrogen evolution reaction (HER) is often kinetically more favored, resulting in unsatisfactory CO2RR selectivity in aqueous solutions.10–15 Several strategies have been reported to improve the selectivity of CO2RR over HER in aqueous solutions, including the use of strong basic solutions,16,17 the introduction of cationic surfactants on electrode surfaces,18,19 the employment of gas diffusion electrodes,20,21 and the utilization of supercritical CO2.22,23 Still, designing and developing electrocatalysts, whose active sites have intrinsically high selectivity for CO2RR, and understanding the underlying mechanisms are of fundamental significance and are the subject of the research in this paper. Molecular catalysts have clear and controllable structures and thus have benefits for the study of structure-function relationships in catalysis.24,25 A variety of metal complexes of polypyridines,26–28 cyclams,29–31 porphyrins,32–38 and corroles39,40 have been identified as efficient CO2RR electrocatalysts in nonaqueous solutions. By studying these molecular catalysts, knowledge of improving catalytic performance has been gained, including tuning electronic structures,41,42 installing proton relays,43,44 and introducing hydrogen-bonding and electrostatic interactions.34,45–48 However, due to their limited water solubility and poor electronic conductivity, molecular catalysts have to be loaded on electrode materials for electrocatalysis in aqueous solutions.7,49 Because of the weak interactions between catalyst molecules and electrodes, they generally show low electrocatalytic activity and are easily exfoliated under violent gas evolution conditions.50,51 Strategies to improve the activity and durability of molecular catalysts on electrode materials have been reported, such as grafting catalyst molecules on materials via strong π–π interactions or covalent bonds,50,52,53 and directly growing frameworks of catalyst molecules on supports.54 Particularly, using electrode materials as templates, frameworks grown on electrode surfaces have displayed improved activity and durability compared with respective molecules simply loaded on electrodes.55,56 However, unlike molecular catalysts, whose structures can be well controlled, the active site structures of frameworks and derived heterogenous materials are difficult to be systematically modified.57 Therefore, compared with simple molecular catalysts, further tuning the CO2RR performance of frameworks is more challenging from the standpoint of molecular design and synthesis. Herein, we report on exploring Co porphyrin polymers with fine-tuned electronic structures for the electrocatalytic CO2RR in aqueous solutions. Metal porphyrins are shown to be active and selective for the CO2-to-CO conversion in nonaqueous solutions, but they usually display relatively poor selectivity for CO2RR in aqueous media due to the competing HER. Three polymers were grown on carbon nanotubes (CNTs), and the resulting catalysts [email protected], [email protected], and [email protected] were more active and durable than their corresponding monomers for CO2RR. More importantly, by tuning the electronic structures of these polymers with different porphyrin meso-substituents, [email protected] and [email protected] showed an improved selectivity for CO2RR compared with [email protected]. Theoretical studies suggest that the electron-rich CoI centers of CoP and CoP-Ph are more favorable than the electron-deficient CoI centers of CoP-F to bind and activate CO2. This work presents an example of tuning the electronic structures of covalent porphyrin polymers to improve CO2RR selectivity in aqueous solutions. Results and Discussion Covalent Co porphyrin polymers were synthesized according to reported methods.55,56 Co porphyrin monomers, CoP, CoP-Ph, and CoP-F, were synthesized (Figure 1a, details of synthesis and characterization are described in the Supporting Information). The triisopropylsilyl-protected CoP ( Supporting Information Scheme S1, Figures S1–S4, and Table S1) was structurally characterized, showing that the Co ion was located at the center of the porphyrin ring with a four-coordinated square-planar geometry ( Supporting Information Figure S5). Bond valance sum and charge balance calculations suggested a CoII electronic structure. By Hay-coupling the alkyne groups of Co porphyrins with CNTs, covalent porphyrin polymers were grown on the surface of CNTs, giving [email protected], [email protected], and [email protected], respectively (Figure 1b). Figure 1 | (a) Molecular structures of Co porphyrin monomers, CoP, CoP-Ph, and CoP-F. TBAF, tetrabutylammonium fluoride; TIPS, triisopropylsilyl; TMS, trimethylsilyl. (b) Schematic diagram showing the synthesis of [email protected], [email protected], and [email protected] with CNT templates. Download figure Download PowerPoint The successful synthesis of covalent Co porphyrin polymers on CNTs was confirmed. High-resolution transmission electron microscopy (HRTEM) imaging of [email protected] showed the formation of wrapped amorphous polymers, with a thickness of 3–7 nm, on the surface of CNTs (Figure 2a). Scanning electron microscopy (SEM) analysis excluded the presence of unsupported polymers in the bulk sample of [email protected] ( Supporting Information Figure S6). X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray (EDX) mapping images showed the presence of Co and N (Figures 2b–2d). In the Co 2p region of XPS, the two peaks at 781.5 and 796.5 eV were attributed to the Co 2p3/2 and Co 2p1/2,50 respectively (Figure 2c). These values are consistent with the CoII oxidation state that we determined from crystallographic studies, indicating that the Co coordination and electronic structures remained unchanged during polymerization. In the N 1s spectrum, the peak at 398.3 eV was attributed to porphyrin N atoms (Figure 2d), while the peak at 399.7 eV was due to residual N-methylpyrrolidone, which was used as the solvent in the polymerization.55 The coupling between alkyne groups of CoP was supported by infrared studies. As shown in Figure 2e, the C≡C (2100 cm−1) and C≡C–H (3300 cm−1) peaks of CoP disappeared in [email protected], while all other porphyrin-related peaks remained unchanged. Note that the C≡C resonance peak is known to significantly decrease in intensity upon coupling.58,59 The intact Co porphyrin units in [email protected] were further confirmed by UV–vis spectroscopy, which displayed the characteristic Soret and Q bands of CoP ( Supporting Information Figure S7). All these results confirmed the formation of covalent CoP polymers on CNTs. Similar results were obtained for [email protected] ( Supporting Information Figures S8 and S9) and [email protected] ( Supporting Information Figures S10 and S11). Figure 2 | (a) HRTEM image and (b) EDX mapping of C, N, and Co for [email protected]. XPS analysis of [email protected] in the (c) Co 2p and (d) N 1s region. (e) Infrared spectra of CNT, [email protected], and CoP. Download figure Download PowerPoint Electrochemical measurements were then performed to study the redox properties of the generated covalent Co porphyrin polymers. The cyclic voltammogram (CV) of [email protected], loaded on a glassy carbon (GC) electrode, displayed a redox couple at E1/2 = −1.22 V versus ferrocene in dimethylformamide (DMF) ( Supporting Information Figure S12). Importantly, the CV of CoP, when dissolved in DMF and using a freshly cleaned GC electrode, displayed the same redox couple at E1/2 = −1.21 V versus ferrocene ( Supporting Information Figure S13 and Table S2). This redox event was assigned to the CoII/I couple.36 This result strongly supports the maintenance of the CoP structure in the resulting polymer. The CoII/I redox couple of [email protected] (E1/2 = −1.27 V vs ferrocene) and [email protected] (E1/2 = −1.12 V vs ferrocene), when loaded on GC electrodes for CV measurements in DMF, was also identical to that of the corresponding monomer, CoP-Ph (E1/2 = −1.27 V vs ferrocene) and CoP-F (E1/2 = −1.07 V vs ferrocene), respectively ( Supporting Information Figures S12 and S13 and Table S2). Notably, compared with CoP and CoP-Ph, the CoII/I redox couple of CoP-F anodically shifted by >140 mV. This large anodic shift was consistent with the strong electron-withdrawing feature of the fluorinated meso-phenyl substituents of CoP-F and thus shows the crucial effect of these meso-substituents on tuning the electronic structure of metal porphyrins. Electrocatalytic CO2RR was then measured in CO2-saturated 0.5 M KHCO3 aqueous solutions (pH 7.3) using a gas-tight H-type electrochemical cell (Figure 3a). In aqueous solution studies, all reported potentials are referenced to RHE. The linear sweep voltammogram (LSV) of [email protected] showed pronounced catalytic currents (Figure 3b). As a control, we loaded CoP monomers on CNTs. This CoP/CNT was much less efficient than [email protected] for CO2RR under the same conditions ( Supporting Information Figure S14). Similarly, [email protected] and [email protected] were also more efficient than their corresponding monomers ( Supporting Information Figures S15 and S16). These results indicate that covalent Co porphyrin polymers are more favorable for CO2RR than Co porphyrin monomers. Figure 3 | (a) Schematic illustration of the H-type electrochemical cell for CO2RR. (b) LSVs of [email protected], [email protected], and [email protected] in CO2-saturated 0.5 M KHCO3 solutions (pH 7.3) at a scan rate of 5 mV/s without iR compensation. (c) FEs obtained at potentials from −0.47 to −0.87 V. (d) Partial current densities for the CO production. (e) Stability test of [email protected] by electrolysis at −0.57 V with FEs measured every 10 h. Download figure Download PowerPoint Compared with [email protected], the LSVs of [email protected] and [email protected] displayed smaller and cathodically shifted catalytic currents (Figure 3b). This result thus suggests that the electronic structure of Co porphyrin polymers plays a crucial role in tuning the CO2RR activity. Next, we performed electrolysis to determine the faradic efficiency of the CO production (FECO). With an applied potential of −0.47 V, the FECO of [email protected] was 83.9%, and the FEH2 was 9.8% (Figure 3c and Supporting Information Table S3). Notably, high FECO (>95%) was obtained with [email protected] in a wide potential range of −0.57 to −0.87 V (overpotential range 460–760 mV). This performance is remarkable for the CO2-to-CO conversion utilizing Co-based electrocatalysts ( Supporting Information Table S4). Similarly, [email protected] also displayed fairly high selectivity for CO2RR with FECO close to 80% (Figure 3c). However, unlike [email protected] and [email protected], the electron-deficient [email protected] displayed very low FECO ( 80%) (Figure 3c). Note that no other gas and/or liquid products were found in the electrolysis with all three polymers. The electrolysis current densities of these polymers under different potentials are shown in Supporting Information Figures S17–S19. Importantly, the same selectivity trend was observed by using Co porphyrin monomers simply adsorbed on CNTs, showing that CoP/CNT (FECO > 85%) and CoP-Ph/CNT (FECO > 73%) are much more selective than CoP-F/CNT (FECO < 12%) for electrocatalytic CO2-to-CO conversion during electrolysis at −0.57 V ( Supporting Information Figure S20 and Table S5). These results suggest that in addition to their activity, the selectivity of Co porphyrin polymers can likewise be greatly improved by tuning electronic structures. Because of the larger catalytic current and higher FECO value, the CO partial current density (jCO) of [email protected] far surpassed that of [email protected] and [email protected] (Figure 3d). The turnover number (TON) for the CO2-to-CO conversion with [email protected] was determined to be 7806 in a 1-h electrolysis at −0.57 V, giving a turnover frequency (TOF) of 2.2 s−1 (calculation details are described in the Supporting Information). These values are larger than those of [email protected] (TON = 3351, TOF = 0.9 s−1) and [email protected] (TON = 369, TOF = 0.1 s−1). In addition, stability tests of [email protected] showed its long-term durability and selectivity for electrocatalytic CO2-to-CO conversion. No obvious decay of current and FECO was observed during 100-h electrolysis at −0.57 V ( Supporting Information Figure S17 and Figure 3e). In contrast, electrolysis using CoP/CNT showed rapid current loss in 95%) and [email protected] (FECO > 80%) much more selective than [email protected] (FECO < 20%) for the CO2-to-CO conversion. As a result, this work presents a strategy to fine tune the electronic structure of covalent porphyrin polymers and highlights the benefits of using rationally designed molecular electrocatalysts. Supporting Information Supporting Information is available and includes additional experimental details, synthetic procedures, characterization data (1H NMR spectra, high-resolution mass spectra, SEM images, UV–vis spectra, and infrared spectra), electrochemical measurement data, performance comparison of Co porphyrin polymers with reported Co-based electrocatalysts, and crystallographic data for TIPS-protected CoP, as well as theoretical calculations. Conflict of Interest The authors declare no conflicts of interests. Funding Information We are grateful for financial support from the National Natural Science Foundation of China (nos. 21773146 and 22003036), the Fok Ying-Tong Education Foundation for Outstanding Young Teachers in University, the Fundamental Research Funds for the Central Universities, and the Research Funds of Shaanxi Normal University (nos. 2020CBLZ005, GK202103045, and GK202103033). U.-P.A. thanks the Fraunhofer Internal Programs for their support under Grant No. Attract 097-602175 and the DFG under Germany’s Excellence Strategy—EXC-2033—Projektnummer 390677874 “RESOLV”. References 1. Hepburn C.; Adlen E.; Beddington J.; Carter E. A.; Fuss S.; Mac Dowell N.; Minx J. C.; Smith P.; Williams C. K.The Technological and Economic Prospects for CO2 Utilization and Removal.Nature2019, 575, 87–97. Google Scholar 2. Wang G.; Chen J.; Ding Y.; Cai P.; Yi L.; Li Y.; Tu C.; Hou Y.; Wen Z.; Dai L.Electrocatalysis for CO2 Conversion: From Fundamentals to Value-Added Products.Chem. Soc. 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