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. 2024 Nov 16;14:28300. doi: 10.1038/s41598-024-79563-0

Tuning structures and catalysis performance of two-dimensional covalent organic frameworks based on copper phthalocyanine building block and phenyl connector

Yuexing Zhang 1,✉, Junhao Peng 1,#, Guangsong Zhang 1,#, Xingguo Zhang 1, Shuai Zhang 1, Qing Li 1, Guanfeng Tian 1, Xiaoli Wang 1, Ping Wu 1, Xue-Li Chen 2,✉
PMCID: PMC11569124  PMID: 39550466

Abstract

Based on the experimentally reported stable and conductive two-dimensional covalent organic frameworks with copper phthalocyanine (CuPc) as building block and cyan substituted phenyl as connector (CuCOF-CN) as an electrocatalyst for CO2 reduction reaction (RR), first principle calculations were performed on CuCOF-CN and its analog with the CN being replaced by H (CuCOF). Comparatively studied on the crystal structures, electronic properties, and CO2RR performance of the two catalysts found that CuCOF has reduced crystal unit size, more positive charge on Cu and CuPc segments, smaller band gap, and lower reaction barrier for CO2 RR than CuCOF-CN. CuCOF is proposed to be good potential electrocatalyst with good environment friendliness. The substituent effect and structure-property-performance relationship would help for designing and fabricating new electrocatalysts.

Keywords: COF, CO2 reduction reaction, Copper phthalocyanine, Electrocatalyst, First principle calculation

Subject terms: Coordination chemistry, Materials chemistry, Physical chemistry, Theoretical chemistry

Introduction

Increasing energy crisis and global warming problems from carbon dioxide (CO2) emission have been caused by the utilization of non-renewable fossil fuels and mankind’s living requirements1. Reducing the CO2 concentration in the atmosphere therefore is highly desirable by transferring CO2  to other sustainable energies2–6. The thermodynamically stable molecule CO2 is highly inert and the electrochemical CO2 reduction (CO2RR) process is kinetically sluggish requiring very high potential (−1.90V vs.NHE)7,8 Many different kind of materials have been developed to seek highly efficient, selective and stable electrocatalyst that can reduce the activation energy barrier and expedite the kinetics of CO2RR9–11. Cheap transition metal copper-based catalysts had many advantages and were widely developed12–17.

Among the catalysts for CO2 RR, N4-macrocyclic complexes based molecular electrocatalysts including metal porphyrins, phthalocyanines and their related derivatives have emerged as the promising candidates18–22. To solve the problem of the relatively high over-potential due to the poor conductivity and sluggish electron transfer22, efforts have been tried to either coupling metal phthalocyanines or porphyrins with high conductive carbon nanomaterials or designing highly conjugated system20,22,23. A number of two-dimensional (2D) conductive covalent-organic frameworks (COFs) with extensive planar π-conjugation have been shown high electrical conductivity and developed for electrocatalysts24–27.

Series of metal phthalocyanine based 2D-COFs have been developed recently. Liao et al. reported a stable and conductive 2D-COF with copper phthalocyanine as building block and cyan substituted phenyl as connector (CuCOF-CN) in 202228. CuCOF-CN show good electrocatalytic performance for CO2 RR to acetate with a single-product Faradaic efficiency (FE) of 90.3(2)% at − 0.8 V (vs. RHE) and a current density of 12.5 mA cm−2 in 0.1 M KHCO3solution. They also performed theoretical calculation to explain why CuCOF-CN show different catalysis property from other Cu-based catalyst including copper porphyrin and single-atom copper catalyst. However, the synthesis of CuCOF-CN was time-costing and not economy (it was synthesized by a condensation reaction at 150 ℃ for 3 days under vacuum). The crystal structures of the CuCOF-CN was also not discussed. In addition, the phenyl connector contain two -CN group, which is extremely toxic substance and has great harm to the environment and to human beings. Jiang et al. developed a solvent-free, facile, and fast synthesis strategy for fabricating two fully conjugated Pc-based COFs under ionothermal synthesis for 8 h29. One of the COF reported by Jiang et al. show very similar structure as CuCOF-CN reported by Liao et al.28, with the center metal of CuCOF-CN being changed to zinc and the CN substituents replaced with H (ZnCOF). Despite that the zinc center was not good candidate for catalyst, these COFs show high-performance K+storage in potassium-ion batteries in terms of the large reversible capacities, excellent rate performance, and long-term cycling stability. Recently and during the preparation of the present work, Chen et al. further improved the synthesis strategy of 2D-COF and synthesized series metal (M = Fe, Co, Ni, Cu, Zn) phthalocyanine based COFs (MCOFs) by a facile trace-solvent-assisted one-pot self-condensation method30. Among these MCOFs, NiCOF show excellent sensing properties for various analytes including neurotransmitters, organic pollutants, and heavy metal ions, with high sensitivity and low detection limit of 0.53 to 25.66 nM. However, the catalysis performance of these MCOFs were not reported though CuCOF-CN show good CO2 RR performance. The influence of CN substitution on crystal structure, electronic properties, and catalytic performance were not clear. Clarifying these questions with a theoretical prospective work would therefore have great significance.

To further clarify the structures and rule of CN on the CO2 reduction performance, in the present work, we comparatively studied the crystal structures, electronic properties, and CO2 RR performance of CuCOF-CN and CuCOF through first principle calculations. The substituent effect and structure-property-performance relationship would help for designing and fabricating new electrocatalysts.

Computational methods

The initial crystal structures of CuCOF and CuCOF-CN were built with Device Studio program31. Device Studio program provides a number of functions for performing visualization, modeling and simulation. The first principle simulation were performed using DS-PAW software32integrated in Device Studio program. The PBE exchange-correlation functional33and D3BJ Van der Waals correction34 were chosen.

Results and discussion

Structures

Figure 1 shows the optimized crystal structures of CuCOF and CuCOF-CN. Their main structure parameters are tabulated in Table 1. Both CuCOF and CuCOF-CN are 2D planar layer structure without any deviation from the 2D plane. The crystals are both P4/mmm symmetry with a = b and α = β = γ = 90.0º. To avoid interactions between layers, the c-axis are set to 10.000 Å after involving the vacumm layer. The a and b values of CuCOF-CN is somewhat longer than those of CuCOF (20.197 vs. 20.192 Å), indicating that the substitution of H on the phenyl connector in CuCOF with electron-withdrawing CN group slightly enlarge the cell size of the COF crystals. More detail, the Cu-N bonds and the width of phenyl ring of phthalocyanine and the neighbour C4O2 ring all reduce, while the pyrrole ring of Pc and phenyl connector enlarge largely. In addition, CN substitution also induces the increase of height of phenyl connector. The different changes suggest that the electron density in the COF is redistributed due to the involving of electron-withdrawing CN groups in CuCOF-CN, which in turn would induce their different electrocatalytic performance.

Fig. 1.

Fig. 1

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Top (top) and side view (bottom) of the optimized crystal structures of CuCOF (left) and CuCOF-CN (right). (Red: O, gray: C, blue: N, white: H, coral: Cu).

Table 1.

Main structure parameters of the optimized crystal of CuCOF and CuCOF-CN (length in Å, angle in º).

Parameter CuCOF CuCOF-CN
Symmetry group P4/mmm P4/mmm
a 20.192 20.197
b 20.192 20.197
c 10.000 10.000
α 90.0 90.0
β 90.0 90.0
γ 90.0 90.0
Cu-N 1.963 1.961
Width(Py) 2.195 2.197
Width(Ph of Pc) 2.381 2.373
Width(C4O2) 2.356 2.351
Width(Ph connector) 2.403 2.432
Height(Ph connector) 2.799 2.815
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Bader charge

The introduction of electron-withdrawing CN groups would induce the redistribution of electrons. Table 2 shows the calculated Bader charge on each atom of CuCOF and CuCOF-CN as well as the change of Bader charge upon CN substitution. The H atoms of phenyl connector in CuCOF have Bader charge of 0.112 e, while the CN substituents in CuCOF-CN have Bader charge of −0.435 e. The Bader charge on C connected with H or CN changes from negative − 0.179 in CuCOF to positive 1.272 e in CuCOF-CN. The phenyl connector (in a or b direction) and its neighbour four O atoms in CuCOF totally contain Bader charge of −2.068 e. Since there are two connector in each crystal cell and the crystal is neutral, the remaining CuPc segment in CuCOF thus has Bader charge of 4.136 e. For CuCOF-CN, the Bader charge on each connector and CuPc segment increases to −2.452 and 4.904 e, respectively. These results indicate that electron transfer from CuPc segment to the connector and CN substitution on connector increases the electron transfer extent. Considering the Barder charge on Cu atom, Cu in CuCOF however has larger value than that in CuCOF-CN, 1.101 vs. 0.913 e. Large charge on Cu is advantage for CO2 RR reaction.

Table 2.

Calculated bader charge (in e) on each atom of CuCOF and CuCOF-CN (see Fig. 1 for atomic label).

CuCOF CuCOF-CN Change of bader charge
Atomic number Element Bader charge Atomic number Element Bader charge
1 C 0.59784 1 C −0.34203 −0.93987
2 C 0.59784 2 C −0.33591 −0.93375
3 C 0.3899 3 C −0.34191 −0.73181
4 C 0.38819 4 C −0.33602 −0.72421
5 C 0.38819 5 C 0.67422 0.28603
6 C 0.3899 6 C 0.67433 0.28443
7 C 0.59785 7 C 0.67422 0.07637
8 C 0.59785 8 C 0.67433 0.07648
9 C 0.00882 9 C 0.64228 0.63346
10 C 0.00882 10 C 0.64225 0.63343
11 C 0.00882 11 C 0.64223 0.63341
12 C 0.00882 12 C 0.64228 0.63346
13 C 0.00882 13 C 0.64227 0.63345
14 C 0.00882 14 C 0.64223 0.63341
15 C 0.00882 15 C 0.64223 0.63341
16 C 0.00882 16 C 0.64226 0.63344
17 C −0.10487 17 C −1.00724 −0.90237
18 C −0.10487 18 C −0.09079 0.01408
19 C −0.10487 19 C −0.09079 0.01408
20 C 0.10195 20 C −1.00724 −1.10919
21 C 0.10196 21 C −1.00724 −1.1092
22 C 0.10196 22 C −0.09079 −0.19275
23 C 0.10196 23 C −1.00724 −1.1092
24 C −0.10487 24 C −0.09079 0.01408
25 C 0.59277 25 C −0.38101 −0.97378
26 C 0.39143 26 C −0.38116 −0.77259
27 C 0.59277 27 C −0.38116 −0.97393
28 C 0.39143 28 C −0.38101 −0.77244
29 C 0.59278 29 C 0.58038 −0.0124
30 C 0.39144 30 C 0.58022 0.18878
31 C 0.39144 31 C 0.58037 0.18893
32 C 0.59278 32 C 0.58022 −0.01256
33 C 0.99682 33 C 1.37397 0.37715
34 C 0.99682 34 C 1.37433 0.37751
35 C 0.99682 35 C 1.37397 0.37715
36 C 0.99682 36 C 1.37397 0.37715
37 C 0.99682 37 C 1.37436 0.37754
38 C 0.99682 38 C 1.37436 0.37754
39 C 0.99682 39 C 1.374 0.37718
40 C 0.99682 40 C 1.37436 0.37754
41 C −0.01794 41 C 1.2717 1.28964
42 C −0.01794 42 C 1.2717 1.28964
43 C −0.01793 43 C 1.27171 1.28964
44 C −0.01794 44 C 1.2717 1.28964
45 Cu 1.1009 49 Cu 0.9131 −0.1878
46 H 0.070138 50 H 0.356329 0.286191
47 H 0.07014 51 H 0.356392 0.286252
48 H 0.070142 52 H 0.356217 0.286075
49 H 0.070137 53 H 0.356631 0.286494
50 H 0.070138 54 H 0.356769 0.286631
51 H 0.070143 55 H 0.356355 0.286212
52 H 0.070143 56 H 0.356657 0.286514
53 H 0.070141 57 H 0.356594 0.286453
58 N −1.13474 62 N −1.35308 −0.21834
59 N −1.13474 63 N −1.35302 −0.21828
60 −1.13474 64 N −1.35304 −0.2183
61 N −1.13474 65 N −1.35295 −0.21821
62 −1.23937 66  N −1.49621 −0.25684
63 N −1.23937 67 N −1.49621 −0.25684
64 −1.23937 68  N −1.49621 −0.25684
65 N −1.23937 69 N −1.49621 −0.25684
66 O −1.05733 70 O −1.19894 −0.14161
67 O −1.05733 71 O −1.19894 −0.14161
68 O −1.05733 72 O −1.19894 −0.14161
69 O −1.05733 73 O −1.19894 −0.14161
70 O −1.05733 74 O −1.19894 −0.14161
71 O −1.05733 75 O −1.19894 −0.14161
72 O −1.05733 76 O −1.19894 −0.14161
73 O −1.05733 77 O −1.19894 −0.14161
54 H 0.111745 45 C 0.7974
55 H 0.111748 46 C 0.7974
56 H 0.111757 47 C 0.7974
57 H 0.111753 48 C 0.7974
78 58 −1.2327
79 59  N −1.23243
80 60 N −1.23239
81 61 N −1.23252
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Band structure

Figure 2 shows the calculated projected band structure of CuCOF and CuCOF-CN between − 2 and 2 eV. The calculated Fermi energies of CuCOF and CuCOF-CN are − 3.04 and − 3.40 eV, respectively. The lower Fermi energy upon electron-withdrawing CN substitution is consistent with the common knowledge that electron-withdrawing groups would lower the orbital energy for molecule. Worth noting that when aligning the Fermi energy of both CuCOF and CuCOF-CN to 0 eV, the bands of CuCOF-CN appear above the corresponding bands of CuCOF. For CuCOF, the band around 0 eV is mainly composed from the p orbital of N atoms and d orbital of Cu. The band around − 0.5 eV of CuCOF including the p orbital of both C and O atoms, while that below it is mainly from C p orbital. Band around − 1.5 eV have large contribution from O p orbital in addition to major content from C p orbital. The bands around − 1.7 eV are composed from p orbital of both C and N. Similarly, the conduction band around 0.7 eV are also composed from p orbital of both C and N atoms. The shape and composition of band structures of CuCOF-CN are very similar to those of CuCOF. Some new bands appear around 1.6 eV in CuCOF-CN, which are composed of p orbitals of C and N and may due to the contribution of the CN substituents. The band gap from conducting band bottom to valence band top for CuCOF is 0.69 eV, much smaller than the gap for CuCOF-CN (0.88 eV), indicating that the conductivity of CuCOF is better than CuCOF-CN. Good conductivity is advantage for improving the electrocatalytic performance.

Fig. 2.

Fig. 2

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Projected band structure of CuCOF (red dot line) and CuCOF-CN (black line).

Density of states

The projected density of states (PDOS) of CuCOF and CuCOF-CN are shown in Fig. 3. In line with the assignments in Band structure section, PDOS peak around 0 eV are mainly contributed from the Cu d orbital and N p orbital, while the other peaks are attributed from the p orbital of C, N, and O atoms. The PDOS peaks of CuCOF are stronger than those of CuCOF-CN, indicating CN substitution reduces the electron density in the range of −2 to 2 eV. Large electron density on CuPc segment is advantage for CO2RR reaction.

Fig. 3.

Fig. 3

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Projected density of states of CuCOF (top) and CuCOF-CN (bottom).

CO2 RR

Figure 4 shows the free energy diagram of CO2 RR on CuCOF and CuCOF-CN surface at U = 0 V. The structures of the main intermediates are given in Fig. 5. For both catalysts, the formation of *COOH is the rate determine step, with reaction energy of 1.75 and 1.78 eV for CuCOF and CuCOF-CN, respectively. The smaller reaction energy for CuCOF than CuCOF-CN indicates that changing CN groups to H is advantage for CO2 RR. The desorption of CO need very small energy of only 0.13 and 0.14 eV for CuCOF and CuCOF-CN, respectively. The smaller reaction energy for CO desorption in CuCOF comparing to CuCOF-CN is also advantage for the whole CO2 RR process. The different free energy of the intermediates for CuCOF and CuCOF-CN could be explained from the main structure parameter of the intermediates. The Cu-C distance of *CO2 for CuCOF is shorter than that for CuCOF-CN (Fig. 5), well explaining the better stability of the former than the latter. Similarly, the longer Cu-C distance of *CO for CuCOF than CuCOF-CN reasons the less stable fact for the former than the latter. Though the Cu-C length of *COOH for CuCOF is slightly longer than that of CuCOF-CN, the more positive charge of Cu in the former than the latter render CuCOF-COOH more stable than CuCOF-CN-COOH.

Fig. 4.

Fig. 4

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The free energy diagram of CO2RR on CuCOF (black) and CuCOF-CN (red) at U = 0 V.

Fig. 5.

Fig. 5

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Optimized crystal structure of the intermediates (*CO2, left; *COOH, middle; *CO, right; * being the catalyst) during CO2 RR with CuCOF (top two lines for top and side views, respectively) and CuCOF-CN (bottom two lines) as catalyst. (Red: O, gray: C, blue: N, white: H, coral: Cu).

Conclusion

The crystal structures, electronic properties, and CO2RR performance of CuCOF and CuCOF-CN were comparatively studied through first principle calculations. CuCOF was found to have reduced crystal unit size, more positive charge on Cu, smaller band gap, and lower reaction barrier for CO2 RR, in comparing with CuCOF-CN. The good CO2 RR catalytic performance and lower poisonousness for CuCOF than CuCOF-CN renders it good potential electrocatalyst with good environment friendliness.

Acknowledgements

Financial supports from National Natural Science Foundation of China (52460023, 22478366), Natural Science Foundation of Shandong Province (2023TSGC0018), Natural Science Foundation of Jianxi Province (20224BAB213031), and Dezhou University (2023xjrc111) are acknowledged. This work was also supported by funding from Shandong Provincial Key Laboratory of Monocrystalline Silicon Semiconductor Materials and Technology (2023KFKT012). We gratefully acknowledge HZWTECH for providing computation facilities.

Author contributions

Yuexing Zhang conceived the idea, performed the DFT calculations and wrote the original draft. Junhao Peng, Guangsong Zhang, and Xingguo Zhang performed addition DFT calculations, analyzed calculation data, and revised the manuscript. Shuai Zhang, Qing Li, Guanfeng Tian, Xiaoli Wang, and Ping Wu discussed the results and revised the manuscript. Yuexing Zhang and Xue-Li Chen supervised and directed the projects and revised the manuscript. All authors reviewed the manuscript.

Data availability

Data availability The data of this work including the input and output calculation files are available upon requirement from the corresponding authors.

Declarations

Competing interests

The authors declare no competing interests.

Footnotes

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

These authors contributed equally to this work.

Contributor Information

Yuexing Zhang, Email: zhangyuexing@sdu.edu.cn.

Xue-Li Chen, Email: xueli089@foxmail.com.

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