Phthalocyanine-based bimetallic atom single-layer structure model, construction method and application
By embedding metal atoms into a phthalocyanine-based monolayer supercell to construct a phthalocyanine-based bimetallic atom monolayer structure model, the problems of low activity and insufficient stability of electrochemical CO2 reduction catalysts were solved, achieving efficient and selective CO2 reduction to C1 products.
Patent Information
- Application Number
- CN202511019690.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-23
- Publication Date
- 2026-01-16
AI Technical Summary
Existing electrochemical CO2 reduction catalysts suffer from low catalytic activity, poor selectivity, high overpotential, and dependence on noble metals, and diatomic catalysts lack stability.
A phthalocyanine-based bimetallic atom monolayer structure model was constructed. By embedding metal atoms in a two-dimensional phthalocyanine-based monolayer supercell, a structural model with good stability was screened using energy calculations and molecular dynamics simulations. The catalytic selectivity was optimized by Gibbs free energy calculations to suppress the hydrogen evolution reaction and improve CO2 conversion efficiency.
It achieves high stability, low limiting potential and high selectivity in reducing CO2 to C1 products, and has good prospects for industrial application.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of electrocatalysis technology, specifically relating to the phthalocyanine bimetallic atomic monolayer structure model, construction method, and application. Background Technology
[0002] Electrochemical reduction of CO2 has become an energy-saving and environmentally friendly alternative to thermocatalysis and photocatalysis, enabling the direct production of value-added chemicals. However, catalysts for electrochemical CO2 reduction still suffer from problems such as low catalytic activity, poor selectivity, high overpotential, and dependence on precious metals. Therefore, developing efficient and low-cost catalysts is crucial.
[0003] In recent years, people have been dedicated to exploring new catalysts to improve the efficiency and selectivity of CO2RR. Due to the fact that diatomic catalysts (DACs) introduce additional functional sites, their catalytic performance can be precisely tuned to meet the requirements of complex reactions, which has attracted increasing attention.
[0004] Shang et al. used density functional theory (DFT) calculations to study the application of C3N-supported monometallic (M / C3N) and bimetallic (M1M2 / C3N) catalysts in the electrochemical nitrogen reduction reaction (NRR). Their results showed that the synergistic effect of the two atoms in M1M2 / C3N generated more flexible adsorption sites for intermediates, decoupling the adsorption free energy of key intermediates and breaking the inherent scaling relation limitations of the limiting potential. Notably, the optimal limiting potential of M1M2 / C3N increased from -0.63 V to -0.20 V. However, existing biatomic catalysts lack stability; metal atoms are prone to cohesion or migration, and their electronic structure regulation mechanism remains unclear. Summary of the Invention
[0005] In view of this, some embodiments disclose a phthalocyanine-based bimetallic atom monolayer structure model, which includes two-dimensional periodic coordination structural units, represented as TM1TM2@Pc; wherein TM1 and TM2 are any one of the metal atoms Cr, Mn, Fe, Co, and Ni, respectively, Pc is a phthalocyanine-based monolayer supercell, and TM1 and TM2 are anchored to the macrocycle center site and adjacent bridge sites of the phthalocyanine-based monolayer supercell in an intercalation coordination manner.
[0006] Furthermore, some embodiments disclose a phthalocyanine-based bimetallic atomic monolayer structure model, where the lattice constant of the phthalocyanine-based monolayer supercell is... A phthalocyanine monolayer supercell contains twelve nitrogen atoms, thirty carbon atoms, and eight hydrogen atoms, wherein the distance between a carbon atom and its adjacent nitrogen atom is approximately [missing information]. The distance between adjacent carbons is approximately
[0007] On the other hand, some embodiments disclose a method for constructing a phthalocyanine-based bimetallic atomic monolayer structure model, including the following steps:
[0008] S1. Construct a two-dimensional extended phthalocyanine-based bimetallic atom monolayer structure model and perform optimization calculations;
[0009] S2. Based on binding energy and molecular dynamics simulations, two-dimensional extended phthalocyanine bimetallic atomic monolayer structure models that meet the structural stability requirements are screened as candidate structure models.
[0010] S3. Based on the free energy barrier of CO2 adsorption and activation and CO2 reduction reaction, the candidate structural model with the best CO2 reduction catalytic activity is selected from the candidate structural models as the optimal structural model.
[0011] S4. Using Gibbs free energy calculations, the active sites of the hydrogen evolution reaction in the optimal structural model are revealed, and the trend of the competitive reaction difference between CO2 reduction and hydrogen evolution reaction is established.
[0012] S5. By applying an external potential, the catalytic selectivity parameters of the optimal structural model are optimized to obtain the optimal structural model that inhibits the hydrogen evolution reaction and improves the CO2 conversion efficiency as the phthalocyanine diatomic monolayer structure model.
[0013] Furthermore, in the method for constructing the phthalocyanine-based bimetallic atomic monolayer structure model disclosed in some embodiments, the binding energy in step S2 is calculated by the following formula:
[0014]
[0015] in, For binding energy, E Pc E TM1TM2@Pc E represents the total energy of a single Pc ring and the coordination structure unit TM1TM2@Pc, respectively. TM1-sing atom E TM2-single atom These represent the total energy of metal atoms TM1 and TM2, respectively.
[0016] In some embodiments, the method for constructing a phthalocyanine-based bimetallic atomic monolayer structure model includes step S2, in which a 10ps molecular dynamics simulation at 500K is performed to evaluate the thermal stability of the two-dimensional extended phthalocyanine-based bimetallic atomic monolayer structure model.
[0017] In some embodiments, the method for constructing a phthalocyanine-based bimetallic atom monolayer structure model includes step S3, in which the CO2 reduction reaction is the reduction of CO2 to C1 products under electrochemical conditions, wherein the C1 products include one or more of CO, HCOOH, CH3OH and CH4.
[0018] In the method for constructing the phthalocyanine-based bimetallic atom monolayer structure model disclosed in some embodiments, in step S5, when a potential of -0.2V (vs RHE) is applied, the selectivity of CrFe@Pc for reducing CO2 to HCOOH, CH3OH and CH4 is stronger than that for the hydrogen evolution reaction.
[0019] In the method for constructing the phthalocyanine-based bimetallic atomic monolayer structure model disclosed in some embodiments, in step S5, CrCo@Pc exhibits the best selectivity for reducing CO2 to HCOOH under the same operating potential.
[0020] On the other hand, some embodiments disclose the application of the phthalocyanine-based bimetallic atomic monolayer structure model, which is used as a CO2 reduction electrocatalyst.
[0021] Furthermore, the application of the phthalocyanine-based bimetallic atom monolayer structure model disclosed in some embodiments enables CO2 to be reduced to C1 products under the catalytic action of CO2 reduction electrocatalysts. The C1 products include one or more of CO, HCOOH, CH3OH, and CH4.
[0022] The method for constructing the phthalocyanine-based bimetallic atom monolayer structure model disclosed in this invention involves embedding and fixing bimetallic atoms on a two-dimensional extended phthalocyanine monolayer to obtain the phthalocyanine-based bimetallic atom monolayer structure model. Based on its structural stability and thermal stability, this model can be used as a CO2 reduction electrocatalyst to efficiently electroreduc CO2 to C1 products. It has the advantages of high stability, low limiting potential and high selectivity, and has good application prospects in the industrialization of CO2 reduction electrocatalysts. Attached Figure Description
[0023] Figure 1 , one Schematic diagram of the two-dimensional extended phthalocyanine-based bimetallic monolayer structure model disclosed in these embodiments;
[0024] Figure 2 , one A schematic diagram of a coordination structure unit disclosed in these embodiments;
[0025] Figure 3 , one These embodiments disclose a schematic diagram showing the change of total energy of 500K simulated TM1TM2@Pc over time;
[0026] Figure 4 , one Schematic diagram of CO2 adsorption and charge density difference on the CrTM2@Pc configuration disclosed in these embodiments;
[0027] Figure 5 , oneThe free energy change diagrams for the CO2 reduction reaction to produce CO and HCOOH disclosed in these embodiments;
[0028] Figure 6 , one The free energy change diagrams for CO2 reduction to CH3OH and CH4 disclosed in these embodiments;
[0029] Figure 7 , one The limiting potential diagrams for the reduction of CO2 to CO, HCOOH, CH3OH and CH4 disclosed in these embodiments. Detailed Implementation
[0030] The term "embodiment" used herein, as an example, is not necessarily to be construed as superior to or better than other embodiments. Performance testing in these embodiments of the invention, unless otherwise specified, employs conventional testing methods in the art. It should be understood that the terminology used in these embodiments is merely for describing particular implementations and is not intended to limit the scope of the disclosure of these embodiments.
[0031] Unless otherwise stated, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments of this invention pertain; other experimental methods and technical means not specifically noted in the embodiments of this invention refer to experimental methods and technical means commonly used by one of ordinary skill in the art.
[0032] The terms “basic” and “approximately” used in this document are to describe small fluctuations. For example, they can mean less than or equal to ±5%, such as less than or equal to ±2%, such as less than or equal to ±1%, such as less than or equal to ±0.5%, such as less than or equal to ±0.2%, such as less than or equal to ±0.1%, such as less than or equal to ±0.05%. Numerical data presented or expressed in range format in this document are used for convenience and brevity only, and should therefore be flexibly interpreted to include not only the explicitly listed values that define the range, but also all independent values or subranges contained within that range. For example, a numerical range of “1–5%” should be interpreted to include not only the explicitly listed values from 1% to 5%, but also the independent values and subranges within the indicated range. Thus, this numerical range includes independent values such as 2%, 3.5%, and 4%, and subranges such as 1%–3%, 2%–4%, and 3%–5%, etc. This principle also applies to ranges that list only one value. Furthermore, this interpretation applies regardless of the width of the range or the characteristics described.
[0033] In this document, including in the claims, conjunctions such as "comprising," "including," "with," "having," "containing," "involving," and "accommodating" are understood to be open-ended, meaning "including but not limited to." Only the conjunctions "consisting of" and "composed of" are closed conjunctions.
[0034] To better illustrate the content of this invention, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that the invention can be practiced even without certain specific details. In the embodiments, some methods, means, instruments, and devices well-known to those skilled in the art are not described in detail, in order to highlight the main points of the invention.
[0035] Without conflict, the technical features disclosed in the embodiments of the present invention can be combined arbitrarily, and the resulting technical solution belongs to the content disclosed in the embodiments of the present invention.
[0036] The technical details are further illustrated below with reference to the embodiments.
[0037] Some embodiments disclose a phthalocyanine-based bimetallic atom monolayer structure model, which includes a two-dimensional periodic coordination unit, denoted as TM1TM2@Pc; wherein TM1 and TM2 are any one of the metal atoms Cr, Mn, Fe, Co, and Ni, respectively, and Pc is a phthalocyanine-based monolayer supercell. TM1 and TM2 are anchored to the macrocycle center site and adjacent bridge sites of the phthalocyanine-based monolayer supercell in an intercalation coordination manner.
[0038] Some embodiments disclose a phthalocyanine-based bimetallic atomic monolayer structure model, where the lattice constant of the phthalocyanine-based monolayer supercell is... A phthalocyanine monolayer supercell contains twelve nitrogen atoms, eight carbon atoms, and thirty hydrogen atoms, wherein the distance between a carbon atom and its adjacent nitrogen atom is approximately [missing information]. The distance between adjacent carbons is approximately
[0039] Some embodiments disclose a method for constructing a phthalocyanine-based bimetallic atomic monolayer structure model, including the following steps:
[0040] S1. Construct a two-dimensional extended phthalocyanine-based bimetallic atom monolayer structure model and perform optimization calculations;
[0041] S2. Based on binding energy and molecular dynamics simulations, two-dimensional extended phthalocyanine bimetallic atomic monolayer structure models that meet the structural stability requirements are screened as candidate structure models.
[0042] S3. Based on the free energy barrier of CO2 adsorption and activation and CO2 reduction reaction, the candidate structural model with the best CO2 reduction catalytic activity is selected from the candidate structural models as the optimal structural model.
[0043] S4. Using Gibbs free energy calculations, the active sites of the hydrogen evolution reaction in the optimal structural model are revealed, and the trend of the competitive reaction difference between CO2 reduction and hydrogen evolution reaction is established.
[0044] S5. By applying an external potential, the catalytic selectivity parameters of the optimal structural model are optimized to obtain the optimal structural model that inhibits the hydrogen evolution reaction and improves the CO2 conversion efficiency as the phthalocyanine diatomic monolayer structure model.
[0045] In the method for constructing the phthalocyanine-based bimetallic atomic monolayer structure model disclosed in some embodiments, the binding energy in step S2 is calculated by the following formula:
[0046]
[0047] in, For binding energy, E Pc E TM1TM2@Pc E represents the total energy of a single Pc ring and the TM1TM2@Pc coordination structure unit, respectively. TM1-sing atom E TM2-single atom These represent the total energy of metal atoms TM1 and TM2, respectively.
[0048] In some embodiments, the method for constructing a phthalocyanine-based bimetallic atomic monolayer structure model includes step S2, in which a 10ps molecular dynamics simulation at 500K is performed to evaluate the thermal stability of the two-dimensional extended phthalocyanine-based bimetallic atomic monolayer structure model.
[0049] In some embodiments, the method for constructing a phthalocyanine-based bimetallic atom monolayer structure model includes step S3, in which the CO2 reduction reaction is the reduction of CO2 to C1 products under electrochemical conditions, wherein the C1 products include one or more of CO, HCOOH, CH3OH and CH4.
[0050] In the method for constructing the phthalocyanine-based bimetallic atom monolayer structure model disclosed in some embodiments, in step S5, when a potential of -0.2V vs RHE is applied, the selectivity of CrFe@Pc for reducing CO2 to HCOOH, CH3OH and CH4 is stronger than that for the hydrogen evolution reaction.
[0051] In the method for constructing the phthalocyanine-based bimetallic atomic monolayer structure model disclosed in some embodiments, in step S5, CrCo@Pc exhibits the best selectivity for reducing CO2 to HCOOH under the same operating potential.
[0052] The application of the phthalocyanine-based bimetallic atomic monolayer structure model disclosed in some embodiments, which is used as a CO2 reduction electrocatalyst.
[0053] The application of the phthalocyanine-based bimetallic atom monolayer structure model disclosed in some embodiments enables the reduction of CO2 to C1 products under the catalytic action of CO2 reduction electrocatalysts. The C1 products include one or more of CO, HCOOH, CH3OH, and CH4.
[0054] In some embodiments, the method for constructing the phthalocyanine-based bimetallic atomic monolayer structure model includes the following steps:
[0055] (1) Construct a two-dimensional extended phthalocyanine-based bimetallic atom monolayer structure model. The monolayer structure model contains periodic coordination structure units, each of which includes two metal atoms. Perform geometric optimization calculations on the structure model.
[0056] Typically, the structural model contains two-dimensional periodic coordination structural units, which are represented as TM1TM2@Pc; where TM1 and TM2 are any one of the metal atoms Cr, Mn, Fe, Co, and Ni, respectively, and Pc is a phthalocyanine monolayer supercell. TM1 and TM2 are anchored to the macrocycle center site and adjacent bridge sites of the phthalocyanine monolayer supercell in an intercalation coordination manner.
[0057] As an optional embodiment, the coordination unit is an extended phthalocyanine monolayer supercell, which comprises a two-dimensional periodic structure of fifty atoms, including twelve nitrogen atoms, eight carbon atoms, and thirty hydrogen atoms, with a supercell lattice constant of approximately [value missing]. The distance between carbon and its neighboring nitrogen atom is approximately The distance between adjacent carbon atoms is approximately Figure 1 This is a schematic diagram of a two-dimensional extended phthalocyanine-based bimetallic monolayer structure model. Figure 2 for Figure 1 A schematic diagram of a coordination structure unit in a structural model; Figure 2 The left image is a top view, and the right image is a side view; Figure 2 The model shows that in the phthalocyanine-based bimetallic atom monolayer structure TM1TM2@Pc, Pc is a phthalocyanine macrocycle, and TM1 and TM2 are two independent metal atoms. The bimetallic atoms are anchored to the central site and adjacent bridge sites of the phthalocyanine macrocycle in an intercalation coordination manner. The bimetallic atoms TM1 and TM2 are independently selected from Cr, Mn, Fe, Co, and Ni, respectively.
[0058] (2) Based on binding energy calculation and molecular dynamics simulation, models with structural stability were selected from the two-dimensional extended phthalocyanine bimetallic atomic monolayer structure model as candidate structure models.
[0059] As an optional embodiment, the structural stability of the phthalocyanine diatomic monolayer configuration is evaluated using the binding energy, which is calculated by the following formula:
[0060]
[0061] Where ΔE is the binding energy, E Pc E TM1TM2@Pc E represents the total energy of a single Pc ring and the TM1TM2@Pc coordination structure unit, respectively. TM1-sing atom E TM2-single atom These represent the total energy of metal atoms TM1 and TM2, respectively; the bimetallic atom combinations can be CrCr, CrMn, CrFe, CrCo, MnMn, MnFe, MnFe, MnCo, MnNi, FeFe, FeCo, FeNi, CoCo, CoNi, NiNi;
[0062] Generally, if the calculated binding energy is positive, it indicates that TM1TM2@Pc is thermodynamically stable. As shown in Table 1, the calculated binding energy E of the phthalocyanine diatomic monolayer is... b The results show that bimetallic atoms can be stably embedded in a two-dimensional extended phthalocyanine monolayer structure.
[0063] Table 1. Calculation results of binding energies for different phthalocyanine diatomic monolayer configurations.
[0064] Dimers <![CDATA[E b (eV)]]> CrCr@Pc 16.15 CrMn@Pc 16.25 CrFe@Pc 17.39 CrCo@Pc 17.68 CrNi@Pc 16.97 MnMn@Pc 16.26 MnFe@Pc 17.44 MnCo@Pc 17.61 MnNi@Pc 16.89 FeFe@Pc 18.19 FeCo@Pc 18.29 FeNi@Pc 19.68 CoCo@Pc 18.43 CoNi@Pc 17.72 NiNi@Pc 17.62
[0065] As an optional embodiment, molecular dynamics simulations are used to evaluate the thermal stability of the phthalocyanine-based bimetallic atomic monolayer configuration under certain environmental conditions. For example... Figure 3 The figure shows the change of total energy of TM1TM2@Pc over time under 500K conditions simulated in AIMD (ab initio molecular dynamics). It can be seen that the energy of different TM1TM2@Pc systems exhibits a near-equilibrium periodic fluctuation, indicating that they have good thermal stability.
[0066] Generally, the efficiency of phthalocyanine-based bimetallic monolayer catalysts in the electrocatalytic reduction of CO2 mainly depends on the adsorption of CO2 and initial activation of the catalyst, which directly relates to the catalyst's performance. For example... Figure 4 As shown, CrTM2@Pc (TM2 represents Cr, Mn, Fe, and Co) exhibits a clear linear deflection curve after CO2 adsorption, with a bond angle range of 125.85° and a carbon-metal distance of [missing information]. These structural changes indicate that the CrTM2@Pc catalyst is stable for CO2 chemisorption and is beneficial for CO2 activation.
[0067] Generally, the CO2 reduction reaction is a process of forming reaction intermediates through proton-coupled electron transfer (PCET), where atoms combine with hydrogen to achieve optimal CO2 reduction performance. The Gibbs free energy ΔG is used to mitigate reaction obstacles; the Gibbs free energy ΔG is defined as:
[0068] ΔG=ΔE+ΔE ZPE -TΔS+ΔG u +ΔG pH
[0069] Where ΔE is the total energy difference between reactants and products calculated by DFT; ΔE ZPE Let TΔS (T = 298.15 K) be the contribution of zero-point energy and entropy to ΔG, respectively; ΔG U Let ΔG be the applied electrode potential, and ΔG be the effect of pH on Gibbs free energy. Assuming pH is zero under acidic conditions, the zero-point energy and entropy of the intermediate substances in the CO2RR process are calculated using vibrational frequencies, and the free molecule E is obtained based on the calculated vibrational frequencies. ZPE and TΔS;
[0070] Generally, the limiting potential U L It is an important parameter for evaluating catalyst performance; U L The calculation formula is:
[0071] U L =-ΔG / e
[0072] Where -ΔG is the change in Gibbs free energy during the rate-limiting step;
[0073] (3) By calculating the free energy barrier of CO2 adsorption and activation and CO2 reduction reaction of candidate structural models, the optimal structural model with the best catalytic activity for CO2 reduction is determined from the candidate structural models; usually, the two-dimensional extended phthalocyanine bimetallic atom monolayer structure model is used as a carrier to simulate the CO2 adsorption and activation process, and the reaction free energy is calculated to select the target model.
[0074] As an optional embodiment, such as Figure 5 As shown, the coordination structure unit TM1TM2@Pc (where TM1TM2 is CrCr, CrMn, CrFe, CrCo) was screened and showed good catalytic activity for the electrocatalytic reduction of CO2 to CO and HCOOH; furthermore... Figure 6 As shown, the coordination structure unit TM1TM2@Pc (where TM1TM2 is CrCr, CrMn, CrFe, CrCo) was screened and showed good catalytic activity for the electrocatalytic reduction of CO2 to CH3OH and CH4.
[0075] (4) The active sites of the hydrogen evolution reaction (HER) of the optimal structural model were revealed by Gibbs free energy calculation, and the trend of the difference between the competitive reaction of CO2 reduction and HER was established.
[0076] (5) By applying an external potential, the catalytic selectivity parameters of the optimal structural model are optimized to obtain a phthalocyanine-based biatomic monolayer catalyst configuration that suppresses HER side reactions and improves CO2 conversion efficiency.
[0077] Generally, the limiting potential U L U is a key parameter in the electrochemical reduction reaction of CO2 (CO2RR), representing the minimum potential required for a specific reaction to reach equilibrium under specific electrochemical conditions. In the electrochemical reduction reaction of CO2, U... L The level directly reflects the catalyst's ability to produce a specific product, such as CO, HCOOH, CH3OH, or CH4. Higher U values indicate higher levels of this catalyst. L This means that a higher overpotential is required to generate the product, making the reaction more difficult to proceed; Figure 7 The limiting potential (UL) diagrams for the formation of CO, HCOOH, CH3OH, and CH4 are listed, as well as the free energy step diagrams for HER on TM1TM2@Pc and the limiting potential difference diagrams for CO2RR and HER on TM1TM2@Pc under different applied potentials, with limiting potentials U being 0, -0.1, -0.2, and -0.3 V (vs RHE). Among them, (a) summarizes the limiting potentials (UL) of the C1 products produced on CrCr / CrMn / CrFe / CrCo@Pc. L );
[0078] The hydrogen evolution reaction (HER) is considered a competing reaction to the CO2RR; when the Gibbs free energy ΔG of the *H intermediate... H When it is close to zero, because * The energy barriers for H generation and desorption are lowered, making the HER reaction thermodynamically more likely to occur; the Gibbs free energy on the catalyst CrTM2@Pc (TM2=Cr,Mn,Fe,Co) in HER is as follows: Figure 7 As shown in (b);
[0079] Generally, the dominance of HER in practical applications can be mitigated by adjusting the catalyst electronic structure, optimizing electrolyte pH, and adjusting the application potential. Therefore, the selectivity of CO2RR can be improved by applying an application potential; Figure 7 As can be seen from (c), (d), (e), and (f), when the applied potential U = -0.2V (vs RHE), CrFe@Pc exhibits stronger selectivity for HCOOH, CH3OH, and CH4 than HER; CrCo@Pc shows the best selectivity for HCOOH at the same applied potential; generally, within a certain range, applying the applied potential can improve the selectivity of CO2RR.
[0080] This application discloses a method for preparing a two-dimensional extended phthalocyanine monolayer supported transition metal diatomic catalyst (TM1TM2@Pc) and its application in CO2 electrocatalytic reduction. By embedding and fixing TM1 and TM2 (TM1 and TM2 are independently selected from Cr, Mn, Fe, Co, and Ni, respectively) into a two-dimensional extended phthalocyanine monolayer, the structural and thermal stability of TM1 and TM2 enables efficient reduction of CO2 to produce C1 products. The two-dimensional extended phthalocyanine monolayer supported transition metal diatomic catalyst possesses advantages such as high stability, low limiting potential, and high selectivity. In particular, the CrTM2@Pc configuration exhibits excellent electrocatalytic performance and is suitable for industrial applications of CO2RR.
[0081] The technical solutions and technical details disclosed in the embodiments of this invention are merely illustrative of the inventive concept of this invention and do not constitute a limitation on the technical solutions of the embodiments of this invention. Any conventional changes, substitutions, or combinations made to the technical details disclosed in the embodiments of this invention have the same inventive concept as this invention and are within the protection scope of the claims of this invention.
Claims
1. A phthalocyanine-based bimetallic atomic monolayer structure model, characterized by, The structural model comprises two-dimensional periodic coordination structure units represented as TM1TM2@Pc; wherein TM1 and TM2 are any one of Cr, Mn, Fe, Co and Ni, and Pc is a phthalocyanine-based monolayer supercell, and TM1 and TM2 are anchored at the macrocyclic central site and adjacent bridge site of the phthalocyanine-based monolayer supercell in an embedded coordination manner.
2. The phthalocyanine-based bimetallic atomic monolayer structure model of claim 1, wherein, The lattice constant of the phthalocyanine-based monolayer supercell is The phthalocyanine-based monolayer supercell contains twelve nitrogen atoms, thirty carbon atoms, and eight hydrogen atoms, wherein the distance between carbon and adjacent nitrogen atoms is about The distance between adjacent carbons is about 3. The method of constructing a phthalocyanine-based bi-metallic atomic monolayer structure model according to claim 1 or 2, characterized in that, The construction method comprises the following steps: S1, constructing a two-dimensional extended phthalocyanine-based bimetallic atom monolayer structural model and performing optimization calculation; S2, based on binding energy and molecular dynamics simulation, screening a two-dimensional extended phthalocyanine-based bimetallic atom monolayer structural model meeting the structural stability requirement as a candidate structural model; S3, based on the free energy barrier of CO2 adsorption and activation and CO2 reduction reaction, screening a candidate structural model with the optimal CO2 reduction catalytic activity as an optimal structural model; S4, using Gibbs free energy calculation to reveal the hydrogen evolution reaction active site of the optimal structural model, and establishing the competition reaction difference trend of CO2 reduction and hydrogen evolution reaction; S5, by applying an external potential, optimizing the catalytic selectivity parameters of the optimal structural model, and obtaining an optimal structural model that suppresses the hydrogen evolution reaction and improves the CO2 conversion efficiency as a phthalocyanine-based bimetallic atom monolayer structural model.
4. The construction method according to claim 3, characterized in that, In step S2, the binding energy is calculated by the following formula: wherein, E is the binding energy, Pc E TM1TM2@Pc E TM1-sing atom E TM2-single atom E E is the total energy of the individual Pc ring and TM1TM2@Pc coordination structural unit, respectively, E E is the total energy of the TM1 and TM2 metal atoms, respectively, and a positive binding energy indicates the formation of an energetically stable complex.
5. The construction method of claim 3, wherein, In step S2, 10 ps of molecular dynamics simulation at 500 K is used to evaluate the thermal stability of the two-dimensional extended phthalocyanine-based bimetallic atom monolayer structural model.
6. The construction method of claim 3, wherein, In step S3, the CO2 reduction reaction is the reduction of CO2 to C1 products under electrochemical conditions, and the C1 products include one or more of CO, HCOOH, CH3OH and CH4.
7. The construction method of claim 3, wherein, In step S5, when the applied potential is-0.2 V (vs RHE), the selectivity of CrFe@Pc for reducing CO2 to HCOOH, CH3OH and CH4 is stronger than that of the hydrogen evolution reaction.
8. The construction method of claim 3, wherein, In step S5, under the same action potential, the selectivity of CrCo@Pc for reducing CO2 to HCOOH is the best.
9. Use of the phthalocyanine-based bimetallic atomic monolayer structure model according to claim 1 or 2, characterized in that, The phthalocyanine-based bimetallic atom monolayer structural model is used as a CO2 reduction electrocatalyst.
10. Use according to claim 9, characterized in that, Under the catalysis of the CO2 reduction electrocatalyst, CO2 is reduced to C1 products, and the C1 products include one or more of CO, HCOOH, CH3OH and CH4.