CN114843534A - Method for efficiently designing potential ORR and NRR catalysts based on air as reaction gas source - Google Patents

Method for efficiently designing potential ORR and NRR catalysts based on air as reaction gas source Download PDF

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CN114843534A
CN114843534A CN202210584678.3A CN202210584678A CN114843534A CN 114843534 A CN114843534 A CN 114843534A CN 202210584678 A CN202210584678 A CN 202210584678A CN 114843534 A CN114843534 A CN 114843534A
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CN114843534B (en
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刘超
金璐雅
陈明伟
王道淼
漆小鹏
刘美玲
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Guorui Kechuang Rare Earth Functional Materials Ganzhou Co ltd
Jiangxi University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a method for efficiently designing potential ORR and NRR catalysts based on air as a reaction air source, which is characterized in that a single-atom catalyst model is constructed based on different N-C coordination environments and different active site Tm atoms, and a potential ORR or NRR catalyst which is suitable for air as a reaction air source is rapidly positioned by carrying out layer-by-layer progressive screening of stability analysis, competitive adsorption of air main components and desorption of substances based on a first principle density functional theory. The invention can quickly realize the ORR and NRR catalyst design by taking the air source as the reaction gas source, and improves the catalyst design efficiency and the air source adaptability. The large-scale use of the related catalyst can promote the popularization of new energy, reduce environmental pollution and protect ecological environment.

Description

Method for efficiently designing potential ORR and NRR catalysts based on air as reaction gas source
Technical Field
The invention provides a method for efficiently designing potential ORR and NRR catalysts based on air as a reaction air source, and belongs to the technical field of air purification catalysts.
Background
Energy crisis and environmental pollution are serious global issues, and there is an urgent need to find efficient and powerful electrochemical energy conversion and storage systems/devices in the field of electrocatalytic material science to enable sustainable future. Oxygen Reduction Reaction (ORR) and Nitrogen Reduction Reaction (NRR) play a significant role in oxygen electrocatalytic technology.
ORR background significance: the proton membrane fuel cell has advantages of high efficiency and low emission compared to petroleum combustion, but the major obstacle to commercialization of the fuel cell is the slow kinetics of the fuel cell cathode ORR, which may result in a 30% reduction in the efficiency of the proton membrane fuel cell, so in order to solve this problem of the proton membrane fuel cell, it is necessary to select a suitable catalyst for use in the fuel cell to increase its efficiency, so that it can be widely used in social life. The ecological environment can be protected while the social and economic benefits are improved. Noble platinum metals are commonly used as ORR catalysts. The large-scale practical use of these renewable energy devices is greatly hampered if the precious and expensive precious metal-based electrocatalysts cannot be replaced by other low-cost, precious metal-free, yet highly efficient and durable electrodes. The exploration of cheap, efficient and stable bifunctional non-rare metal (NPM) substitutes is of particular significance today.
NRR background significance: ammonia is one of the chemical products with the largest yield in the world and plays an important role in the global economy. Currently, global ammonia production is mainly derived from the traditional haber ammonia synthesis process: namely, high-purity nitrogen and hydrogen are converted into ammonia gas by using an iron-based catalyst under the conditions of high temperature and high pressure. The N ≡ N bond in nitrogen has stronger bond energy (945kJ mol) -1 ) The process needs to realize the activation of nitrogen under high temperature (300- 2 The emission amounts account for 1-3% and 1.6-3% of the total amount of the whole world, respectively. The haber process for synthesizing ammonia has high energy consumption and serious pollution. Therefore, the method for synthesizing ammonia with environmental protection and low energy consumption is of great significance to sustainable development of national economy. The electrochemical synthesis method of ammonia can make thermodynamics non-spontaneousThe synthesis ammonia reaction is not or less limited by thermodynamic equilibrium under the promotion of electric energy, and realizes the normal-temperature and normal-pressure synthesis of ammonia, thereby becoming a research field which is concerned by much.
For example, the synthesis of monatomic catalysts: 2-methylimidazole 2-MeIm with Zinc nitrate Zn (NO) 3 ) 2 According to the mass ratio of 1: 2 is miscible in a proper amount of methanol CH 3 In OH solvent, ZIF8 solution was prepared. Then adding a transition metal-acetylacetone compound Tm- (acac) with the same mass as that of the zinc nitrate X Stirring for 0.5 hour, transferring to a polytetrafluoroethylene hydrothermal synthesis reaction kettle, heating to 120 ℃, and preserving heat for 4 hours. Centrifuging at high speed by a centrifuge to obtain precipitate, and passing through methanol CH 3 OH cleaning, vacuum drying at constant temperature of 60 ℃ for 12 hours to obtain packaged Tm- (acac) X Tm @ ZIF 8. Putting the prepared precursor Tm @ ZIF8 into a tube furnace, and flowing N 2 Under the condition, the temperature is raised to 920 ℃ (slightly higher than the boiling point 907 ℃ of Zn at the heating rate of 5 ℃/min, Zn is evaporated while high boiling point transition metal Tm is remained), the temperature is kept for 2 hours, and furnace annealing is carried out to the room temperature. Then using appropriate amount of H at room temperature 2 SO 4 And (3) pickling the powder for 2 hours to remove potential large-particle-size metal substances, finally centrifugally washing the powder by using ultrapure water, and drying the powder in vacuum at a constant temperature of 60 ℃ for 24 hours to obtain the transition metal doped porous carbon-based single-atom catalyst.
Characterization phase information: the BET specific surface area and the pore size distribution were measured by a nitrogen adsorption apparatus. The structure and phase measurements were performed on the synthesized catalyst samples by X-ray diffractometry. Observing the microstructure and the morphology of the glass by depending on a Transmission Electron Microscope (TEM) and a Scanning Electron Microscope (SEM); detecting the content and distribution of different elements in the synthetic catalyst by an X-ray energy spectrum analyzer (EDS); and then the content of the transition metal element is accurately measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And obtaining the integral phase information of the catalyst at the microscopic level through related test analysis. Meanwhile, the relevant information of the configuration of the active center of the synthetic catalyst can be further obtained through a high-angle annular dark field scanning electron microscope HAADF-STEM and selective area electron diffraction SAED; performing X-ray photoelectron spectroscopy research on an XPS spectrometer system to test active center configuration elements and the valence state of the active center configuration elements in a catalyst sample; and (3) characterizing the coordination relation of the active center configuration based on an X-ray absorption near-edge spectrum XANES, an expanded X-ray absorption fine structure EXAFS and the like. The test characterization is combined to comprehensively provide specific information of Tm active sites and N-C coordination environment.
Electrochemical testing: 5mg of catalyst sample was dispersed in 480. mu.L of ethanol mixture, 480. mu.LH 2 O and 40. mu.L of 5% ethanol solution of perfluorosulfonic acid were degraded by sonication for 0.5 hour. The catalyst was then dropped onto a polished glassy carbon rotating disk electrode RDE or rotating disk ring electrode RRDE having a diameter d of 5mm and dried at room temperature. The loading capacity of the catalyst is 0.5mg/cm 2 。
ORR: the test was carried out at room temperature using a three-electrode system, acidic environment: the electrolyte was 0.1M HClO 4 Saturated N of 2 /O 2 In the water solution, the reference electrode is a saturated calomel electrode SCE, and the counter electrode is a carbon electrode. All measured potentials were switched to the reversible hydrogen electrode potential RHE. Firstly, circulating voltammetry CV scanning is carried out to calculate the electric double layer capacitance C dl And electrochemical specific surface area ECSA; then carrying out Linear Sweep Voltammetry (LSV) scanning to obtain an ORR initial potential E onset Half-wave potential E 1/2 And the limit diffusion current density DLCD, so as to obtain the overpotential eta of the electro-catalysis ORR, obtain the Tafel slope through the fitting of an LSV curve, determine the RDS of the reaction speed limiting step, obtain a Nyquist diagram based on the EIS test of the electrochemical impedance spectrum, and obtain the charge transfer resistance Rct; finally the transition frequency TOF of the catalyst was explored by testing the CV curve in neutral phosphate buffered saline PBS. The stable durability of the catalyst was analyzed by a cyclic durability test and a potentiostatic durability test. The electron transfer number n in the ORR process is calculated from the slope of the Koutecky-Levich (K-L) curve, and the side reaction H is calculated based on the electron transfer number n 2 O 2 The yield of (a).
NRR: the NRR electrochemical performance of various catalysts was studied on a typical H-cell of CHI660 electrochemical workstation of chenhua, shanghai, using Nafion 117 as an anion exchange membrane. Electrochemical measurements were performed at room temperature using a three-electrode system, in which ammonia was measured colorimetrically, hydrogen was detected with a gas chromatograph (GC Agilent 7890B), and the by-product hydrazine was characterized by the Watt method and the christip method. And obtaining the catalytic performance parameters such as Faraday efficiency FE and ammonia yield in the NRR process.
The above method cannot directly utilize air, and needs pure oxygen and nitrogen to study participation in the reaction respectively. The pure oxygen and nitrogen need to be separated industrially by taking air as raw material (the air is liquefied at high pressure and low temperature, the boiling point of nitrogen is-195.8 ℃, the boiling point of oxygen is-183 ℃, and the gas and liquid can be separated by controlling the temperature to be more than-195.8 ℃ and less than-183 ℃). The separation process has high energy consumption, the pure gas needs to be stored and transported through a high-pressure gas cylinder, the process is complex, the period is long, the cost is high, and certain safety exists. In addition, pure gas is used as a gas source, and related equipment needs a butt joint high-pressure gas cylinder device, so that the equipment structure is complicated.
The research and development process of the catalyst based on the experimental synthesis of the catalyst, the analysis of the characterization phase information and the electrochemical test of the catalytic performance faces the challenges of long research and development period, large consumption of manpower and material resources, more three wastes, time and labor consumption in treatment and the like, and in addition, the blind preparation of the catalyst can not be really put into practical use easily due to the defects of unknown sensitivity of the catalyst to other gases, unknown catalytic mechanism and the like.
Disclosure of Invention
Throughout the entire electrochemical catalytic process of ORR and NRR, involving rather complex reaction pathways and slow kinetics, the selection of a suitable electrocatalyst is crucial for catalytic activity, durability, product selectivity and practical cost. Because the main component in the air is N 2 And O 2 Also contains a small amount of H 2 O and CO 2 Equal gas, and small amount of H 2 O and CO 2 When the gas is introduced into the solution, the gas is dissolved in water, and the content of the gas is low, so that the influence on the acidity of the proton membrane fuel cell and the NRR catalyst is easy to influence on the environment and is nearly zero. And the reactant of ORR is O 2 The reactant of NRR is N 2 Therefore, the most economical, convenient and safe reactant for ORR and NRR is derived from air, which contains a small amount of H 2 O and CO 2 Can be dissolved in water, so that the Tm-N-C coordination relation is established to regulate N 2 And O 2 Selective adsorption study to screen for potentialORR and NRR catalysts provide guidance.
According to theory, model construction for analysis and calculation is an important mode means of scientific research, important data support is provided for further experimental analysis, and how to quickly determine that efficient selection of potential ORR/NRR catalysts is a very important technology according to theoretical research provides a simple and easy advanced screening process for efficiently selecting potential ORR/NRR catalyst models, wherein air can be directly introduced into the catalysts.
The invention avoids preparing pure O 2 /N 2 The complex and energy-consuming process of the method, the air is directly introduced into the catalyst, and the method is more convenient and energy-saving. The method is based on different N-C coordination environments and different active site Tm atoms to construct a single-atom catalyst model, and the potential ORR or NRR catalyst which is suitable for air as a reaction air source is rapidly positioned by developing stability analysis based on a first principle → air main component competitive adsorption → layer-by-layer progressive screening of product desorption.
The specific method comprises the following steps:
a method for efficiently designing potential ORR and NRR catalysts based on air as a reaction gas source, comprising the steps of:
s1, constructing substrate catalyst models of all transition metals including single-vacancy and double-vacancy and N-doped graphene with different concentrations based on first principle density functional theory, and respectively recording the models as Tm-N X -C 3-X -Gra and Tm-N X -C 4-X -Gra; wherein Tm-N is converted according to a nitrogen-carbon combination configuration 2 -C 2 the-Gra configuration is divided into five-membered ring type pen, para type opp and six-membered ring type hex;
s2, regarding a double-vacancy catalyst model formed by doping N-coordinated single transition metal with graphene, according to the formation energy delta E f Calculation of equation (1) and binding energy Δ E b Calculating the formation energy delta E of all the pre-screened models by the calculation formula (2) f And binding energy Δ E b (ii) a According to Δ E f <0eV and Δ E b <E coh Screening a stable catalyst configuration; e coh The energy is the metal cohesive energy;
Figure BDA0003662982790000041
Figure BDA0003662982790000042
wherein
Figure BDA0003662982790000043
And E Gra Respectively represent a double-vacancy type single-atom catalyst Tm-N X -C 4-X Catalyst model N of Gra, deficient in transition Metal X -C 4-X System energy of Gra and graphene Gra, E C 、E Tm 、E N Respectively represent the energy of the single atom C, N, Tm;
for a single-vacancy catalyst model, its energy of formation Δ E f And binding energy Δ E b Respectively as calculation formulas (3) and (4); wherein
Figure BDA0003662982790000044
And
Figure BDA0003662982790000045
respectively represent a single-vacancy type monatomic catalyst Tm-N X -C 3-X Catalyst model N for Gra and deficient transition metals X -C 3-X -Gra system energy;
Figure BDA0003662982790000046
Figure BDA0003662982790000047
s3 construction of O under different adsorption modes 2 The adsorption model and the optimized structure are adopted, the adsorption model with the lowest energy is selected, and the O of the catalyst is calculated according to the formula (5) 2 The adsorption energy of (c);
Figure BDA0003662982790000048
wherein
Figure BDA0003662982790000049
Means that the catalyst adsorbs O 2 The total energy of the system (2) is,
Figure BDA00036629827900000410
refers to a single O 2 The energy of the molecule, sub, is the catalyst substrate model, the single-vacancy and double-vacancy models, respectively denoted as Tm-N X -C 3-X -Gra and Tm-N X -C 4-X -Gra；
S4 construction of N under different adsorption modes 2 The adsorption model and the optimized structure are adopted, the adsorption model with the lowest energy is selected, and the N of the catalyst is calculated according to the formula (6) 2 The adsorption energy of (c);
Figure BDA00036629827900000411
wherein
Figure BDA00036629827900000412
Means that the catalyst adsorbs N 2 The total energy of the system (2) is,
Figure BDA00036629827900000413
refers to a single N 2 The energy of the molecule;
s5, comparing the same substrates, to O 2 And to N 2 When adsorption energy of (1) is in the range of O 2 Adsorption energy equal or approximately equal to N 2 Adsorption energy means that the co-adsorption of oxygen and nitrogen exists by taking air as a gas source, and ORR and NRR coexist in the follow-up process; this case is neither suitable for NRR nor ORR, left off;
s6, when
Figure BDA00036629827900000414
I.e. O 2 Adsorption capacity>N 2 Description of the adsorption CapacityThe catalyst will preferentially adsorb oxygen;
Figure BDA00036629827900000415
the smaller the size
Figure BDA00036629827900000416
Then O is selectively adsorbed 2 The stronger the ability of (c); because of the consideration of catalyst cyclicity, the product must be easily desorbed or not adsorbed; the ORR reaction product is H 2 O, therefore, further study of H 2 Adsorption energy of O according to formula (7); if it is
Figure BDA00036629827900000417
That is to say H 2 Adsorption capacity of O<O 2 Adsorption capacity if
Figure BDA00036629827900000418
The product can not be desorbed spontaneously, but the reactant which is easy to be adsorbed strongly occupies the adsorption site to cause desorption; if when it is used
Figure BDA00036629827900000419
The product has a tendency to desorb spontaneously; both cases show satisfaction
Figure BDA00036629827900000420
The catalyst is suitable for use in ORR; otherwise, it is not satisfied
Figure BDA00036629827900000421
The ORR is not suitable and should be omitted;
Figure BDA0003662982790000051
wherein
Figure BDA0003662982790000052
Means that the catalyst adsorbs H 2 The total energy of the system of O,
Figure BDA0003662982790000053
means single H 2 The energy of the O molecule;
s7, when
Figure BDA0003662982790000054
I.e. O 2 Adsorption capacity<N 2 In case of adsorption capacity, the reaction product is NH due to NRR 3 Therefore, further exploration of NH 3 According to formula (8); if it is
Figure BDA0003662982790000055
Namely NH 3 Adsorption capacity of<N 2 Adsorption capacity, the catalyst can be recycled for NRR reaction, i.e., can be suitably used for NRR; otherwise, the method is used
Figure BDA0003662982790000056
Indicating the active site adsorption product NH 3 Too strong a capacity, i.e. catalyst active sites are covered by product NH 3 Passivation, which cannot be circularly eliminated;
Figure BDA0003662982790000057
wherein
Figure BDA0003662982790000058
Means that the catalyst adsorbs NH 3 The total energy of the system (2) is,
Figure BDA0003662982790000059
refers to a single NH 3 The energy of the molecule;
and (3) integrating the progressive screening of the steps S2-S7, narrowing the range of research models, quickly and accurately positioning the required models, obtaining potential ORR/NRR catalyst models, and providing design guidance for developing NRR and ORR catalysts which take air as a reaction gas source for experiments.
The technical scheme of the invention has the following beneficial effects:
in the industrial separation method, air is liquefied at high pressure and low temperature, the boiling point of nitrogen is-195.8 deg.C, the boiling point of oxygen is-183 deg.C, and the temperature is controlledThe gas and the liquid can be separated at the temperature of between-195.8 and-183 ℃. The invention directly takes the air as a reaction gas source, and does not need to realize the N in the air by a strategy of separating the gases according to the different boiling points of the nitrogen and the oxygen 2 And O 2 The air is separated firstly, and the air is introduced into the electrolyte through the air inlet end to participate in the reaction. The use of a high-pressure gas cylinder is avoided, the butt joint equipment of high-pressure gas is reduced, the working procedures are simplified, and meanwhile, the safety is improved. In addition, the method has the advantages of saving the production cost and the transportation cost of the air source, avoiding unnecessary energy waste and the like.
Based on the design method provided by the invention, the ORR and NRR catalyst design taking the air source as the reaction gas source can be quickly realized, and the catalyst design efficiency and the air source adaptability are improved. The large-scale use of the related catalyst can promote the popularization of new energy, reduce environmental pollution, protect ecological environment, help China to realize double-carbon emission reduction tasks and improve the scientific and technological competitiveness of catalytic industry.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiment.
The process of the present invention, as shown in FIG. 1, is achieved by progressive screening for efficient selection of ORR and NRR catalysts; selective adsorption of O based on Tm-N-C coordination relation regulation 2 /N 2 (ii) a The specific technical description scheme is as follows:
a method for efficiently designing potential ORR and NRR catalysts based on air as a reaction gas source, comprising the steps of:
s1, constructing substrate catalyst models of all transition metals including single-vacancy and double-vacancy and N-doped graphene with different concentrations based on first principle density functional theory, and respectively recording the models as Tm-N X -C 3-X -Gra and Tm-N X -C 4-X -Gra; wherein Tm-N is converted according to a nitrogen-carbon combination configuration 2 -C 2 the-Gra configuration is divided into five-membered ring type pen, para type opp and six-membered ring type hex;
s2 bis formed for N-coordinated single transition metal doped grapheneVacancy catalyst model, energy of formation Δ E f Calculating the formation energy delta E of all the pre-screened models by the calculation formula (1) and the combination energy delta Eb calculation formula (2) f And binding energy Δ E b (ii) a According to Δ E f <0eV and Δ E b <E coh Screening a stable catalyst configuration; e coh The energy is the metal cohesive energy;
Figure BDA0003662982790000061
Figure BDA0003662982790000062
wherein
Figure BDA0003662982790000063
And E Gra Respectively represent a double-vacancy type single-atom catalyst Tm-N X -C 4-X Catalyst model N of Gra, deficient in transition Metal X -C 4-X System energy of Gra and graphene Gra, E C 、E Tm 、E N Respectively representing the energy of a single atom C, N, Tm;
for a single-vacancy catalyst model, its energy of formation Δ E f And binding energy Δ E b Respectively as calculation formulas (3) and (4); wherein
Figure BDA0003662982790000064
And
Figure BDA0003662982790000065
respectively represent a single-vacancy type monatomic catalyst Tm-N X -C 3-X Catalyst model N for Gra and deficient transition metals X -C 3-X -Gra system energy;
Figure BDA0003662982790000066
Figure BDA0003662982790000067
s3 construction of O under different adsorption modes 2 The adsorption model and the optimized structure are adopted, the adsorption model with the lowest energy is selected, and the O of the catalyst is calculated according to the formula (5) 2 The adsorption energy of (c);
Figure BDA0003662982790000068
wherein
Figure BDA0003662982790000069
Means that the catalyst adsorbs O 2 The total energy of the system (2) is,
Figure BDA00036629827900000610
refers to a single O 2 The energy of the molecule, sub, is the catalyst substrate model, the single-vacancy and double-vacancy models, respectively denoted as Tm-N X -C 3-X -Gra and Tm-N X -C 4-X -Gra；
S4 construction of N under different adsorption modes 2 The adsorption model and the optimized structure are adopted, the adsorption model with the lowest energy is selected, and the N of the catalyst is calculated according to the formula (6) 2 The adsorption energy of (c);
Figure BDA00036629827900000611
wherein
Figure BDA00036629827900000612
Means that the catalyst adsorbs N 2 The total energy of the system (2) is,
Figure BDA00036629827900000613
refers to a single N 2 The energy of the molecule;
s5, comparing the same substrates, to O 2 And to N 2 When adsorption energy of (1) is in the range of O 2 Adsorption energy equal or approximately equal to N 2 Adsorption energy meansIf air is used as a gas source, the co-adsorption of oxygen and nitrogen exists, and ORR and NRR coexist in a mixed manner in the follow-up process; this case is neither suitable for NRR nor ORR, left off;
s6, when
Figure BDA0003662982790000071
I.e. O 2 Adsorption capacity>N 2 When the adsorption capacity is high, the catalyst can preferentially adsorb oxygen;
Figure BDA0003662982790000072
the smaller the size
Figure BDA0003662982790000073
Then O is selectively adsorbed 2 The stronger the ability of (c); because of the consideration of catalyst cyclicity, the product must be easily desorbed or not adsorbed; the ORR reaction product is H 2 O, therefore, further study of H 2 Adsorption energy of O according to formula (7); if it is
Figure BDA0003662982790000074
That is to say H 2 Adsorption capacity of O<O 2 Adsorption capacity if
Figure BDA0003662982790000075
The product can not be desorbed spontaneously, but the reactant which is easy to be adsorbed strongly occupies the adsorption site to cause desorption; if when it is used
Figure BDA0003662982790000076
The product has a tendency to desorb spontaneously; both cases show satisfaction
Figure BDA0003662982790000077
The catalyst is suitable for use in ORR; otherwise, it is not satisfied
Figure BDA0003662982790000078
The ORR is not suitable and should be omitted;
Figure BDA0003662982790000079
wherein
Figure BDA00036629827900000710
Means that the catalyst adsorbs H 2 The total energy of the system of O,
Figure BDA00036629827900000711
means single H 2 The energy of the O molecule;
s7, when
Figure BDA00036629827900000712
I.e. O 2 Adsorption capacity<N 2 In case of adsorption capacity, the reaction product is NH due to NRR 3 Therefore, further exploration of NH 3 According to formula (8); if it is
Figure BDA00036629827900000713
Namely NH 3 Adsorption capacity of<N 2 Adsorption capacity, the catalyst can be recycled for NRR reaction, i.e., can be suitably used for NRR; otherwise, the reverse is carried out
Figure BDA00036629827900000714
Indicating the active site adsorption product NH 3 Too strong a capacity, i.e. catalyst active sites are covered by product NH 3 Passivation, which cannot be circularly eliminated;
Figure BDA00036629827900000715
wherein
Figure BDA00036629827900000716
Means that the catalyst adsorbs NH 3 The total energy of the system (2) is,
Figure BDA00036629827900000717
refers to a single NH 3 The energy of the molecule;
and (3) integrating the progressive screening of the steps S2-S7, narrowing the range of research models, quickly and accurately positioning the required models, obtaining potential ORR/NRR catalyst models, and providing design guidance for developing NRR and ORR catalysts which take air as a reaction gas source for experiments.

Claims (2)

1. The method for efficiently designing the potential ORR and NRR catalysts based on air as a reaction air source is characterized in that a single-atom catalyst model is constructed based on different N-C coordination environments and different active site Tm atoms, and the potential ORR or NRR catalysts which adapt to air as a reaction air source are rapidly positioned by carrying out layer-by-layer progressive screening of stability analysis, competitive adsorption of air main components and desorption of substances according to a first principle density functional theory.
2. The method for efficient design of potential ORR and NRR catalysts based on air as a reactive gas source as claimed in claim 1, comprising the following steps:
s1, constructing substrate catalyst models of all transition metals including single-vacancy and double-vacancy and N-doped graphene with different concentrations based on first principle density functional theory, and respectively recording the models as Tm-N X -C 3-X -Gra and Tm-N X -C 4-X -Gra; wherein Tm-N is converted according to a nitrogen-carbon combination configuration 2 -C 2 the-Gra configuration is divided into five-membered ring type pen, para type opp and six-membered ring type hex;
s2, regarding a double-vacancy catalyst model formed by doping N-coordinated single transition metal with graphene, according to the formation energy delta E f Calculating the formation energy delta E of all the pre-screened models by the calculation formula (1) and the combination energy delta Eb calculation formula (2) f And binding energy Δ E b (ii) a According to Δ E f <0eV and Δ E b <E coh Screening a stable catalyst configuration; e coh The energy is the metal cohesive energy;
Figure FDA0003662982780000011
Figure FDA0003662982780000012
wherein
Figure FDA0003662982780000013
And E Gra Respectively represent a double-vacancy type single-atom catalyst Tm-N X -C 4-X Catalyst model N of Gra, deficient in transition Metal X -C 4-X System energy of Gra and graphene Gra, E C 、E Tm 、E N Respectively representing the energy of single atoms C, Tm and N;
for a single-vacancy catalyst model, its energy of formation Δ E f And binding energy Δ E b Respectively as calculation formulas (3) and (4); wherein
Figure FDA0003662982780000014
And
Figure FDA0003662982780000015
respectively represent a single-vacancy type monatomic catalyst Tm-N X -C 3-X Catalyst model N for Gra and deficient transition metals X -C 3-X -Gra system energy;
Figure FDA0003662982780000016
Figure FDA0003662982780000017
s3 construction of O under different adsorption modes 2 The adsorption model and the optimized structure are adopted, the adsorption model with the lowest energy is selected, and the O of the catalyst is calculated according to the formula (5) 2 The adsorption energy of (c);
Figure FDA0003662982780000018
wherein
Figure FDA0003662982780000019
Means that the catalyst adsorbs O 2 The total energy of the system (2) is,
Figure FDA00036629827800000110
refers to a single O 2 The energy of the molecule, sub, is the catalyst substrate model, the single-vacancy and double-vacancy models, respectively denoted as Tm-N X -C 3-X -Gra and Tm-N X -C 4-X -Gra；
S4 construction of N under different adsorption modes 2 The adsorption model and the optimized structure are adopted, the adsorption model with the lowest energy is selected, and the N of the catalyst is calculated according to the formula (6) 2 The adsorption energy of (c);
Figure FDA0003662982780000021
wherein
Figure FDA0003662982780000022
Means that the catalyst adsorbs N 2 The total energy of the system (2) is,
Figure FDA0003662982780000023
refers to a single N 2 The energy of the molecule;
s5, comparing the same substrates, to O 2 And to N 2 When adsorption energy of (1) is in the range of O 2 Adsorption energy equal or approximately equal to N 2 Adsorption energy means that the co-adsorption of oxygen and nitrogen exists by taking air as a gas source, and ORR and NRR coexist in the follow-up process; this case is neither suitable for NRR nor ORR, left off;
s6, when
Figure FDA0003662982780000024
I.e. O 2 Adsorption capacity>N 2 When the adsorption capacity is high, the catalyst can preferentially adsorb oxygen;
Figure FDA0003662982780000025
the smaller the size
Figure FDA0003662982780000026
Then O is selectively adsorbed 2 The stronger the ability of (c); because of the consideration of catalyst cyclicity, the product must be easily desorbed or not adsorbed; the ORR reaction product is H 2 O, therefore, further study of H 2 Adsorption energy of O according to formula (7); if it is
Figure FDA0003662982780000027
That is to say H 2 Adsorption capacity of O<O 2 Adsorption capacity if
Figure FDA0003662982780000028
The product can not be desorbed spontaneously, but the reactant which is easy to be adsorbed strongly occupies the adsorption site to cause desorption; if when it is used
Figure FDA0003662982780000029
The product has a tendency to desorb spontaneously; both cases show satisfaction
Figure FDA00036629827800000210
The catalyst is suitable for use in ORR; otherwise, it is not satisfied
Figure FDA00036629827800000211
The ORR is not suitable and should be omitted;
Figure FDA00036629827800000212
wherein
Figure FDA00036629827800000213
Means that the catalyst adsorbs H 2 The total energy of the system of O,
Figure FDA00036629827800000214
means single H 2 The energy of the O molecule;
s7, when
Figure FDA00036629827800000215
I.e. O 2 Adsorption capacity<N 2 In case of adsorption capacity, the reaction product is NH due to NRR 3 Therefore, further exploration of NH 3 According to formula (8); if it is
Figure FDA00036629827800000216
Namely NH 3 Adsorption capacity of<N 2 Adsorption capacity, the catalyst can be recycled for NRR reaction, i.e., can be suitably used for NRR; otherwise, the reverse is carried out
Figure FDA00036629827800000217
Indicating the active site adsorption product NH 3 Too strong a capacity, i.e. catalyst active sites are covered by product NH 3 Passivation, which cannot be circularly eliminated;
Figure FDA00036629827800000218
wherein
Figure FDA00036629827800000219
Means that the catalyst adsorbs NH 3 The total energy of the system (2) is,
Figure FDA00036629827800000220
refers to a single NH 3 The energy of the molecule.
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US20140050995A1 (en) * 2011-03-01 2014-02-20 Liming Dai Metal-free oxygen reduction electrocatalysts
US20200127300A1 (en) * 2017-06-13 2020-04-23 The Board Of Trustees Of The Leland Stanford Junior University Electrochemical catalysts with enhanced catalytic activity
US20200343562A1 (en) * 2019-04-24 2020-10-29 Toyota Motor Engineering & Manufacturing North America, Inc. Surface modified platinum or platinum alloy catalyst for oxygen reduction reaction
CN113674812A (en) * 2021-07-30 2021-11-19 哈尔滨工业大学 Design method of metal-nitrogen-carbon nitrogen fixation electrocatalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140050995A1 (en) * 2011-03-01 2014-02-20 Liming Dai Metal-free oxygen reduction electrocatalysts
US20200127300A1 (en) * 2017-06-13 2020-04-23 The Board Of Trustees Of The Leland Stanford Junior University Electrochemical catalysts with enhanced catalytic activity
US20200343562A1 (en) * 2019-04-24 2020-10-29 Toyota Motor Engineering & Manufacturing North America, Inc. Surface modified platinum or platinum alloy catalyst for oxygen reduction reaction
CN113674812A (en) * 2021-07-30 2021-11-19 哈尔滨工业大学 Design method of metal-nitrogen-carbon nitrogen fixation electrocatalyst

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