LU503346B1 - A method for constructing an efficient electrocatalyst for acid-base all-environment oxygen reduction reaction - Google Patents
A method for constructing an efficient electrocatalyst for acid-base all-environment oxygen reduction reaction Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 31
- 239000001301 oxygen Substances 0.000 title claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006722 reduction reaction Methods 0.000 title claims abstract description 21
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 123
- 238000012216 screening Methods 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 3
- 238000001179 sorption measurement Methods 0.000 claims description 70
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 6
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- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 238000005051 zero-point vibrational energy Methods 0.000 claims description 5
- ZAKOWWREFLAJOT-CEFNRUSXSA-N D-alpha-tocopherylacetate Chemical compound CC(=O)OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-CEFNRUSXSA-N 0.000 claims description 4
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000007547 defect Effects 0.000 claims description 2
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- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
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- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention discloses a method for constructing an acid-base all- environment efficient oxygen reduction reaction electrocatalyst, which belongs to the field of catalyst technology. The invention first constructs a pre-screening model for all ORR catalysts; screens the catalyst models based on ΔEf < 0eV and ΔEb>Ecoh; then screens the catalysts sequentially based on ΔE*O2 < -0.5eV, ΔE*O2 < ΔE*H2O, ΔE*O2 > - 1.5eV (acidic) or ΔE*OH > -3.5eV (basic), ΔG*OH > 0.4eV, ΔG*OH < 1.6eV, ΔG*OOH→H2O2>∆G2 screening catalysts; finally, the acid-base all-environment efficient oxygen reduction reaction electrocatalysts were screened according to η acid < 0.8V and η base < 0.8V. The present invention is based on computer to carry out catalyst screening research, which has the advantages of low resource consumption, low carbon and environmental protection, high accuracy and high repeatability.
Description
LU503346
A METHOD FOR CONSTRUCTING AN EFFICIENT ELECTROCATALYST FOR
ACID-BASE ALL-ENVIRONMENT OXYGEN REDUCTION REACTION
The present invention belongs to the field of catalyst technology, and in particular relates to a method of constructing an acid-base all-environment efficient oxygen reduction reaction electrocatalyst.
Fossil fuel combustion produces a large amount of carbon, nitrogen and sulfur containing exhaust gas, on the one hand, the exhaust gas emissions take away a lot of heat energy, resulting in energy waste; on the other hand, toxic exhaust gas, such as
CO, NOx, SO» will lead to serious environmental problems, even non-toxic gases, such as CO» will cause the greenhouse effect. Moreover, traditional fossil fuels are non- renewable resources, and the increasing depletion of resources will definitely lead to an energy crisis. Therefore, there is an urgent need for human society to develop new energy sources to alleviate the growing energy crisis and environmental problems.
As one of the ideal devices for efficient utilization of clean energy (hydrogen energy), hydrogen-oxygen fuel cells play an important role in meeting the urgent need for sustainable energy because of their high energy conversion efficiency, high power density, and clean environment. However, the slow kinetic cathodic oxygen reduction reaction (ORR) is one of the key factors hindering the widespread application of hydrogen-oxygen fuel cells. The ORR equilibrium potential is 1.23V/0.402V in acidic/alkaline environment respectively, i.e., the reaction kinetics of ORR in alkaline environment is faster than that in acidic environment. However, the acidic environment has a higher power density than the alkaline environment. In addition, the conductivity of OH- in the alkaline environment is lower compared to that of H+ in the acidic environment. Also, Ha and O2 must be ultra-pure in the alkaline environment, and the presence of CO» in the gas source can lead to carbonate precipitation in the membrane.
Thus, it can be seen that both acidic and alkaline solution environments have their own advantages, and Pt-based catalysts are currently the mainstream ORR electrocatalysts in the market for general use in acidic and alkaline environments. However, Pt is a precious metal and its large-scale commercial application is seriously hindered by fs scarce resources, high cost, susceptibility to poisoning by CO in the gas source, low durability, etc.
Therefore, for the constraint bottleneck of hydrogen-oxygen fuel cells, it is necessary to design a rapid screening process of an acid-base all-purpose ORR diatomic catalyst with high catalytic efficiency and high stability based on the abundant resources of transition metal Tm and strong multi-electron activity characteristics, combined with the high atomic dispersion rate, active site utilization and strong synergistic effect of diatomic catalysts
The existing technology is based on a large number of experimental attempts, which leads to the waste of many resources such as human, material and financial resources due to the existence of certain unknowns, and faces many challenges such as the ambiguity of the catalytic mechanism. In response to the shortcomings of the existing technology, the present invention provides a method for constructing an acid-base all- environment high-efficiency oxygen reduction reaction electrocatalyst, carries out theoretical research based on the first nature principle, provides a screening method for predicting a high-performance acid-base all-environment ORR catalyst model, explores the catalytic mechanism, and provides effective guidance for experimental synthesis.
To achieve the above purpose, the present invention provides the following solutions:
One of the objects of the present invention is to provide a method for constructing an acid-base all-environment efficient oxygen reduction reaction electrocatalyst, the described method being a screening method for N-ligand bimetallic atom co-doped graphene catalysts, comprising the steps of: (1) Pre-screening models of all ORR catalysts with different bimetallic combinations and different N coordination cases were constructed by VESTA, and the structures were optimized based on the first-nature principle; (2) Calculation of formation energy AE; and binding energy AE, for the pre-screened models described; screening of stable catalyst models based on AE: < OeV and AE; >
Econ (Metal cohesion energy); (3) Construct the adsorption model of catalyst for Oz in different adsorption modes and optimize the structure (choose the lowest energy adsorption model), calculate the adsorption energy of catalyst for O2 AE=o,; screen the catalyst model according to
AE-0,<-0.5€eV to ensure the effective adsorption and activation of catalyst for Oz; 1000068 (4) Construct the H:O adsorption model and optimize the structure, calculate the H>O adsorption energy of the catalyst AE-H,o; in order to avoid solvent passivation of the catalyst and ensure the recyclability of the catalyst, select the catalyst model with weak or no H2O adsorption according to AE+o,< AE+H50; (5) Classification of the catalyst model into acidic (pH=0) and basic (pH=14) environments: a. Acidic environment: According to Sabatier's principle, too strong Oz adsorption will lead to difficult product desorption. Screen the catalyst for proper oxygen adsorption according to AE+0,>-1.5eV, if AE+«0,<-1.5eV, consider the possibility of using Oz as ligand modified catalyst and proceed to step (3) for further screening. b. Alkaline environment: too strong OH adsorption may passivate the catalyst and make the catalysis difficult to cycle. Construct a model for OH adsorption by the catalyst and optimize the structure, calculate the OH adsorption energy AE+ox, screen the catalyst for proper OH adsorption according to AE+ox>-3.5eV, if AE-ox<-3.5eV means OH is difficult to desorb, re-enter OH as ligand to continue screening in step (3). (6) Considering the effect of zero-point vibrational energy and entropy on Gibbs free energy, the OH adsorption model is further calculated to calculate the OH adsorption free energy AG-on, and the catalyst with relatively high catalytic activity is screened according to AG-ox>0.4eV. If AG-on<0.4eV, n is necessarily greater than 0.8V, the catalyst does not have high activity, Acidic environments can be considered for the possibility of O2 as a ligand, while basic environments can be considered for the possibility of OH as a ligand, proceed to step (3) to continue the screening. (7) Screen the catalyst according to AG-on<1.6eV, if AG+-ox>1.6eV, according to the volcano graph of n vs. AG*ox, N must be greater than 0.8V, indicating that the catalyst has a weak adsorption capacity for oxygen, small activation O2 capacity and low catalytic activity, so discard this part of the catalyst. (8) The generation of side reaction H202 will corrode the catalyst and affect the durability of the catalyst, so the possibility of generating H2O2 should be minimized; calculate the Gibbs free energy AG-ooH-H202 for OOH—H202 and the reaction energy
AG» for the second electron step of the main reaction, and screen the catalyst with low side reaction rate according to ÀG-ooH-H202>AGa2. (9) Calculate the magnitude of the overpotential n and screen the acid-base all- environment efficient oxygen reduction reaction electrocatalysts according to n acia < 0.8
V and N pase < 0.8 V.
Further, the formula for calculating the formation energy AEr described in step (2) jg 200340 shown in Eq. 01; and the formula for calculating the binding energy AE» described in Eq. 02 to Eq. 03 is shown in.
AEF=ETm Tma-Nx-Co.x-gra + (4+X) He — (Egra + XUN + UTm1+HTma) Eq.01;
AE64=ETm2-Ny-Ce-x-grat HTm4—ETm1Tm2-Nx-Ce-x-gra Eq.02;
AEv2=ETm4-Ny-Ce-x-grat HTm2—ETm1Tm2-Nx-Ce-x-gra Eq.03;
ETm1Tm2-Nx-C6-x-gra ANd Egra refer to the system energy of the N-C coordination environment with double Tm atoms synergistically constructing doped graphene-type diatomic catalysts and defect-free graphene Gia, respectively; uc and un refer to the system energy of a single C atom and 1/2 Na molecule in graphene Gra, respectively;
MTm¢ and ptm, refer to the energy of single-atom metal Tm1 and Tmz2; ETma-N-Ce.xgra ANd
ETm4-Ne-Cexgra refer to the system energy of N-C coordination double Tm atom co-doped graphene catalyst with Tm1 and Tm2 vacancy defects, respectively.
Further, the adsorption energy AE-o, of the catalyst for O2 as described in step (3) is calculated as shown in Eq. 04.
AE+02= E+02-Tm1Tm2-Nx-C6.x-gra — ETm1Tma-Nx-Ce.xcora — E02 Eq.04;
E*02-Tm1Tm2-Nx-C6.x-gra IS the total system energy of O2 adsorption by the catalyst, and
Eo, is the energy of a single O2 molecule.
Further, the adsorption energy AE>H,o of H20 by the catalyst described in step (4) is calculated as shown in Eq. 05.
AEH20= E*H20-Tm1Tm2-Nx-C6.x-gra — ETm1Tma-Nx-Co.x-gra — EH20 Eq.05;
E-H20-Tm1Tm2-Nx-Ce-x-gra IS the total system energy of HO adsorption by the catalyst, and Expo is the energy of a single H20 molecule
Further, the OH adsorption energy AE-on described in step (5) is calculated as shown in Eq. 06.
AE*ox= E+*oH-Tm1Tm2-Nx-Ce.x-gra — ETm1Tm2-Nx-Cexgra — EoH Eq.06;
E+OH-Tm1Tm2-Ny-Ce.xgr@ is the total system energy of OH adsorption by the catalyst, and Eon is the energy of a single OH.
Further, the OH adsorption free energy AG-ox described in step (6) is calculated as shown in Eq. 07.
AGoH=G*0H-Tm1 Tma-Nx-Ce.x-gra — GTm1Tm2-N-C6xgra-(GH2o — 1/2GH,) Eq.07; | U503346
G+OH-Tm1Tm2-Ny-Ce.x-gra ANd GTm4Tm2-Ny-Cecgra Are the Gibbs free energies of the system with OH adsorbed by the catalyst and the catalyst system alone, respectively, and Gh,o and Gn, are the Gibbs free energies of individual H2O and H2 molecules, respectively.
Further, the Gibbs free energy AG-ooH>H202 for OOH—H202 and the reaction energy AG» for the second electron step of the main reaction described in step (8) are calculated as shown in Eq. 08 and Eq. 09.
AG+ooH>H202=GH202+ GTm4 Tm2-Ny-C6.x-gra—(G+00H-Tm1Tm2-Ny-C6.xgrat(0.5GH,—0.0592xpH))
Eq.08;
AG2=G+0-Tm1Tm2-Nx-Ce-xgrat GH20—(0.5GH,—0.0592xpH)—G+00H-Tm1Tm2-Nx-Ce-xgra Eq.09
G*00H-Tm4Tm2-Ny-Cex-gra ANd G+0-Tm4Tm2-Ny-Ce.xgra refer to the Gibbs free energy of the system in which the catalyst adsorbs OOH and O, respectively, and Gh,o, refers to the
Gibbs free energy of a single H202 molecule.
Further, the equations for calculating N acia and N base AS described in step (9) are shown in Eq. 10 to Eq. 12 as follows.
AG=AEnrT+AZPE-TAS+AGu+AGpH Eq.10;
Ne= 1.23 V + [AG1, AG2, AG3, AG4]mad€ Eq.11;
Nw=0.402 V + [AG1, AG2, AG3, AG4]mad € Eq.12;
AEprTis the reaction energy obtained based on the DFT calculation, AZPE and AS are the changes of zero-point vibrational energy and entropy before and after the reaction, respectively, T is the temperature, and AGu and AGpx are the effects of potential and pH on the reaction free energy AG, respectively.
Further, AGu and AGpH are calculated as shown in Eq. 13 and Eq. 14.
AGu=-neU Eq.13;
AGpH=keT*In10xpH Eg.14: n is the number of electron transfer, U refers to the applied potential, and kg refers to the Boltzmann constant.
Other catalysts can be screened by referring to this method.
Beneficial effects of the present invention. (1) The present invention is based on a high-performance computer for catalyst screening research, which is different from pure experiments with large resource consumption and "three waste emissions", the invention has the advantage of low carbon and environmental protection with minimal resource consumption and no pollution emissions. 7505346
(2) The invention comprehensively considers all possible cases of catalyst systems and provides full coverage of potential configurations, which is different from blind trial and error experiments and helps to avoid the omission of high-performance catalysts.
(3) The invention adopts progressive screening, which is different from pure experimental inefficient blind trial and error, overcomes the disadvantages of high resource consumption and long research period, and is conducive to narrowing the screening scope and quickly locating potential high-performance catalysts.
(4) The invention conducts computational research based on the firstness principle, which is different from the disadvantages such as high experimental chance and low repeatability, and is characterized by high accuracy and high repeatability.
(5) The invention conducts catalyst research from the atomic scale, revealing the catalytic pathway and mechanism of catalysts from the microscopic perspective, filling the shortcomings of experiments for catalysts with unknown mechanism, which is conducive to guiding experimental synthesis and further promotion and application.
LU503346
In order to more clearly illustrate the technical solutions in the embodiments or prior art of the present invention, the following is a brief description of the accompanying drawings to be used in the embodiments, and it is obvious that the accompanying drawings in the following description are only some embodiments of the present invention, and other accompanying drawings can be obtained from these drawings without creative work for those of ordinary skill in the art.
FIG. 1 is a flow chart of the screening of a catalyst for an acid-base all-environment efficient oxygen reduction reaction
To enable a person skilled in the art to better understand the technical solutions of the present invention, the invention is described in further detail below in conjunction with the embodiments.
Example 1
Using ZnCoNe-doped graphene catalyst (ZnCoNs@Gra) as an example. (1) Construction of ZnCoNs@Gra catalyst pre-screening model by VESTA and optimization of the structure based on the first-nature principle. (2) Calculating the formation energy AE=-3.34eV and binding energy AE»,=1.62eV (Econ=1.35eV), AEb,=4.71eV (Ecoh:=4.39eV); the structure of ZNCoNs@Gra was found to be stable based on AEr <0eV and AEp>Econ. (3) Constructing the adsorption model of catalyst on Oz in different adsorption modes and optimizing the structure (the lowest energy adsorption model was selected), calculating the adsorption energy of catalyst on O2 AE+oz = -2.12eV, which indicates the effective adsorption and activation of ZNCoNs@Gra on Oz according to AE+02 < -0.5eV. (4) Constructing a model for the adsorption of H2O by the catalyst and optimizing the structure, calculating the adsorption energy of the catalyst on HO AEH,o = -0.54eV, which indicates the weak adsorption of HO by ZnCoNe@Gra according to AE+0,<
AE-H20, which effectively avoids solvent passivation of the catalyst and ensures the recyclability of the catalyst. (5) The catalyst model was divided into two environments, acidic (pH=0) and basic (pH=14).
a. Acidic environment: consider the possibilty of O2 as ligand modification (ZNCoNsO2@Gra) based on AE-0,<-1.5eV and proceed to step (3) to continue the 999346 screening. (i) Construct the adsorption model of catalyst for O2 under different adsorption modes of
ZnCoNsO2@Gra and optimize the structure (choose the lowest energy adsorption model), calculate the adsorption energy of ZnCoNsO:@Gra for O2 AE+0o,=-0.94eV, according to AE-0,<-0.5eV, ZnCoNsO@Gra ensures the effective adsorption and activation of O2. (ii) Construct the adsorption model of ZNCoNs0:@Gra on H>O and optimize the structure, calculate the adsorption energy of catalyst on H20 AE-H,0=-0.34eV, according to AE+0o,< AE+,0, which indicates that ZnCoNsO2@Gra weakly adsorbs on H2O, which effectively avoids the catalyst from solvent passivation and ensures the recyclability of the catalyst. (iii) According to AE+0,>-1.5eV, ZnCoNsO2@Gra has proper adsorption for oxygen. (4) Considering the effect of zero-point vibrational energy and entropy on Gibbs free energy, the OH adsorption model was further calculated and the OH adsorption free energy AG-on=1.12eV was calculated, and according to AG-ox>0.4eV it is known that
ZnCoNsO2@Gra is a catalyst with relatively high catalytic activity. (5) according to AG-ox<1.6eV screening it can be known that ZnNCoNsO2,@Gra has a stronger activation of oxygen and higher catalytic activity. (6) Calculate the Gibbs free energy of OOH—H202 AG-o0H-H202=-0.60eV and the reaction energy of the second electron step of the main reaction AGz=-1.76eV, based
ON AG*+00H-H202>AGz it is known that ZNCoNs02@Gra has low side reaction incidence. b. Alkaline environment: too strong OH adsorption may passivate the catalyst and make the catalysis difficult to cycle. Construct the model of OH adsorption by catalyst and optimize the structure, calculate the OH adsorption energy AE+ox=-3.84eV, according to
AE+ox<-3.5eV indicates that OH is difficult to desorption, re-enter OH as ligand (ZnCoNsOH@Gra) to continue the screening in step (3). (i) Construct the adsorption model of catalyst for O2 under different adsorption modes of
ZnCoNsOH@Gra and optimize the structure (choose the lowest energy adsorption model), calculate the adsorption energy of ZnCoNeOH@Gra for O2 AE+0,=-1.36eV, according to AE-0,<-0.5eV, ZNCoNsOH@Gra ensures the effective adsorption and activation of O2.
(ii) Constructing the adsorption model of ZNCoNsOH@Gra on H20 and optimizing the structure, calculating the adsorption energy of catalyst on HO AEiy0=-0.026V 999946 according to AE+0,< AE+H,0, indicating that ZnCoNsOH@Gra weakly adsorbs on Hz0, which effectively avoids the catalyst from solvent passivation and ensures the recyclability of the catalyst. (iif) According to AE+0,>-1.5eV, ZnCoNeOH@Gra has proper adsorption for oxygen. (4) Considering the effect of zero-point vibrational energy and entropy on the Gibbs free energy, the OH adsorption model was further calculated and the OH adsorption free energy AG-on = 0.50 eV was calculated. According to AG-on>0.4 eV it is known that
ZnCoNsOH@Gra is a catalyst with relatively high catalytic activity. (5) Screening based on AG-on<1.6eV shows that ZnCoNsOH@Gra has a stronger activation of oxygen and higher catalytic activity. (6) Calculate the Gibbs free energy of OOH—Hz202 AG+ooH-H20,=-0.18eV and the reaction energy of the second electron step of the main reaction AGz=-1.67eV, based
ON AG+ooH-H20,>AG2 it is known that ZnCoNsOH@Gra has low side reaction incidence. (6) Calculation of the overpotential n magnitude, N acia = 0.54 V and n base = 0.73 V.
According to n acid < 0.8 V and n base < 0.8 V ZnCoNe@Gra is found to be an acid-base all-environment efficient oxygen reduction reaction electrocatalyst.
Contrast ratio 1 1. Precursor strategy for the synthesis of transition metal-doped carbon-based diatomic catalysts 2-Methylimidazole 2-Melm and zinc nitrate Zn (NO3)2 were mixed and dissolved in an appropriate amount of methanol CH3sOH solvent by 1:2 mass to prepare ZIF8 solution.
Then the transition metal-acetylacetonate compounds Tm1(acac)x and Tmz(acac)x were added with zinc nitrate by the same mass and stirred for 0.5 h. Then it was transferred to a polytetrafluoroethylene hydrothermal synthesis reactor heated to 120 °C and held for 4 h. The precipitate was obtained by centrifugation at high speed and washed by methanolic CH3O0H, and then dried under vacuum at a constant temperature of 60°C for 12 h to obtain the precursor Tm1Tm2@ZIF8 encapsulating Tm(acac)x.
The prepared precursor Tm1Tm2@ZIF8 was placed in a tube furnace and heated to 918°C (slightly above the Zn boiling point of 907°C, evaporating Zn while leaving the high boiling point of the transition metal Tm) at a rate of 5°C/min under flowing Na and held for 2 hours, and annealed to room temperature with the furnace. Then the powder was acid-washed with 0.5 mol H2SO4 for 2 h at room temperature to remove the potential large-size metal material, and finally washed by centrifugation with ultrapure water and dried under vacuum at 60 °C for 12 h to obtain the transition metal-doped porous carbon-based diatomic catalyst. 17000868 2. Modern analytical techniques to characterize the microscopic physical phase information of the synthesized catalysts
The BET specific surface area and pore size distribution were determined by nitrogen adsorption instrument. The structure and physical phase of the synthesized catalyst samples were determined by X-ray diffractometer. The microstructure and morphology were observed by transmission electron microscope TEM and scanning electron microscope SEM; the content and distribution of different elements in the synthesized catalysts were detected by X-ray energy spectrum analyzer EDS; and the elemental content of transition metals was accurately determined by inductively coupled plasma mass spectrometer ICP-MS. The overall physical phase information of the catalyst at the microscopic level was obtained by relevant test analysis.
Further information on the active center configuration of the synthesized catalysts can be obtained by high angle annular dark field scanning electron microscopy HAADF-
STEM and selected area electron diffraction SAED; X-ray photoelectron spectroscopy (XPS) system was used to test the active center configuration elements and their chemical valence states in the catalyst samples; X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) were used to determine the catalyst content and distribution. XANES and extended X-ray absorption fine structure EXAFS were used to characterize the coordination relationships of the active center configuration. The above-mentioned tests provide comprehensive information on the Tm active site and N-C coordination environment. 3. In situ testing of ORR catalytic performance and mechanism by electrochemistry combined with spectroscopy
A 5 mg sample of catalyst was dispersed in a mixture of 480 uL ethanol, 480 uL H2O and 40 uL 5% PFOS ethanol solution degraded by acoustic degradation for 0.5 hr. The catalyst was then dropped on a polished glassy carbon rotating disc electrode RDE or rotating disc ring electrode RRDE with diameter d=5 mm and dried at room temperature.
The catalyst loading was ~0.5 mg/cm?.
Tests were performed at room temperature using a three-electrode system with acidic and alkaline environments: the electrolyte was a saturated N2/O2 aqueous solution of 0.1 M HCIO4 and 0.1 M KOH, respectively, the reference electrode was a saturated glycol electrode SCE, and the counter electrode was a carbon electrode. All measured potentials were calculated according to Equation (1) and converted to the reversible hydrogen electrode potential RHE. 7505346
ERHE = ESCE + 0.059 x pH + 0.2412 V (1).
Firstly, cyclic voltammetry CV scan was carried out to calculate the bilayer capacitance
Ca and electrochemical specific surface area ECSA; subsequently, linear scanning voltammetry LSV scan was carried out to obtain the ORR onset potential Eonset, half- wave potential E12 and limiting diffusion current density DLCD, and then the electrocatalytic ORR overpotential n was obtained, and the Tafel slope was obtained by fitting the LSV curve, determining the The reaction limit step RDS was determined by fitting the LSV curve to obtain the Tafel slope, and the charge transfer resistance Rct.
The Nyquist plot was obtained based on the electrochemical impedance spectroscopy
EIS test, and finally the conversion frequency TOF of the catalyst was investigated by testing the CV curve in neutral phosphate buffered saline PBS.
The electron transfer number n during ORR was calculated from the slope of the
Koutecky-Levich (K-L) curve: j* = je! + (Bw1/2)!, B = 0.62nFCOD0%3V-1% (2).
Equation (2) in jk and j represent the kinetic control current density at constant potential and the total reaction current density measured, respectively, w is the rotation rate of the disc electrode, F is the Faraday constant 96485 C/mol, Co is the volume concentration of O2 1.2 x 10° mol/cm?, Do is the diffusion coefficient of O2 in 0.1 M
HCIO4 or 0.1 M KOH solution 1.9 x 10°cm?/s, and V represents the viscosity of the electrolyte 0.01 cm?/s. The yield of the side reaction H202 was calculated based on the electron transfer number n by the relationship between the electron transfer number n and the yield of hydrogen peroxide H2O2 shown in Equation 3. n=4ia/(ia+i/N), H202%=200id/(iaxN+ir) (3). la is the disc current density, ir is the ring current density, and Pt ring current collection efficiency N=0.37.
Contrast 1 has the following drawbacks. (1) This existing technology of experimental synthesis, then characterization of the catalyst, and finally electrochemical testing of the performance, due to its unknown nature leads to the possible synthesis of insufficient catalyst performance, resulting in a waste of time, energy, material resources and other resources in various aspects. @)Multiple steps in the test procedure and many variables in the process conditions lead to low reproducibility of the test results. (3)Long test cycle, covering catalyst preparation, catalyst characterization, and catalytic performance testing, in addition to subsequent process optimization and performance improvement also face the disadvantage of long cycle time. (4)Multiple test consumables and large "three waste" emissions, including catalyst preparation and catalytic performance testing, and the oor subsequent optimization of process and performance improvement also face the challenges of many test consumables and large "three waste" emissions. (5) The cost of experimental research is high, including catalyst preparation, catalyst characterization and catalytic performance testing, especially catalyst characterization is time-consuming and expensive.
This invention is based on first principles of theoretical calculations, which has the advantages of low resource consumption, low time cost, no pollution emission, high repeatability, and provides accurate guidance for experimental synthesis, thus providing a guarantee for the promotion of hydrogen-oxygen fuel cells. It also effectively enhances the high value-added utilization of mineral resources and the scientific and technological competitiveness of the catalytic industry, helps realize the promotion and application of new energy vehicles, and comprehensively promotes the optimization of energy industry structure and ensures energy security.
The above-described embodiments are only a description of the preferred way of the present invention, not a limitation of the scope of the present invention. Without departing from the spirit of the design of the present invention, all kinds of deformations and improvements made to the technical solutions of the present invention by the ordinary skilled person in the art shall fall within the scope of protection determined by the claims of the present invention.
Claims (9)
- CLAIMS LU5033461. A method for constructing an acid-base all-environment efficient oxygen reduction reaction electrocatalyst, characterized in that said method is a screening method for N- ligand bimetallic atom co-doped graphene catalysts, comprising the steps: (1) constructing a pre-screening model for all ORR catalysts; (2) calculation of formation energy AEr and the binding energy AEs for the pre-screening models; screening the catalyst models based on AE<0eV and AEp>Econ; (3) constructing a model for the adsorption of O2 by the catalyst and calculating the adsorption energy AE+o2 of the catalyst for O2; screening the catalyst model based on AE+o» < -0.5eV, (4) constructing a model for the adsorption of H2O by the catalyst and calculating the adsorption energy of AE«20 by the catalyst; screening the catalyst model according to AE+02<AE*H20; (5) classify the catalyst model into two environments, acidic and basic:a. acidic environment: screen the catalyst based on AE+o2>-1.5eV, if AE+0o2<-1.5eV, proceed to step (3) to continue screening;b. alkaline environment: construct a model of OH adsorption by the catalyst, calculate the OH adsorption energy AE+oH, screen the catalyst based on AE+ox>-3.5eV, if AE+oH<-3.5eV, proceed to step (3) to continue screening; (6) calculate the OH adsorption free energy AG-on, plot the overpotential n against the volcano curve of AG-on and screen the catalyst according to AG+on>0.4eV; if AG-on<0.4eV, proceed to step (3) for further screening; (7) screen the catalyst based on AG-on < 1.6 eV and discard this part of the catalyst if AG+ox > 1.6 eV; (8) calculate the Gibbs free energy AG+ooH>H202 for OOH—H202 and the reaction energy AG: for the second electron step of the main reaction, and screen the catalyst based on AG*ooH—H202>AGz: (9) calculate the magnitude of the overpotential n and screen acid-base all-environment efficient oxygen reduction reaction electrocatalysts based on N acia < 0.8 V and n pase <0.8 V.2. The method for constructing an acid-base all-environment efficient oxygen reduction reaction electrocatalyst according to claim 1, characterized in that step (2) the formation energy AEf is calculated as shown in Eq. 01; the binding energy AE» is calculated as shown in eq. 02 to eq. 03. 7505346 AE=Etm1Tma-Nx-C6-x-grat(4+X) Hc—-(EgratXUN+UTm4 +HTm2) eq.01 ; AEb1=ETmy-Nx-Co.x-grat MTm—E Tm Tmz-Nx-Co.x-ora eq.02; AEb;=ETmi-Nx-Co.x-grat MTmo—E Tm Tma-Nx-Co.x-gra eq.03; among them, Etmitm2-Nx-cex-gra @nd Ega refer to the system energy of the N-C coordination environment with double Tm atoms in concert to construct doped graphene- based diatomic catalysts and defect-free graphene Gra, respectively; Uc and pn refer to the system energy of a single C atom and 1/2 Na molecule in graphene Gra, respectively; UTm1 and ptm refer to the energy of single-atom metal TM4 and Tmo respectively; ETmz-Nx-C6-xgra and ETmi-Nx-C6-xgra refer to the system energy of N-C coordination double Tm atom co-doped graphene catalysts with Tm1 and Tm» vacancy defects, respectively.3. The method for constructing an acid-base all-environment efficient oxygen reduction reaction electrocatalyst according to claim 1, characterized in that step (3) the adsorption energy AE-o2 of the catalyst for O2 is calculated as shown in eq. 04. AE+02= E*02-Tm1Tm2-Nx-C6-x-gra — ETm1Tma-Nx-C6-x-gra — Eo2 eq.04 ; E+02-Tm1Tm2-Nx-C6-x-gra IS the total system energy of O2 adsorption by the catalyst and Eoz is the energy of a single O2 molecule.4. The method for constructing an acid-base all-environment efficient oxygen reduction reaction electrocatalyst according to claim 1, characterized in that step (4) the adsorption energy AE-+20 Of the catalyst for H2O is calculated as shown in eq. 05. AEH20= E*H20-Tm4Tm2-Nx-C6-x-gra — ETm1Tm2-Nx-C6-x-gra — EH20 eq.05; E-H20-Tm1Tm2-Nx-C6-x-gra IS the total system energy of HO adsorption by the catalyst and Enzo is the energy of a single H20 molecule.5. The method for constructing an acid-base all-environment efficient oxygen reduction reaction electrocatalyst according to claim 1, characterized in that the OH adsorption 9946 energy AE-on of step (5) is calculated as shown in eq. 06. AE*ox= E*oH-Tm1Tmo-Nx-Cg.x-gra — ETm1Tmo-Nx-Cg.x-gra — EoH eq.06; E+OH-TM1Tm2-Nx-C6-x-gra IS the total system energy of OH adsorption by the catalyst and EOH is the energy of a single OH.6. The method for constructing an acid-base all-environment efficient oxygen reduction reaction electrocatalyst according to claim 1, characterized in that the OH adsorption free energy AG*OH of step (6) is calculated as shown in eq. 07. AG+oH=G-0H-Tm1Tm2-Nx-Ce.x-gra — GTm1Tm>-Ny-C6.x-gra-(GH20 — 1/2GHj) eq.07 G*OH-Tm1Tm2-Nx-Cé-x-gra ANd GTm1Tm2-Nx-C6-x-gra are the Gibbs free energies of the system with OH adsorbed by the catalyst and the system with the catalyst alone, respectively, and Gro and Ghz are the Gibbs free energies of individual HO and Hz molecules, respectively.7. The method for constructing an acid-base all-environment efficient oxygen reduction reaction electrocatalyst according to claim 1, characterized in that the Gibbs free energy AGrooH-H202 for step (8) OOH—H202 and the reaction energy AG2 for the second electron step of the main reaction are calculated as shown in eq. 08 and eq. 09. AG+ooH>H202=GH202+ GTm4 Tm2-Ny-C6.x-gra—(G+00H-Tm1Tm2-Ny-C6.xgrat(0.5GH,—0.0592xpH))eq.08; AG2=G+0-Tm 1 Tma-Nx-Co-x-grat GH20—(0.5GH,—0.0592xpH)—G+00H-Tm1Tm2-Nx-Ce.xgra €q.09 G-+O0H-Tm1Tm2-Nx-C6-x-gra aNd G-O-Tm1Tm2-Nx-C6-xgra refer to the Gibbs free energy of the system in which the catalyst adsorbs OOH and O, respectively, and GH2o2 refers to the Gibbs free energy of a single H202 molecule.8. The method for constructing an acid-base all-environment efficient oxygen reduction reaction electrocatalyst according to claim 1, characterized in that step (9) n acid and 17905346 base are calculated as shown in eq. 10~ eg. 12 as follows. AG=AEnr+AZPE-TAS+AGu+AGpH eq.10; Ne= 1.23 V + [AG1, AG2, AG3, AG4]mad€ eq.11; Nw=0.402 V + [AG1, AG2, AG3, AG4]mad € eq.12; AEbrT is the reaction energy based on DFT calculations, AZPE and AS are the change in zero-point vibrational energy and entropy before and after the reaction, respectively, T is the temperature, and AGu and AGpH are the effect of potential and pH on the reaction free energy AG, respectively.9. The method for constructing an acid-base all-environment efficient oxygen reduction reaction electrocatalyst according to claim 8, characterized in that AGu and AGpH are calculated as shown in eq. 13 and eq. 14. AGu=-neU eq.13; AGpH=keTxIn10xpH eq.14 ; n is the number of electron transfers; U is the applied potential and kB is the Boltzmann constant.
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