CN110364230B - Method for rapidly screening organic base in reaction of preparing formic acid from carbon dioxide and hydrogen under catalysis of copper - Google Patents
Method for rapidly screening organic base in reaction of preparing formic acid from carbon dioxide and hydrogen under catalysis of copper Download PDFInfo
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Abstract
The invention provides a method for rapidly screening organic alkali in a reaction of preparing formic acid from carbon dioxide and hydrogen under catalysis of copper, belonging to the field of computational chemistry. In the reaction of preparing formic acid by catalyzing carbon dioxide with a copper-organic base ligand, the influence of different organic bases on the structure of a copper complex and the reaction rate-determining step potential barrier is calculated by simulating the reaction process by using an M06 functional and a 6-31G group, so that the organic base with the best activity is effectively predicted and screened, repeated experimental investigation and comparison in a laboratory are omitted, and the method is simple and reasonable, easy to operate, low in cost, accurate in result and has potential practical value.
Description
Technical Field
The invention belongs to the technical field of computational chemistry, and particularly relates to a method for rapidly screening organic base in a reaction of preparing formic acid from carbon dioxide and hydrogen under catalysis of copper.
Background
Hydrogen energy is regarded as the clean energy with the most development potential in the 21 st century, however, hydrogen is flammable and explosive gas, and the storage and transportation of hydrogen are crucial technologies, and the hydrogen energy utilization is a bottleneck towards scale.
The formic acid obtained by carbon dioxide hydrogenation is liquid at room temperature, and can beIs safe to store and transport and is a renewable hydrogen storage material. Meanwhile, formic acid is not only a common chemical fuel, but also a basic organic chemical raw material, and is widely used in the fields of pesticides, dyes, medicines and the like. From CO 2 And H 2 The direct catalytic synthesis of formic acid is a reaction with high atom economy, and can reduce the dependence on fossil resources and meet the current green chemical development trend.
From CO 2 And H 2 The direct synthesis of formic acid belongs to an adverse reaction from the thermodynamic point of view, but the Gibbs function of the whole reaction can be changed after the transition metal catalyst is added, so that the reaction becomes a thermodynamically favorable reaction, thereby developing CO 2 The research field of the high-efficiency hydrogenation catalyst is very active. Among the transition metal catalysts that have been developed, ruthenium and iridium complexes have high catalytic yields. Subsequently, low cost copper complexes were demonstrated to catalyze CO efficiently 2 The catalytic activity of the copper complex depends on the alkaline ligand, and the alkalinity and the steric hindrance of the alkaline ligand influence the activity of the copper complex and the yield of the formic acid to a great extent.
At present, the research on the activity influence of an alkali ligand on a copper complex is mainly carried out on experiments through spectrum and mass spectrum, but the types of organic bases are various, and the adoption of the spectrum to search the structure-activity relationship between different organic bases and the activity of the copper complex is difficult to realize intuitively and accurately, and the process is complicated and consumes much time.
Disclosure of Invention
In order to overcome the defects, the invention provides a method for rapidly screening organic alkali in the reaction of preparing formic acid from carbon dioxide and hydrogen under the catalysis of copper. The method can effectively predict the optimal organic base influencing the catalytic activity in the reaction of preparing formic acid by catalyzing carbon dioxide with copper, and has the advantages of simplicity, reasonability, easy operation, low cost, accurate result and potential practical value.
The technical scheme adopted for realizing the purpose is as follows: a method for rapidly screening organic alkali in a reaction of preparing formic acid from carbon dioxide and hydrogen under the catalysis of copper comprises the following steps:
step 1: selecting an organic base complex with high catalytic efficiency, and designing a detailed reaction path according to a chemical basic principle;
step 2: drawing an intermediate body of a designed path and a structural formula on a transition state through ChemDraw, and manufacturing a Gaussian input file on the basis;
and step 3: optimizing an intermediate and a transition state structure of a designed path by using different functional and 6-31G-base groups through quantum chemical simulation software Gaussian09, and extracting a Gibbs free energy correction value from an output xx.log file;
and 4, step 4: performing solvation single-point calculation on the structure obtained in the step 3 by adopting an m06 functional, a 6-311+ G base group and a polarization continuous medium model (PCM), extracting electronic energy from an output xx.log file, and adding the electronic energy and the Gibbs free energy correction value obtained in the step 3 to obtain an absolute free energy value of an intermediate or a transition state;
and 5: drawing a potential energy profile diagram of the reaction path according to the obtained absolute free energy value, finding out a reaction speed-determining step, a related intermediate and a transition state thereof, and calculating a speed-determining step energy barrier;
step 6: replacing the intermediate related to the speed-determining step and the organic base ligand in the transition state structure with another organic base ligand, and recalculating the speed-determining step energy barrier;
and 7: repeating the step 6 to obtain a plurality of decision step energy barriers of the organic base, comparing the energy barrier lists, and determining the ligand with the minimum energy barrier as the optimal copper catalyst active organic base ligand;
further, in the above technical solution, the organic base is selected from DBU, TMG or TBD.
Further, in the technical scheme, the M06 functional is replaced by B3LPY, PBE, PW91 and M05 for calculation simulation, and the results are not as close as those of M06 and experimental values.
Further, in the technical scheme, a calculation functional method is determined by comparing with an experimental real result, and other alkali optimization simulation is performed, so that the best catalytic organic base ligand in a plurality of organic bases is determined. Meanwhile, key length, key angle, charge distribution, natural bond orbit and front line orbit analysis are carried out on a key structure, and the rule of influence of the ligand on the activity of the copper catalyst is searched.
Advantageous effects of the invention
Experiment on the mechanism study, the reaction mechanism is shown in fig. 1. The reaction process is researched by nuclear magnetic spectrum, and the reaction mixture is continuously taken out for many times in the reaction process, separated and purified, and then subjected to nuclear magnetic resonance 1 HNMR and 31 and (4) PNMR analysis, namely judging the corresponding intermediate structure from the spectrogram, and further inferring the reaction mechanism. The method can only indirectly obtain the information of the reaction intermediate, and is difficult to capture the information of the active intermediate and the transition state. The study of the experiment on the activity of different organic bases needs to change the organic bases and repeatedly carry out organic reactions, and the materials are time-consuming and labor-consuming.
The method can be used for predicting the influence of various organic bases on the catalytic activity of the copper complex. The method can predict the catalytic activity of the copper complex influenced by various organic bases by only one computer and corresponding computer application software, and experiments prove that the conclusion obtained by the method is consistent with organic experimental data, the result is accurate and reliable, and the conclusion can theoretically reveal the mechanism and the rule of the influence of the ligand on the activity of the copper catalyst and can be applied to actual work.
By using the convenience of theoretical research, the influence of a series of different organic bases on the structure of the copper complex and the reaction rate-determining step potential barrier is quickly simulated, and compared with an experimental method, the method is time-saving and labor-saving, and can avoid the waste of manpower and financial resources.
The method is simple and reasonable, easy to operate, low in cost and high in practical value, and has reference significance for research and development of organic alkali copper complex catalysts.
Drawings
FIG. 1 is a schematic diagram of the reaction principle of copper-catalyzed alkali-promoted reaction of carbon dioxide and hydrogen to formic acid in the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Screening a calculation method: the MSE results obtained using different calculation methods are shown in the following table:
TABLE 1 different calculation methods vs. MSE
Algorithm of mean square error MSE:
table 1 shows different calculation methods, giving different mean square error values. And selecting an M06 method for selecting the optimal value of the MSE according to the mean square error result. Note that the PBE results are close to the mean square error of M06, but since the PBE method is not commonly used to calculate transition calculations catalytic, M06 is the best.
Example 1
Step 1: a detailed path for catalyzing carbon dioxide hydrogenation to prepare formic acid by using the tridentate phosphorus-based copper complex as a catalyst is designed, and a structural formula of a path-designed intermediate and a transition state is drawn through ChemDraw and is shown in figure 1;
and 2, step: drawing all molecular structures on the path of the graph 1 by using a GaussView5.0 program, and manufacturing a Gaussian input file on the basis;
and step 3: the calculation work is submitted by using quantum chemistry simulation software Gaussian09, an M06 functional and a genecp base group, optimizing an intermediate and a transition state structure of a designed path by using a keyword "opt", wherein for the intermediate, an input command is "opt freqM 06/genecp", for the transition state, an input command is "opt ═ (calfc, ts, noeigent) freq M06/genecp", both genecps correspond to Lanl2DZ/6-31G, a pseudopotential base group Lanl2DZ is used for metal atoms Cu, 6-31G base group is used for non-metal atoms such as C, P, H, N, O, and a Gibbs Free Energy correction value "Thermal corotection Gieggbs Free Energy" is extracted from an output xx.
And 4, step 4: and (3) carrying out high-precision solvation single-point calculation on the optimized structure obtained in the step (3) by adopting a polarization continuous medium model (PCM), wherein the input command is as follows: the term "metal atom" refers to a metal atom Cu, and represents a pseudo-potential group lanl2DZ for a metal atom Cu, and a group 6 to 31G for a non-metal atom C, P, H, N, O, and the electronic energy "HF ═ xxxx.xxxx" is extracted from an output xx.log file after the end of a calculation task.
And 5: as shown in table 2, the absolute free energy G is obtained by adding the energies of the first two columns, then the first structure is selected as a zero point, the relative free energy Δ G is obtained by calculation, the transition state TS2 is judged as a speed-determining step from the value of the relative free energy, and the activation energy barrier Δ G is 29.5 kcal/mol;
TABLE 2 calculated Gibbs free energy in transition State
Step 6: replacing DBU in the two structures of 1-DBU and TS1 with TMG, and recalculating the speed-dependent step energy barrier, as shown in Table 3;
and 7: and (3) replacing DBU in the two structures of 1-DBU and TS1 with TBD, and recalculating the determined step energy barrier, as shown in Table 3, wherein the obtained determined step energy barriers of different organic bases are consistent with the TOF (time of flight) of the catalytic activity of the copper complex determined by the test, and the higher the energy barrier is, the smaller the TOF is.
Table 3 TOF value results calculated with different bases using M06
And step 8: and (3) analyzing the key structure by bond length, bond angle, charge distribution, natural bond orbit and front line orbit, and searching the rule of the influence of the ligand on the activity of the copper catalyst.
Comparative example 1
The specific steps are the same as example 1, except that B3LYP is adopted to replace M06 in step 3; the TOF results obtained in step 7 are shown in table 4, and it can be seen from table 4 that the results calculated using B3LYP do not agree with the actual sequence of experimental values (ACS cat. 2015,5,5301).
TABLE 4 TOF values calculated for various bases using B3LYP
Those skilled in the art to which the present invention pertains can also make appropriate changes and modifications to the above-described embodiments, based on the description in the above specification. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention.
Claims (2)
1. A method for rapidly screening organic alkali in a reaction of preparing formic acid from carbon dioxide and hydrogen under the catalysis of copper is characterized by comprising the following steps:
step 1: selecting an organic base complex with high catalytic efficiency, and designing a detailed reaction path according to a chemical basic principle;
step 2: drawing an intermediate body of a design path and a structural formula on a transition state through ChemDraw, and manufacturing a Gaussian input file on the basis;
and 3, step 3: optimizing an intermediate and a transition state structure of a designed path by using a quantum chemistry simulation software Gaussian09 and adopting an M06 functional and a 6-31G base group, and extracting a Gibbs free energy correction value from an output xx.log file;
and 4, step 4: carrying out solvation single-point calculation on the structure obtained in the step 3 by adopting an M06 functional, a 6-311+ G-base group and a polarization continuous mediator model PCM, extracting electronic energy from an output xx.log file, and adding the electronic energy and the Gibbs free energy correction value obtained in the step 3 to obtain an absolute free energy value of an intermediate or a transition state;
and 5: drawing a potential energy profile diagram of the reaction path according to the obtained absolute free energy value, finding out a reaction speed-determining step, a related intermediate and a transition state thereof, and calculating a speed-determining step energy barrier;
step 6: replacing the intermediate related to the speed-determining step and the organic base ligand in the transition state structure with another organic base ligand, and recalculating the speed-determining step energy barrier;
and 7: and (6) repeating the step 6 to obtain a plurality of decision step energy barriers of the organic base, comparing the energy barrier lists, and determining the ligand with the minimum energy barrier as the optimal copper catalyst active organic base ligand.
2. The method for rapidly screening the organic base in the reaction of preparing the formic acid from the carbon dioxide and the hydrogen catalyzed by the copper according to claim 1, which is characterized in that: the organic base is selected from DBU, TMG or TBD.
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