CN110364230A - A kind of quick screening copper catalysis carbon dioxide reacted with hydrogen formic acid in organic base method - Google Patents
A kind of quick screening copper catalysis carbon dioxide reacted with hydrogen formic acid in organic base method Download PDFInfo
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- CN110364230A CN110364230A CN201910775106.1A CN201910775106A CN110364230A CN 110364230 A CN110364230 A CN 110364230A CN 201910775106 A CN201910775106 A CN 201910775106A CN 110364230 A CN110364230 A CN 110364230A
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Abstract
The present invention provides a kind of quickly screening copper catalysis carbon dioxide reacted with hydrogen formic acid in organic base method, belong to calculating chemical field.In copper-organic base ligand catalysis carbon dioxide formic acid reaction, by carrying out Reaction process Simulation using using M06 functional, 6-31G* base group, calculate influence of the different organic bases to copper complex structure, reaction rate determining step potential barrier, the optimal organic base of activity is filtered out to be effectively predicted, it eliminates laboratory and repeats experiment investigation comparison, this method advantages of simple itself, easy to operate, inexpensive, result is accurate, has potential practical value.
Description
Technical field
The invention belongs to calculate technical field of chemistry, and in particular to a kind of quickly to screen copper catalysis carbon dioxide and hydrogen system
The method of organic base in formic acid reaction.
Background technique
Hydrogen Energy is considered as 21 century most potential clean energy resource, however hydrogen is flammable explosive gas, storage
It is vital technology with transport, has become the bottleneck that hydrogen utilization moves towards scale.
The formic acid that hydrogenation of carbon dioxide obtains is liquid at room temperature, safely can store and transport, and is that one kind can be again
Raw hydrogen storage material.Meanwhile formic acid is not only common chemical fuel or a kind of basic organic chemical industry raw material, is used extensively
In pesticide, dyestuff, medicine and other fields.By CO2And H2Formic acid directly is catalyzed and synthesized, is the very high reaction of Atom economy,
It is possible that reducing our dependences to fossil resource, meet contemporary green chemistry trend.
By CO2And H2Formic acid is directly synthesized, a unfavorable reaction is belonged to for thermodynamics, but transition gold is added
It can change the Gibbs function entirely reacted after metal catalyst, to become the reaction of favorable thermodynamics, thus develop CO2It is high
It is very active to imitate hydrogenation catalyst research field.In the transition-metal catalyst developed, ruthenium and complex of iridium have compared with
High catalysis yield.Then, inexpensive copper complex is proved efficiently be catalyzed CO2Hydrogen formic acid is added to react, however copper
Complex-catalyzed activity size depends on aar ligand, and alkalinity, the steric hindrance of aar ligand all largely affect copper complex
Activity and formic acid yield.
Aar ligand is explored at present, and spectrum, Mass Spectra are mainly experimentally carried out to the activity influence of copper complex, but
Organic base is many kinds of, is not only difficult to intuitive standard using the active structure-activity relationship that spectrum seeks different organic bases and copper complex
Really, and process is cumbersome quite time-consuming.
Summary of the invention
In order to overcome drawbacks described above, the present invention provides a kind of quickly screening copper catalysis carbon dioxide and hydrogen formic acid are anti-
The method for answering middle organic base.This method, which can be effectively predicted in copper catalysis carbon dioxide formic acid reaction, influences the best of catalytic activity
Organic base, this method advantages of simple itself, easy to operate, inexpensive, result is accurate, has potential practical value.
Technical solution used for the above purpose is: a kind of quickly to screen copper catalysis carbon dioxide and hydrogen first
The method of organic base, includes the following steps: in acid reaction
Step 1: the higher organic base complex of selective catalysis efficiency designs detailed reaction road according to chemical basic principle
Diameter；
Step 2: the structural formula on the intermediate and transition state of design path being drawn by ChemDraw, is made on this basis
Make the input file of Gaussian；
Step 3: institute is optimized using different functionals, 6-31G* base group by quantum chemical modelling software Gaussian09
The intermediate and transition state structures of design path extract Gibbs free energy correction value from the xx.log file of output；
Step 4: being tied using m06 functional, 6-311+G** base group, polarization continuous media model (PCM) to obtained by step 3
Structure carries out the calculation of solvation single-point, extracts electronics energy from the xx.log file of output, electronics can be free with gibbs that step 3 obtains
Can correction value be added to obtain intermediate or the absolute freedom of transition state and can be worth；
Step 5: the potential energy profile figure for drawing response path can be worth according to obtained absolute freedom, find out reaction rate determining step,
And its related intermediate and transition state, calculate rate determining step energy barrier；
Step 6: organic aar ligand in the relevant intermediate of rate determining step and transition state structures being replaced with another organic
Aar ligand recalculates rate determining step energy barrier；
Step 7: repeating step 6, obtain the rate determining step energy barrier of multiple organic bases, these energy barrier lists are compared, energy
It builds minimum ligand and is determined as best copper catalyst reactive organic base ligand；
Further, in the above-mentioned technical solutions, organic base is selected from DBU, TMG or TBD.
Further, in the above-mentioned technical solutions, M06 functional B3LPY, PBE, PW91 and M05 is replaced with to calculate
Simulation, result are close not as good as M06 and experiment value.
Further, in the above-mentioned technical solutions, it by being compared with experiment legitimate reading, determines and calculates functional side
Method carries out other alkali Optimized Simulateds, so that it is determined that being most preferably catalyzed organic aar ligand in numerous organic bases.In combination with to key
Structure carries out bond distance, bond angle, charge population, natural bond track, frontier orbit analysis, seeks ligand to copper catalyst activity influence
Rule.
Invention beneficial effect
The research to mechanism is tested, reaction mechanism is shown in Fig. 1.Reaction process is studied by magnetic resonance spectroscopy, is adopted
Reaction mixture is taken out with continuous several times during the reaction, after separating-purifying, carries out nuclear magnetic resonance1HNMR and31PNMR analysis,
Corresponding intermediate structure is determined from spectrogram, and then speculates reaction mechanism.This method can only obtain reaction intermediate letter indirectly
Breath, is difficult to capture reactive intermediate and transition state information.Experiment needs to change organic to the active research of different organic bases
Alkali, repeats organic reaction, and consumptive material takes time and effort.
Influence of a variety of organic bases to copper complex catalytic activity can be predicted using the method for the present invention.Only need a meter
Calculation machine and corresponding computer application software can be calculated, can on a variety of organic bases influence copper complex catalytic activity into
Row prediction, it is demonstrated experimentally that the conclusion that the method for the present invention obtains is consistent with Organic Experiment data, as a result accurately and reliably, conclusion
Not only ligand can have theoretically been disclosed to the mechanism of copper catalyst activity influence and its rule but also can apply in real work.
Using the convenience of theoretical research, a series of different organic bases of Fast simulation are to copper complex structure, reaction rate determining step
The influence of potential barrier, waste that is time saving compared to experimental method, laborsaving, can avoid manpower, financial resources.
The method of the present invention advantages of simple, operation is easy, at low cost, has very high practical value, organic base copper is matched
The research and development of mixture catalyst have reference.
Detailed description of the invention
Fig. 1 is that copper is catalyzed the reaction principle schematic diagram that alkali promotes carbon dioxide to react generation formic acid with hydrogen in the present invention.
Specific embodiment
Calculation method is screened: using different calculation methods, obtained MSE result is as shown in the table:
The different calculation method of table 1 and MSE relationship
The algorithm of mean square deviation MSE:Table 1 shows different calculation methods, provides
Different mean square deviations.According to mean square deviation as a result, the M06 method of selected MSE optimum value.It should be noted that PBE result and M06
Mean square deviation is close, but since PBE method is not commonly used to calculate transition calculating catalysis, using M06 as best.
Embodiment 1
Step 1: using three tooth phosphorus base copper complexes as catalyst, designing its detailed road for being catalyzed hydrogenation of carbon dioxide formic acid
Diameter draws the structural formula of design path intermediate and transition state by ChemDraw, as shown in Figure 1；
Step 2: drawing all molecular structures on the path Fig. 1 with GaussView5.0 program, make on this basis
The input file of Gaussian；
Step 3: key is used using M06 functional, genecp base group by quantum chemical modelling software Gaussian09
Word " opt " optimizes the intermediate and transition state structures in designed path, submits and calculates operation, for intermediate, the order of input
It is " opt freqM06/genecp ", for transition state, the order of input is " opt=(calcfc, ts, noeigent) freq
M06/genecp ", the genecp in the two both correspond to Lanl2DZ/6-31G*, represent and use pseudo potential for metallic atom Cu
Base group lanl2DZ uses 6-31g* base group for non-metallic atoms such as C, P, H, N, O, from output after calculating task
Xx.log file extracts Gibbs free energy correction value " Thermal correctionto Gibbs Free Energy ".
Step 4: the optimization structure that step 3 obtains being carried out using polarization continuous media model (PCM) high-precision molten
Agent single-point is calculated, input order are as follows: scrf=(pcm, solvent=acetonitrile) m06/genecp, wherein genecp
Corresponding to lanl2DZ/6-311+G**, represents and Pseudopotential basis set lanl2DZ is used for metallic atom Cu, for C, P, H, N, O
Equal non-metallic atoms use 6-31G* base group, and extracting electronics from the xx.log file of output after calculating task can " HF=
xxxx.xxxx”。
Step 5: as shown in table 2, the energy addition of first two columns just being obtained into absolute freedom energy G, then chooses first knot
Structure is zero point, and opposite free energy △ G is calculated, and judges that transition state TS2 for rate determining step, is activated from the numerical value of opposite free energy
Energy barrier △ △ G is 29.5kcal/mol；
Gibbs free energy calculated value in 2 transition state of table
Step 6: the DBU in two structures of 1-DBU and TS1 being replaced with into TMG, rate determining step energy barrier is recalculated, such as 3 institute of table
Show；
Step 7: the DBU in two structures of 1-DBU and TS1 is replaced with into TBD, recalculates rate determining step energy barrier, such as table 3,
The rate determining step energy barrier of obtained different organic bases and the catalytic activity TOF of the copper complex of test measurement are in the same size, and energy barrier is got over
Height, TOF are smaller.
The different alkali of table 3 calculate TOF value result using M06
Step 8: bond distance, bond angle, charge population, natural bond track, frontier orbit analysis being carried out to key structure, seeks and matches
Rule of the body to copper catalyst activity influence.
Comparative example 1
The specific steps are the same as those in embodiment 1, and difference is in step 3 to substitute M06 using B3LYP；TOF result is obtained in step 7
For table 4, as can be seen from Table 4 using the calculated result of B3LYP and experiment actual value sequence (ACS Catal.2015,5,
5301) not consistent.
The different alkali of table 4 calculate TOF value result using B3LYP
The description of book according to the above description, those skilled in the art in the invention can also carry out above embodiment
Change and modification appropriate.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to of the invention
Some modifications and changes should also be as falling into the scope of the claims of the present invention.
Claims (2)
1. a kind of quickly screening copper catalysis carbon dioxide reacted with hydrogen formic acid in organic base method, which is characterized in that wrap
Include following steps:
Step 1: the higher organic base complex of selective catalysis efficiency designs detailed response path according to chemical basic principle；
Step 2: the structural formula on the intermediate and transition state of design path being drawn by ChemDraw, is made on this basis
The input file of Gaussian；
Step 3: designed road is optimized using M06 functional, 6-31G* base group by quantum chemical modelling software Gaussian09
The intermediate and transition state structures of diameter extract Gibbs free energy correction value from the xx.log file of output；
Step 4: using M06 functional, 6-311+G** base group, polarization continuous media model (PCM) to step 3 resulting structures into
Row solvation single-point is calculated, and extracts electronics energy from the xx.log file of output, electronics can be rectified with the Gibbs free energy that step 3 obtains
Positive value addition, which obtains intermediate or the absolute freedom of transition state, to be worth；
Step 5: the potential energy profile figure for drawing response path can be worth according to obtained absolute freedom, find out reaction rate determining step, and its
Related intermediate and transition state calculate rate determining step energy barrier；
Step 6: organic aar ligand in the relevant intermediate of rate determining step and transition state structures being replaced with into another organic base and is matched
Body recalculates rate determining step energy barrier；
Step 7: repeating step 6, obtain the rate determining step energy barrier of multiple organic bases, these energy barrier lists are compared, energy barrier is most
Small ligand is determined as best copper catalyst reactive organic base ligand.
2. method of the quick predict organic base to copper catalyst activity influence according to claim 1, it is characterised in that: organic
Alkali is selected from DBU, TMG or TBD.
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| CN114067923A (en) * | 2021-11-17 | 2022-02-18 | 郑州轻工业大学 | Screening method for Lewis acid catalyzed diazo compound activation mode |
| CN114582431A (en) * | 2022-03-16 | 2022-06-03 | 内蒙古工业大学 | (bipy) CuⅡReaction mechanism research and analysis method for catalytic oxidation of-TEMPO/organic base catalytic system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113831260A (en) * | 2020-06-08 | 2021-12-24 | 南京工业大学 | Verification method for designed propylene hydrocyanation reaction route based on quantitative calculation |
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| CN114582431A (en) * | 2022-03-16 | 2022-06-03 | 内蒙古工业大学 | (bipy) CuⅡReaction mechanism research and analysis method for catalytic oxidation of-TEMPO/organic base catalytic system |
| CN114582431B (en) * | 2022-03-16 | 2023-03-17 | 内蒙古工业大学 | (bipy) Cu Ⅱ Reaction mechanism research and analysis method for catalytic oxidation of-TEMPO/organic base catalytic system |
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