Method for accurately and rapidly predicting catalytic active sites of heteroatom-doped amorphous carbon

A technology of amorphous carbon and catalytic activity, applied in chemical property prediction, computational theoretical chemistry, instrumentation, etc., can solve the problem of not accurately reflecting the dynamic electron gain and loss process of the catalytic process

Active Publication Date: 2022-05-17
HARBIN INST OF TECH
View PDF8 Cites 1 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, traditional activity descriptors such as atomic charge population, spin population, and p-band density of states only consider the static electronic structure of the catalyst, and do not accurately reflect the dynamic electron gain and loss process in the catalytic process.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Method for accurately and rapidly predicting catalytic active sites of heteroatom-doped amorphous carbon
  • Method for accurately and rapidly predicting catalytic active sites of heteroatom-doped amorphous carbon
  • Method for accurately and rapidly predicting catalytic active sites of heteroatom-doped amorphous carbon

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Example 1: with SO 2 The initial step in the catalytic oxidation reaction O 2 Activation as an example, using the GaussView program to construct an aromatic carbon cluster model containing 6 aromatic rings and Zig-zag edges modified with carboxyl, hydroxyl, cyclic ether, lactone, and carbonyl groups, and using the Gaussian 09 program, in M06-2X / 6 The geometric configuration was optimized at the -31G(d,p) level to obtain a stable aromatic carbon cluster model. Further, the Multiwfn program and the Hirshelf method are used to calculate the single-point energy and atomic charge population of the aromatic carbon clusters at the same level under the condition of electroneutrality and one unit negative charge, and obtain the Mulliken electronegativity χ and the electrophilic Fukui function f - . further calculate f - / χ evaluates the ability of each carbon atom in the aromatic carbon cluster to accept electrons. Afterwards, through geometry optimization and subsequent fre...

Embodiment 2

[0054] Example 2: O predicted for Example 1 2 The site with the strongest activation ability, that is, the edge carbon atom of the aromatic carbon cluster of the Zig-zag edge modified cyclic ether, was calculated using the Gaussian 09 program to calculate SO 2 Gibbs free energy changes in catalytic oxidation elementary reaction pathways. Specifically, using the TS method, the transition state structure is searched at the M06-2X / 6-31G(d,p) level, and the geometric configuration of the transition state and the corresponding reactants, products, and intermediates is performed at the same calculation level. Optimization and frequency analysis to obtain Gibbs free energy correction. Furthermore, the single-point energy of reactants, products, intermediate products, and transition states is calculated at the M06-2X / def2-TZVPP level, and the Gibbs free energy barrier of each elementary reaction step is obtained by combining the free energy correction amount. SO 2 The Gibbs free en...

Embodiment 3

[0055] Embodiment 3: Based on the prediction result of the present invention, the HNO of active coke 6M 3 The solution was mixed according to the mass ratio of 1:5, and after being magnetically stirred for 24 hours under the condition of heating in a water bath at 80°C, it was placed in a horizontal tube furnace at a flow rate of 200mL min -1 N 2 Atmosphere, at 10°C min -1 The rate was increased from room temperature to 600 °C and maintained for 1 h to prepare the activated coke catalyst with directional modification of aromatic ring ether. Based on the prepared activated coke catalyst, to SO 2 Catalytic oxidations were tested for catalytic activity as probe reactions. The test condition is 200ppm SO 2 , 5vol-% O 2 , N 2 As carrier gas, the total gas flow is 200mLmin -1 , the reaction temperature is 50°C, and the mass of catalyst added is 0.1 g. The saturated sulfur capacity of activated coke modified by aromatic ring ether is 155 μmol g -1 , is the liquid phase oxida...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

PropertyMeasurementUnit
Sizeaaaaaaaaaa
Login to view more

Abstract

A method for accurately and rapidly predicting catalytic active sites of heteroatom-doped amorphous carbon belongs to the technical field of surface catalysis, and comprises the following steps: constructing a heteroatom-doped aromatic carbon cluster model and performing geometric configuration optimization; calculating Mulliken electronegativity x of the heteroatom doped aromatic carbon cluster after geometric configuration optimization by adopting a density functional theory; calculating an electrophilic well function value f-of each carbon atom in the heteroatom-doped aromatic carbon cluster by adopting a wave function analysis method; calculating a ratio f <-> / x of an electrophilic Fuji function value of each carbon atom in the heteroatom-doped aromatic carbon cluster after geometric configuration optimization to Mulliken electronegativity; and calculating a reaction path of the primarily screened active site catalytic element, obtaining a free energy barrier according to a calculation result, and screening sites with high catalytic activity. The invention provides a descriptor for accurately predicting the catalytic activity of the amorphous carbon-based catalyst, guides the design and construction of the amorphous carbon-based catalyst, and directly describes the essential process of dynamic electron transfer in the catalytic reaction.

Description

technical field [0001] The invention belongs to the technical field of surface catalysis, and in particular relates to a method for accurately and quickly predicting catalytic active sites of heteroatom-doped amorphous carbon materials. Background technique [0002] Heterogeneous catalysis is a core technology in the fields of environmental protection, chemical production, and energy utilization. Low-cost, high-performance catalyst materials are the key to efficient catalysis. Carbon materials have the advantages of high element abundance, large specific surface area, and good structure adjustability, and have great application potential in the field of catalysis. Carbon materials can be further divided into crystalline carbon with periodic infinite extension of the basal plane and amorphous carbon with stacking of small-sized (<10nm) aromatic carbon clusters according to the structure. Among them, amorphous carbon (carbon black, activated coke, activated carbon, porous ...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
IPC IPC(8): G16C20/30G16C10/00
CPCG16C20/30G16C10/00Y02E60/50
Inventor 孙飞曲智斌谢亮李旭函杨潮伟高继慧
Owner HARBIN INST OF TECH
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap