Silica-LDH Core-Shell Catalysts for CO2 Hydrogenation

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Solution Overview

Problem

Current catalysts for hydrogenating CO2 to methanol, such as Cu/ZnO-based systems, require improvement in catalytic properties and efficiency, particularly in terms of copper loading and stability.

Innovation Solution

Development of silica core-layered double hydroxide (LDH) core-shell particles with a high content of Cu2+ and Zn2+ ions, which are synthesized through a process involving coprecipitation and thermal treatment, forming a catalyst precursor that exhibits enhanced catalytic activity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If traditional Cu/ZnO-based catalysts are used for CO2 hydrogenation, then catalytic activity can be achieved, but copper loading must be high and stability is insufficient

Engineering Contradiction:
Improvecatalyst stabilityVSAvoidcopper loading
Core Design Contradiction:
ReliabilityVSQuantity of substance

Solution Approach 1:

The patent employs a core-shell composite structure where silica forms the core and layered double hydroxide (containing Cu2+ and Zn2+ ions) forms the shell. This composite architecture allows copper to be highly dispersed in the LDH shell, achieving high catalytic activity with lower overall copper loading while the silica core provides structural stability and prevents copper aggregation, thereby improving catalyst stability.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention concentrates copper ions specifically in the layered double hydroxide shell layer, creating a localized high-copper region that provides sufficient catalytic activity. The silica core remains copper-free, providing structural support without contributing to copper loading. This spatial distribution of copper achieves high activity with low overall copper content while maintaining stability.

Inventive Principle:
Principle #3Local quality

2Reliability

If copper loading is reduced to improve stability, then catalyst stability increases, but catalytic activity decreases

Engineering Contradiction:
Improvecatalyst stabilityVSAvoidcatalytic activity
Core Design Contradiction:
ReliabilityVSProductivity

Solution Approach 1:

The layered double hydroxide shell contains inherent porosity and a high surface area that allows efficient mass transport of reactants to the copper active sites. The porous LDH structure accommodates copper ions in a dispersed manner, maximizing the number of accessible active sites per unit of copper, thereby maintaining high catalytic activity even with reduced overall copper loading.

Inventive Principle:
Principle #31Porous materials

Solution Approach 2:

Copper ions are localized within the LDH shell where they provide high catalytic activity per unit mass. The high surface area and specific structure of the LDH shell create numerous accessible copper sites, ensuring that reducing overall copper loading does not significantly impact activity while improving stability.

Inventive Principle:
Principle #3Local quality

3Reliability

If silica core-LDH shell structure is adopted, then copper dispersion and stability improve, but manufacturing complexity increases

Engineering Contradiction:
Improvecatalyst stabilityVSAvoidstructure complexity
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The silica core is prepared first as a pre-formed support structure, and then the layered double hydroxide shell is grown on its surface in a subsequent step. This sequential preparation approach, where the core is prepared in advance and the shell is added afterward, simplifies the overall manufacturing process compared to attempting to create the core-shell structure in a single step, making the complex structure more manufacturable.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The layered double hydroxide acts as an intermediary layer between the silica core and the catalytic reaction environment. This LDH shell mediates the interaction between copper ions and reactants, providing a stable platform that simplifies the overall catalyst design while achieving the desired performance.

Inventive Principle:
Principle #24Intermediary (Mediator)

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The silica-LDH core-shell catalysts demonstrate improved catalytic performance for CO2 hydrogenation to methanol, with increased activity and stability even at lower copper loading compared to traditional catalysts, and exhibit a more efficient conversion process.

Implementation Method 1

the surface of Cu is generally accepted to provide catalytic active sites, although the role(s) of the ZnO support is still not clear

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

contacting: silica particles, an aqueous solution of layered double hydroxide-forming metal cations, said metal cations comprising Cu2+

Methodology Applied
Scientific EffectCoprecipitation: Coprecipitation

Implementation Method 3

the catalyst precursor is a thermally treated form of the particle of the first or third aspects

Methodology Applied
Scientific EffectThermal treatment: Heat Treatment

Data Source

PatentEP4414069A1Core-shell materials
Publication Date: 2024.08.14 SCG CHEM CO LTD
  • EP4414069A1 patent drawingFigure 1(a)~1(b)
  • EP4414069A1 patent drawingFigure 2
  • EP4414069A1 patent drawingFigure 3

AI summary

New core-shell silica-LDH particles useful as starting materials in the formation of catalysts are described, as well as methods of preparing the core-shell particles. Also described are catalyst precursors and catalysts formed from the core-shell particles, the catalysts being suitable for catalysing the hydrogenation of CO2 (or CO) to methanol.