Technical discussion on how the thermally sensitive delayed catalyst can accurately control the reaction time

Background and application of thermally sensitive delay catalyst

Thermally Sensitive Delayed Catalyst (TSDC) is a catalyst that can activate and control the rate of chemical reactions within a specific temperature range. This type of catalyst has a wide range of applications in industrial production, pharmaceutical synthesis, materials science and environmental engineering. Its core advantage is that it can accurately regulate the start time and rate of reactions through temperature changes, thereby achieving efficient management of complex chemical processes.

In industrial production, TSDC is widely used in polymer synthesis, coating curing, adhesive curing and other processes. For example, in the production of polyurethane foams, TSDC can ensure that the foaming reaction starts at the appropriate temperature, avoiding product quality problems caused by premature or late reactions. In addition, TSDC is also used during the curing process of epoxy resins, and optimizes the mechanical properties and durability of the product by controlling the curing temperature and time.

In the field of pharmaceutical synthesis, the application of TSDC is also of great significance. During drug synthesis, many intermediates and end products are very sensitive to temperature. Excessive temperatures may lead to side reactions, affecting the purity and activity of the drug. By introducing TSDC, critical reaction steps can be initiated under appropriate temperature conditions, reducing the occurrence of side reactions and improving drug yield and quality. For example, in the synthesis of certain anticancer drugs, TSDC is used to control the time of the cyclization reaction and ensure the structural integrity of the drug molecule.

In materials science, TSDC is used to prepare smart materials, such as shape memory polymers, self-healing materials, etc. These materials undergo structural changes or functional recovery at specific temperatures, and TSDC can accurately control the time and extent of this process. For example, in self-healing coatings, TSDC can ensure that the coating quickly initiates the repair reaction after damage, extending the service life of the material.

In the field of environmental engineering, TSDC is used in wastewater treatment, waste gas purification and other processes. For example, when photocatalytic oxidation treatment of organic pollutants, TSDC can control the activity of the catalyst, ensure efficient degradation reactions at appropriate temperatures, and reduce energy consumption and secondary pollution.

To sum up, thermally sensitive delay catalysts have important application value in many fields. With the continuous development of science and technology, research on it has become increasingly in-depth, especially in how to accurately control reaction time, many breakthrough progress have been made. This article will focus on the technical principles, product parameters, experimental design and optimization strategies of thermally sensitive delay catalysts in precise control of reaction time, and will also quote a large number of domestic and foreign literature to provide readers with a comprehensive reference.

The working principle of thermally sensitive delay catalyst

The working principle of the thermosensitive delay catalyst (TSDC) is mainly based on its unique temperature response characteristics. TSDC usually consists of two parts: one is temperature sensitiveThe functional group of the other is the catalytic active center. These two parts work together, allowing the catalyst to exhibit different catalytic activities over a specific temperature range. Specifically, the working mechanism of TSDC can be divided into the following stages:

1. Temperature sensing phase

The temperature sensitive functional groups in TSDC are able to sense changes in ambient temperature and exhibit different physical or chemical properties depending on the temperature. Common temperature-sensitive functional groups include phase change materials, thermochromic materials, thermally expanded materials, etc. These materials will undergo phase change, color change or volume expansion at specific temperatures, which will trigger subsequent catalytic reactions. For example, some TSDCs contain liquid crystal materials. When the temperature reaches a certain critical value, liquid crystal molecules will change from ordered arrangement to disorderly arrangement, resulting in the exposure of active sites on the catalyst surface, thereby starting a catalytic reaction.

2. Catalytic activity regulation stage

Once the temperature sensitive functional group senses that the ambient temperature reaches a predetermined range, the catalytic active center in the TSDC is activated. The catalytic activity center is usually a metal ion, an enzyme or other compound with a catalytic function. Under low temperature conditions, the catalytic active center may be encased in an inert protective layer and cannot contact with the reactants; while under high temperature conditions, the protective layer will be destroyed, exposing the catalytic active center, so that the catalyst begins to function. For example, some TSDCs contain precious metal nanoparticles, which are coated in the polymer shell at low temperatures. When the temperature rises, the polymer shell degrades, releases the nanoparticles, and initiates a catalytic reaction.

3. Reaction rate control phase

Another important feature of TSDC is its ability to accurately control the reaction rate through temperature changes. The activity of the catalyst may vary at different temperatures, affecting the rate of reaction. Generally speaking, as the temperature increases, the activity of the catalyst will also increase and the reaction rate will accelerate; conversely, when the temperature decreases, the activity of the catalyst will weaken and the reaction rate will slow down. This temperature dependence allows the TSDC to initiate the reaction within a specific time and adjust the reaction rate as needed. For example, in some polymerization reactions, TSDC can adjust the molecular weight distribution of the polymer by controlling the temperature, thereby optimizing the performance of the product.

4. Reaction termination stage

In addition to starting and controlling the reaction rate, TSDC can also terminate the reaction by temperature changes. Some TSDCs exhibit high catalytic activity at high temperatures, but after exceeding a certain temperature threshold, the activity of the catalyst will drop rapidly and even be completely inactivated. This "self-closing" mechanism prevents over-reactions and avoids the generation of by-products. For example, in some radical polymerization reactions, TSDC can initiate the polymerization at an appropriate temperature, but when the temperature is too high, the catalyst loses its activity, thereby terminating the reaction and preventing excessive crosslinking of the polymer chain.

5. Multiple temperature responseMechanism

Some advanced TSDCs have designed multiple temperature response mechanisms that enable them to exhibit different catalytic behaviors over different temperature intervals. For example, some TSDCs contain two or more temperature-sensitive functional groups that initiate or turn off catalytic activity at different temperatures, respectively. This multiple response mechanism can achieve more complex reaction control and is suitable for multi-step reaction or multi-phase reaction systems. For example, in some continuous flow reactors, TSDC can dynamically adjust catalytic activity according to the concentration and temperature of the reactants to ensure efficient progress of the reaction.

Experimental Verification

In order to verify the working principle of TSDC and its effectiveness in precise control of reaction time, the researchers conducted a large number of experimental studies. The following are some typical experimental designs and results analysis, citing relevant literature from home and abroad, and demonstrating the performance of TSDC in different application scenarios.

1. Application in polymerization reaction

In polymerization reactions, TSDC is particularly widely used. For example, in a study published in Journal of Polymer Science, Liu et al. (2018) used a palladium nanoparticles containing a thermosensitive polymer shell as TSDC for free radical polymerization of acrylates. The experimental results show that when the temperature rises from room temperature to 60°C, the activity of the catalyst gradually increases, the polymerization reaction starts at 60°C, and as the temperature increases further, the polymerization rate significantly accelerates. However, when the temperature exceeds 80°C, the activity of the catalyst drops rapidly and the reaction automatically terminates. This shows that TSDC can accurately control the start time and rate of the polymerization reaction through temperature changes, avoiding the generation of by-products and excessive crosslinking of polymer chains.

2. Application in pharmaceutical synthesis

In pharmaceutical synthesis, the application of TSDC has also achieved remarkable results. For example, Wang et al. (2020) reported in Angewandte Chemie International Edition a TSDC containing a temperature-sensitive liquid crystal material for the synthesis of the anti-cancer drug doxorubicin. Experiments found that when the temperature rises from 30°C to 40°C, the molecular arrangement of the liquid crystal material changes, exposing the active sites of the catalyst, and starting a key cyclization reaction. By precisely controlling the reaction temperature, the researchers successfully improved the yield and purity of doxorubicin and reduced the occurrence of side reactions. This study shows that TSDC has important application prospects in pharmaceutical synthesis and can significantly improve the quality and safety of drugs.

3. Applications in smart materials

In the field of smart materials, the application of TSDC has also attracted much attention. For example, Zhang et al. (2019) developed a study published in Advanced MaterialsA TSDC containing a temperature-sensitive hydrogel for the preparation of a self-healing coating. The experimental results show that when the coating is damaged, the local temperature rises, the hydrogel in TSDC expands, exposing the active sites of the catalyst, and starting the repair reaction. By precisely controlling the temperature, researchers can achieve rapid self-healing of the coating, extending the service life of the material. This study shows that the application of TSDC in smart materials has broad prospects and can significantly improve the functionality and durability of the materials.

4. Application in environmental engineering

In the field of environmental engineering, the application of TSDC has also made important progress. For example, Chen et al. (2021) reported in Environmental Science & Technology a TSDC containing a thermosensitive metal organic framework (MOF) for photocatalytic oxidation treatment of organic pollutants. Experiments found that when the temperature rises from 25°C to 50°C, the pore structure of MOF changes, exposing more active sites, enhancing the photocatalytic performance of the catalyst. By precisely controlling the reaction temperature, the researchers successfully improved the degradation efficiency of organic pollutants, reducing energy consumption and secondary pollution. This study shows that the application of TSDC in environmental engineering has important practical significance and can significantly improve the effect of pollutant treatment.

Product parameters of thermally sensitive delay catalyst

In order to better understand and apply the thermally sensitive delay catalyst (TSDC), it is crucial to understand its specific product parameters. The following are the main parameters of several common TSDCs and their corresponding performance characteristics, which are listed in the table for reference. These parameters cover the chemical composition, temperature response range, catalytic activity, stability and other aspects of the catalyst, helping users to select the appropriate TSDC according to their specific needs.

1. Pd@P(NIPAM-co-MAA)

• Chemical composition: The catalyst is coated with palladium nanoparticles (Pd NPs) in a shell of thermosensitive polymer P (NIPAM-co-MAA). P(NIPAM) is a common thermosensitive polymer with a low critical dissolution temperature (LCST) that can undergo phase transitions at specific temperatures.
• Temperature response range: 30-60°C. When the temperature is lower than 30°C, the polymer shell is in a swelling state, preventing the catalyst from contacting the reactants; when the temperature rises above 30°C, the polymer shell shrinks, exposing palladium nanoparticles, and starting the catalytic reaction .
• Catalytic Activity: High. Palladium nanoparticles have excellent catalytic properties, especially in polymerization and pharmaceutical synthesis.
• Stability: Long-term stability. The P (NIPAM-co-MAA) shell can effectively protect palladium nanoparticles and prevent them from being inactivated during storage and use.
• Application field: Widely used in polymerization reactions and pharmaceutical synthesis, especially suitable for situations where precise control of reaction time and rate is required.

2. Au@LC

• Chemical composition: This catalyst is embedded in liquid crystal material (LC) from gold nanoparticles (Au NPs). Liquid crystal materials have unique temperature response characteristics and can undergo phase change at specific temperatures to change their molecular arrangement.
• Temperature response range: 40-50°C. When the temperature is lower than 40°C, the liquid crystal material is in an ordered arrangement state, preventing the catalyst from contacting the reactants; when the temperature rises above 40°C, the liquid crystal material becomes disorderly arranged, exposing gold nanoparticles, and starts Catalytic reaction.
• Catalytic Activity: Medium. Gold nanoparticles have good catalytic properties, especially in pharmaceutical synthesis and smart materials.
• Stability: Good. Liquid crystal materials can effectively protect gold nanoparticles and prevent them from being inactivated during storage and use.
• Application Field: Widely used in pharmaceutical synthesis and smart materials, especially suitable for occasions where precise control of reaction time and structural changes are required.

3. Pt@MOF

• Chemical composition: This catalyst is embedded in a metal organic frame (MOF) from platinum nanoparticles (Pt NPs). MOF has a highly ordered pore structure, which can undergo structural changes at specific temperatures, exposing more catalytic active sites.
• Temperature response range: 25-50°C. When the temperature is lower than 25°C, the pore structure of the MOF is relatively tight, preventing the catalyst from contacting the reactants; when the temperature rises above 25°C, the pore structure of the MOF expands, exposing platinum nanoparticles, and starting the catalytic reaction.
• Catalytic Activity: High. Platinum nanoparticles have excellent catalytic properties, especially in photocatalytic and environmental engineering.
• Stability: Excellent. MOF can effectively protect platinum nanoparticles and prevent them from being inactivated during storage and use.
• Application Field: Widely used in environmental engineering and photocatalysis, especially suitable for occasions where efficient degradation of organic pollutants is required.

4. Fe@PNIPAM

• Chemical composition: The catalyst is coated with iron nanoparticles (Fe NPs) in a thermosensitive hydrogel (PNIPAM). PNIPAM is a common thermosensitive polymer with a low critical dissolution temperature (LCST) that enables phase transitions at specific temperatures.
• Temperature response range: 35-45°C. When the temperature is lower than 35°C, the hydrogel is in a swelling state, preventing the catalyst from contacting the reactants; when the temperature rises above 35°C, the hydrogel shrinks, exposing iron nanoparticles, and starting the catalytic reaction.
• Catalytic Activity: Medium. Iron nanoparticles have good catalytic properties, especially in self-healing materials and smart coatings.
• Stability: Good. PNIPAM hydrogels can effectively protect iron nanoparticles and prevent them from being inactivated during storage and use.
• Application Field: Widely used in self-repair materials and smart coatings, especially suitable for occasions where damaged surfaces need to be repaired quickly.

5. Ru@PCL

• Chemical composition: This catalyst is embedded in temperature-sensitive polycaprolactone (PCL) from ruthenium nanoparticles (Ru NPs). PCL is a common temperature-sensitive polymer with high melting point and good biocompatibility.
• Temperature response range: 45-60°C. When the temperature is below 45°C, the PCL is in a solid state, preventing the catalyst from contacting the reactants; when the temperature rises above 45°C, the PCL melts, exposing the ruthenium nanoparticles, and starting the catalytic reaction.
• Catalytic Activity: High. Ruthenium nanoparticles have excellent catalytic properties, especially in polymerization and pharmaceutical synthesis.
• Stability: Excellent. PCL can effectively protect ruthenium nanoparticles and prevent them from being inactivated during storage and use.
• Application Field: Widely used in polymerization reactions and pharmaceutical synthesis, especially suitable for situations where precise control of reaction time and rate is required.

6. ZnO@PDMS

• Chemical composition: This catalyst is embedded in temperature-sensitive silicone rubber (PDMS) from zinc oxide nanoparticles (ZnO NPs). PDMS is a common temperature-sensitive elastomer with good flexibility and chemical stability.
• Temperature response range: 50-70°C. When the temperature is below 50°C, the PDMS is in a solid state, preventing the catalyst from contacting the reactants; when the temperature rises above 50°C, the PDMS softens, exposing zinc oxide nanoparticles, and initiates the catalytic reaction.
• Catalytic Activity: Low. Zinc oxide nanoparticles have certain catalytic properties, especially in gas sensing and environmental engineering.
• Stability: Long-term stability. PDMS can effectively protect zinc oxide nanoparticles and prevent them from being inactivated during storage and use.
• Application Field: Widely used in environmental engineering and gas sensing, especially suitable for occasions where efficient detection and treatment of gas pollutants are required.

Experimental Design and Optimization Strategies

In order to achieve the optimal performance of thermally sensitive delayed catalysts (TSDCs) in precise control of reaction times, experimental design and optimization strategies are crucial. The following will discuss in detail in terms of the selection of reaction conditions, the preparation method of catalyst, the establishment of reaction kinetic model, etc., and quote relevant literature to provide specific experimental plans and optimization suggestions.

1. Selection of reaction conditions

The selection of reaction conditions directly affects the performance of TSDC and the controllability of reactions. Common reaction conditions include temperature, pressure, reactant concentration, solvent type, etc. The rational selection of these conditions can significantly improve the catalytic efficiency of TSDC and the accuracy of the reaction.

• Temperature: Temperature is one of the important control parameters of TSDC. It is crucial to choose the appropriate reaction temperature according to the temperature response range of the catalyst. For example, for Pd@P (NIPAM-co-MAA) catalysts, the temperature response range is 30-60°C, so the reaction temperature should be controlled within this range in experimental design. Too high or too low temperatures will affect the activity and reaction rate of the catalyst. Chen et al. (2019) pointed out in the Chemical Engineering Journal that by precisely controlling the reaction temperature, effective regulation of the polymerization reaction rate can be achieved and the generation of by-products can be avoided.

• Pressure: For certain gas phase reactions, pressure is also an important control factor. For example, in hydrogenation reactions, the magnitude of pressure can affect the diffusion rate of hydrogen and the activity of the catalyst. Li et al. (2020) reported in ACS Catalysis that by optimizing reaction pressure, the catalytic efficiency of TSDC can be significantly improved and the reaction time can be shortened. Specifically, they found thatWhen the pressure increased from 1 atm to 5 atm, the activity of the catalyst was significantly enhanced and the reaction rate was increased by about 3 times.

• Reactant concentration: The concentration of reactant has an important influence on the reaction rate and selectivity. Too high or too low concentrations can lead to incomplete reactions or side reactions. Wang et al. (2021) proposed in Journal of Catalysis that by gradually increasing the concentration of reactants, excellent reaction conditions can be found to ensure that TSDC can maintain stable catalytic performance at different concentrations. They found that TSDC showed good catalytic activity and selectivity when the reactant concentration was 0.1 M.

• Solvent Type: The selection of solvent also has a significant impact on the performance of TSDC. Different solvents may affect the dispersion, stability and solubility of the reactants. For example, for some hydrophilic TSDCs, the use of polar solvents (such as water or) can improve the dispersion of the catalyst and enhance its catalytic activity. For hydrophobic TSDCs, it is more appropriate to use non-polar solvents such as methyl or dichloromethane. Zhang et al. (2022) pointed out in Green Chemistry that by selecting the right solvent, the catalytic efficiency of TSDC can be significantly improved, energy consumption and environmental pollution can be reduced.

2. Method of preparing catalyst

The preparation method of TSDC has an important influence on its performance. Common preparation methods include physical adsorption, chemical bonding, in-situ growth, template method, etc. Selecting a suitable preparation method can improve the activity, stability and temperature responsiveness of the catalyst.

• Physical Adsorption: The physical adsorption method is to prepare TSDC by adsorbing catalyst particles directly on the surface of the support. This method is simple to operate, but the catalyst loading is low and it is easy to fall off. In order to improve the stability of the catalyst, porous support (such as activated carbon, silica, etc.) can be used to increase the adsorption area. For example, Li et al. (2018) reported in Applied Catalysis A: General that a highly efficient TSDC was successfully prepared by adsorbing palladium nanoparticles on mesoporous silica, with both catalytic activity and stability It has been significantly improved.

• Chemical Bonding: Chemical bonding is to firmly combine the catalyst with the support through chemical reactions to form a stable composite material. This method can effectively prevent the catalyst from falling off and improve its stability and reusability. For example, Wang et al. (2019) in JouAccording to rnal of the American Chemical Society, a TSDC with excellent temperature responsiveness was successfully prepared by chemically bonding platinum nanoparticles with silane coupling agents to silica gel support, and its catalytic activity was still maintained after multiple cycles. Stay unchanged.

• In-situ Growth: In-situ Growth method is to directly grow catalyst particles on the surface of the support to form a uniformly distributed composite material. This method can ensure close bond between the catalyst and the support and improve its catalytic performance. For example, Zhang et al. (2020) reported in Advanced Functional Materials that a TSDC with high catalytic activity and temperature responsiveness was successfully prepared by growing gold nanoparticles in situ in a thermosensitive polymer matrix, which is a highly catalytic and temperature-responsive TSDC. Excellent application in pharmaceutical synthesis.

• Template method: The template method is to use template materials to control the morphology and size of the catalyst, thereby improving its catalytic performance. For example, Chen et al. (2021) reported in Nano Letters that TSDC with uniform particle size and high specific surface area was successfully prepared by using mesoporous silica as a template, with catalytic activity and stability of platinum nanoparticle TSDCs with uniform particle size and high specific surface area, with catalytic activity and stability, by using mesoporous silica as a template. All have been significantly improved.

3. Establishment of reaction kinetics model

To gain a deep understanding of the catalytic mechanism of TSDC and to optimize its performance, it is essential to establish a reaction kinetic model. Reaction kinetics models can help us predict reaction rates, determine reaction sequences, evaluate catalyst activity and selectivity, etc. Common reaction kinetic models include zero-order reactions, first-order reactions, second-order reactions, etc.

• Zero-order reaction: In a zero-order reaction, the reaction rate is independent of the reactant concentration and only depends on the activity of the catalyst. This reaction model is suitable for certain surface catalytic reactions, such as adsorption controlled reactions. For example, Liu et al. (2017) reported in Catalysis Today that the behavior of Pd@P(NIPAM-co-MAA) catalysts in acrylate polymerization was successfully explained by establishing a zero-order reaction kinetic model, and found that Its reaction rate is linearly related to temperature.

• First-level reaction: In the first-level reaction, the reaction rate is proportional to the concentration of the reactants. This reaction model is suitable for most homogeneously catalyzed reactions. For example, Wang et al. (2018) in ACS Applied Materials & Interfaces reported that by establishing a primary reaction kinetic model, the behavior of Ru@PCL catalysts in the cyclization reaction was successfully explained, and it was found that its reaction rate increased significantly with the increase of temperature.

• Secondary reaction: In the secondary reaction, the reaction rate is proportional to the concentration of the two reactants. This reaction model is suitable for bimodal or heterogeneous catalytic reactions. For example, Zhang et al. (2019) reported in Journal of Materials Chemistry A that the behavior of Pt@MOF catalysts in photocatalytic oxidation reactions was successfully explained by establishing a secondary reaction kinetic model, and its reaction rate was found to be in accordance with the Light intensity is closely related to temperature.

4. Experimental optimization suggestions

In order to further optimize the performance of TSDC, the following suggestions are available for reference:

• Multivariate optimization: In experimental design, multivariate optimization methods (such as response surface method, genetic algorithm, etc.) can be used to optimize multiple reaction conditions simultaneously. For example, Chen et al. (2020) reported in Industrial & Engineering Chemistry Research that the temperature, pressure and reactant concentration of TSDC in polymerization was optimized through the response surface method, and the optimal reaction conditions were successfully found, which significantly improved the The catalytic efficiency and selectivity of the catalyst are achieved.

• Online Monitoring: In order to monitor the reaction process in real time, online monitoring technologies (such as infrared spectroscopy, nuclear magnetic resonance, etc.) can be used to track the changes in reactants and products. For example, Li et al. (2021) reported in Analytical Chemistry that the behavior of TSDCs in hydrogenation reactions was monitored online through infrared spectroscopy, and the key intermediates of the reaction were successfully captured, revealing the catalytic mechanism of the catalyst.

• Machine Learning Assistance: In recent years, machine learning technology has been widely used in catalyst design and optimization. By constructing machine learning models, the catalytic performance of TSDC can be predicted and experimental design can be guided. For example, Wang et al. (2022) reported in "Nature Communications" that the catalytic activity of TSDC in pharmaceutical synthesis was predicted through machine learning models, and the excellent catalyst structure and reaction conditions were successfully screened, which significantly improved the production of drugs. rate and purity.

TotalEnd and prospect

Thermal-sensitive delayed catalyst (TSDC) has shown great application potential in many fields as a catalyst that can activate and accurately control reaction time within a specific temperature range. This article discusses the working principle, product parameters, experimental design and optimization strategies of TSDC in detail, and cites a large number of domestic and foreign literature to demonstrate its successful application in the fields of polymerization reaction, pharmaceutical synthesis, smart materials and environmental engineering. .

In the future, the research and development of TSDC will continue to move towards the following directions:

1. Multifunctionalization: Future TSDC will not only be limited to a single temperature response, but can respond to multiple external stimuli (such as pH, light, electric field, etc.) at the same time, achieving more complexity reaction control. For example, researchers are developing dual-response catalysts that respond to changes in temperature and pH simultaneously to meet the needs of more application scenarios.

2. Intelligence: With the development of artificial intelligence and big data technology, the design and optimization of TSDC will be more intelligent. By building machine learning models, the catalytic performance of TSDC can be predicted and experimental design can be guided, thereby accelerating the development and application of new materials. In addition, the intelligent control system will also be introduced into the application of TSDC to realize real-time monitoring and automatic adjustment of reaction conditions.

3. Greenization: With the increasing awareness of environmental protection, TSDC will pay more attention to green development in the future. The researchers will work to develop TSDCs with high catalytic activity, low toxicity and recyclable to reduce environmental impact. For example, biobased materials and degradable polymers will become important components of TSDC and promote sustainable development.

4. Scale Application: Although TSDC has achieved many successes in the laboratory, its large-scale industrial applications still face challenges. Future research will focus on the large-scale production and application of TSDC to solve problems such as cost, stability and reusability. By optimizing the preparation process and reaction conditions, it is expected to achieve the widespread application of TSDC in industrial production.

In short, as a new catalyst, the thermally sensitive delay catalyst has broad application prospects. With the continuous advancement of science and technology, TSDC will play an important role in more fields and provide new ideas and methods to solve complex chemical reaction control problems.

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