CN104897508A - Method for testing thermodynamic parameters of functional material - Google Patents
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- CN104897508A CN104897508A CN201410081084.6A CN201410081084A CN104897508A CN 104897508 A CN104897508 A CN 104897508A CN 201410081084 A CN201410081084 A CN 201410081084A CN 104897508 A CN104897508 A CN 104897508A
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
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- 238000010926 purge Methods 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 44
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
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- NYIDSUMRGUILGR-UHFFFAOYSA-N 4-(2-trimethoxysilylethyl)benzenesulfonyl chloride Chemical compound CO[Si](OC)(OC)CCC1=CC=C(S(Cl)(=O)=O)C=C1 NYIDSUMRGUILGR-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention relates to a method for testing the thermodynamic parameters of a functional material. The method comprises the following steps: using a resonant micro-cantilever as a micro-mass sensor, loading the functional material to the free end of the resonant micro-cantilever, testing the adsorption quantity of the functional material to different pressure gases at a specific temperature in real time to obtain the adsorption isotherm of the functional material, further calculating to obtain the thermodynamic parameters of the functional material, and carrying out characteristic assessment on the functional material according to the obtained thermodynamic parameters. The method is advanced, has practical application significance, and also has the characteristics of easy operation and low price.
Description
Technical Field
The invention relates to a method for testing thermodynamic parameters of a material by a variable temperature weighing method, in particular to a resonant micro-cantilever in the aspects of testing and calculating the thermodynamic parameters of a functional material, and belongs to the field of evaluation of the adsorption characteristics of the functional material.
Background
The functional material has important effects on the study of characteristics such as adsorption direction, mode, capacity and the like of gas molecules in a plurality of fields such as public safety, environmental protection, food safety and the like. For example, in order to reduce the atmosphereCarbon dioxide (CO)2) The content of the greenhouse gas is equal, and the research on CO is necessary2The novel adsorbing material has super-large adsorption capacity and certain selectivity; for another example, in order to increase safety of farmers in pesticide spraying, it is necessary to research a new material which has specific adsorption to pesticides such as organic phosphorus and is inexpensive; for another example, in order to manufacture a high-performance sensor that can specifically respond to trace amounts of pesticide residues in agricultural products such as vegetables, it is necessary to know the adsorption characteristics of a sensitive material to pesticide molecules. In all of the above research fields, it is necessary to evaluate the thermodynamic properties of the functional material such as the direction, mode, and capacity of adsorption of gas.
Foreign literature reports have used thermodynamic parameters to evaluate new materials (e.g., metal organic framework compounds) for CO2Adsorption characteristics of (1) (Nature, 2013,495, 80-84). However, the research is based on large-scale equipment such as a gas adsorption instrument, Monte Carlo calculation simulation, a quartz balance, a magnetic suspension balance and the like, and has the defects of high test price, large material consumption, single variety of test gas and the like.
The invention indicates that the resonance type micro-cantilever can be used as a micro-mass sensor, and the adsorption quantity of a material to gas with specified pressure is weighed in real time at constant temperature, so that the characteristic parameters of the material, such as adsorption (or desorption) direction, mode, capacity and the like, can be obtained. The method has positive significance in the fields of functional material adsorption (or desorption) characteristic evaluation and the like, and widens the application field of the resonant micro-cantilever.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for testing thermodynamic parameters of a functional material, and in order to apply a resonant micro-cantilever to the specific evaluation field of adsorption and desorption of the functional material, the method is advanced, has practical application significance, is easy to operate and has low cost.
The invention is realized by the following technical scheme:
a method for testing thermodynamic parameters of a functional material comprises the steps of using a resonant micro-cantilever as a micro-mass sensor, loading the functional material on the free end of the resonant micro-cantilever, testing the adsorption quantity of the functional material to gases with different pressures at a specific temperature in real time to obtain an adsorption isotherm of the functional material, further calculating the thermodynamic parameters of the functional material, and evaluating the characteristics of the functional material according to the obtained thermodynamic parameters.
The functional material is selected from mesoporous materials, polymers, carbon nanotubes, graphene and the like.
The resonance type micro cantilever is an integrated piezoresistive silicon-based micro cantilever.
The mass sensitivity of the resonant micro-cantilever is 1.53 Hz/pg. Wherein Hz is a frequency unit, and 1pg =10-12g。
The thermodynamic parameters include enthalpy change, entropy change, gibbs free energy change, adsorption/desorption equilibrium constants, and coverage.
The objects of the characteristic evaluation of the functional material include an adsorption direction, a desorption direction, an adsorption manner, an adsorption capacity, and the like.
A method for testing thermodynamic parameters of a functional material specifically comprises the following steps:
(1) coating: coating the dispersion liquid of the functional material on the free end of the resonant micro-cantilever by using a micro-operation system, and drying for later use;
(2) aging: placing the resonance type micro-cantilever coated with the functional material in a testing pool capable of stabilizing the temperature, and stably aging under high-purity nitrogen airflow;
(3) baseline testing was performed: fixing the flow of the introduced gas, continuously introducing high-purity nitrogen, and recording the frequency of the resonant micro-cantilever;
(4) and (3) sensitive curve testing: keeping the gas flow rate same as that in the step (3) at a constant temperature, continuously introducing mixed gas of adsorption gas with known concentration and nitrogen for adsorption, acquiring the frequency of the resonant micro-cantilever in real time, continuously introducing high-purity nitrogen with the same flow rate for purging and desorption after the frequency is kept unchanged, and acquiring the frequency of the resonant micro-cantilever in real time until the frequency is kept unchanged; then changing the concentration of the adsorbed gas in the introduced mixed gas, and repeating the test process; obtaining a sensitive curve of the frequency of the resonant micro-cantilever beam changing along with the concentration of the adsorbed gas at the temperature;
(5) adjusting the temperature of the test cell to another constant temperature, and repeating the step (4) to obtain another sensitive curve of the frequency of the resonant micro-cantilever beam changing along with the concentration of the adsorbed gas at another temperature;
(6) and (3) converting the sensitivity curve obtained in the steps (4) and (5) into an adsorption isothermal curve according to the mass sensitivity of the resonant micro-cantilever: namely a relation curve of gas adsorption quantity and pressure under constant temperature;
(7) calculating the change delta H degree of the adsorption enthalpy according to the adsorption isothermal curve and a Clausius-Klebsiella equation;
(8) any one adsorption isothermal curve is taken and transformed into a relation curve of p/V and p, and an adsorption equilibrium constant K and a standard equilibrium constant K DEG are obtained according to the intercept and the slope of the curve;
(9) according to the value of K, calculating the coverage degree theta under specific adsorption gas partial pressure by a Langmuir equation;
(10) according to the K degrees and the test temperature of the adsorption isothermal curve obtained in the step (8), solving the Gibbs free energy change delta G degrees by a Van't Hoff equation;
(11) and (3) according to the numerical values of the Gibbs free energy change delta G DEG and the adsorption enthalpy change delta H DEG, calculating the entropy change delta S DEG according to the definition formula of the Gibbs free energy change.
Wherein,
preferably, the solvent of the dispersion of the functional material is selected from deionized water, ethanol, tetrahydrofuran, and the like.
Preferably, the concentration of the functional material in the dispersion liquid of the functional material is 1-50 mg/mL; the coating weight at the free end of the resonance type micro-cantilever is 0.01-1 microliter.
Preferably, the temperature for drying in step (1) is 60-100 ℃, more preferably 80 ℃.
Preferably, in step (2), the time period for stable aging is 1 to 5 days, more preferably 3 days.
Preferably, the frequency is acquired using a commercial frequency meter, preferably an agilent model 5313A frequency meter.
In the step (7), the method for calculating the change of enthalpy of adsorption Δ H ° is to respectively record the temperatures as T1And T2Two numerical points with the same coverage degree theta are taken from the two adsorption isotherms and are respectively marked as (p)1Theta) and (p)2θ), then Δ H ° is calculated according to the clausius-klebsiron equation. Unless otherwise specified, in the present invention, T is temperature, p is pressure, and θ is adsorption coverage.
The Clausius-Klebsiella equation is as follows:
or an integral expression thereof:
in the step (8), the relationship curve between p/V and p is the Lanmuir equation:
p/V=p/V∞+(KV∞)-1 （Ⅲ）
wherein K is an adsorption equilibrium constant, and a standard equilibrium constant K degree is calculated and solved by a relational expression of K degree = K multiplied by p degree;
wherein p DEG means standard pressure, i.e. p DEG =101325 Pa, and the approximate value is taken during actual calculationAnd (6) handkerchief.
V is the volume of the functional material converted into the standard condition when the partial pressure of the adsorbed gas is p; v∞The gas adsorption amount is converted into the volume under the standard condition under the condition that the functional material reaches saturated adsorption, and then the coverage degree theta = V/V infinity.
The standard conditions are a temperature of 0 deg.C (273.15K) and a pressure of 101.325 kPa (1 atm, 760 mmHg).
In the step (10), the van t hoff equation is:
ΔG°=-RTlnK° （Ⅳ）
in the step (11), the gibbs free energy change is defined as:
ΔG°=ΔH°-TΔS° （Ⅴ）
the technical scheme of the invention can also be as follows:
the application of the resonant micro-cantilever in the thermodynamic parameter test of the functional material is characterized in that the resonant micro-cantilever is used as a micro-mass sensor, the functional material is loaded at the free end of the resonant micro-cantilever, the adsorption quantity of the functional material to gases with different pressures at a specific temperature is tested in real time, the adsorption isotherm of the functional material is obtained, and then the thermodynamic parameter of the functional material is further calculated; then, the characteristic evaluation of the functional material can be carried out according to the obtained thermodynamic parameters; the method specifically comprises the following steps:
(1) coating: coating the dispersion liquid of the functional material on the free end of the resonant micro-cantilever by using a micro-operation system, and drying for later use;
(2) aging: placing the resonance type micro-cantilever coated with the functional material in a testing pool capable of stabilizing the temperature, and stably aging under high-purity nitrogen airflow;
(3) baseline testing was performed: fixing the flow of the introduced gas, continuously introducing high-purity nitrogen, and recording the frequency of the resonant micro-cantilever;
(4) and (3) sensitive curve testing: keeping the gas flow rate same as that in the step (3) at a constant temperature, continuously introducing mixed gas of adsorption gas with known concentration and nitrogen for adsorption, acquiring the frequency of the resonant micro-cantilever in real time, continuously introducing high-purity nitrogen with the same flow rate for purging and desorption after the frequency is kept unchanged, and acquiring the frequency of the resonant micro-cantilever in real time until the frequency is kept unchanged; then changing the concentration of the adsorbed gas in the introduced mixed gas, and repeating the test process; obtaining a sensitive curve of the frequency of the resonant micro-cantilever beam changing along with the concentration of the adsorbed gas at the temperature;
(5) adjusting the temperature of the test cell to another constant temperature, and repeating the step (4) to obtain another sensitive curve of the frequency of the resonant micro-cantilever beam changing along with the concentration of the adsorbed gas at another temperature;
(6) and (3) converting the sensitivity curve obtained in the steps (4) and (5) into an adsorption isothermal curve according to the mass sensitivity of the resonant micro-cantilever: namely a relation curve of gas adsorption quantity and pressure under constant temperature;
(7) calculating the change delta H degree of the adsorption enthalpy according to the adsorption isothermal curve and a Clausius-Klebsiella equation;
(8) any one adsorption isothermal curve is taken and transformed into a relation curve of p/V and p, and an adsorption equilibrium constant K and a standard equilibrium constant K DEG are obtained according to the intercept and the slope of the curve;
(9) according to the value of K, calculating the coverage degree theta under specific adsorption gas partial pressure by a Langmuir equation;
(10) according to the K degree and the test temperature of the adsorption isothermal curve obtained in the step (8), solving the Gibbs free energy change delta G degree by a Van't Hoff equation;
(11) and (3) according to the numerical values of the Gibbs free energy change delta G DEG and the adsorption enthalpy change delta H DEG, calculating the entropy change delta S DEG according to the definition formula of the Gibbs free energy change.
The evaluation of the invention is that according to the general theory of physics and chemistry, the absolute value of the enthalpy change DeltaH DEG of adsorption is less than 40kJ/mol and is attributed to physical adsorption, more than 80kJ/mol is attributed to chemical adsorption, and the value between the two is attributed to the force (such as hydrogen bond and the like) which is difficult to define, thereby judging the adsorption form of the material to the special gas.
The invention has the technical effects and advantages that: the resonance type micro-cantilever is applied to the field of evaluation of the adsorption (desorption) characteristics of functional materials, and the method is advanced, has practical application significance, is easy to operate and is low in price.
Drawings
FIG. 1 (a 1) Transmission Electron micrograph of carboxyl functionalized mesoporous nanoparticles
(a2) Resonance type micro cantilever beam time frequency response curve (298K) loaded with carboxyl functionalized mesoporous nano-particles
(a3) Resonance type micro-cantilever time frequency response curve (318K) loaded with carboxyl functionalized mesoporous nano-particles
(a4) Isothermal adsorption curves (298K, 318K) of carboxyl functionalized mesoporous nanoparticles to trimethylamine gas
(b1) Transmission electron microscope photograph of sulfonic acid functionalized mesoporous nano-particles
(b2) Resonant micro-cantilever time frequency response curve (298K) loaded with sulfonic acid functionalized mesoporous nanoparticles
(b3) Resonance type micro-cantilever time frequency response curve (318K) loaded with sulfonic acid functionalized mesoporous nano-particles
(b4) Adsorption isotherm curves (298K, 318K) of sulfonic acid functionalized mesoporous nanoparticles on trimethylamine gas
(c1) Transmission electron microscope photograph of unmodified mesoporous nano-particles
(c2) Resonance type micro cantilever beam time frequency response curve (298K) loaded with unmodified mesoporous nano-particles
(c3) Resonance type micro-cantilever time frequency response curve (318K) loaded with unmodified mesoporous nano-particles
(c4) Adsorption isotherm curves (298K, 318K) of unmodified mesoporous nanoparticles to trimethylamine gas
FIG. 2 Structure of functionalized hyperbranched polymer molecule described in example 2
FIG. 3 (a) time-frequency response curve (283K) of resonant micro-cantilever loaded with functionalized hyperbranched polymer
(b) Resonant micro-cantilever time frequency response curve (298K) loaded with functionalized hyperbranched polymer
(c) Adsorption isotherm curves (283K, 298K) of functionalized hyperbranched polymers on DMMP (dimethyl methylphosphonate)
Detailed Description
The technical solution of the present invention is illustrated by specific examples below. It is to be understood that one or more method steps mentioned in the present invention do not exclude the presence of other method steps before or after the combination step or that other method steps may be inserted between the explicitly mentioned steps; it should also be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Example 1: evaluation of adsorption characteristics of three mesoporous nanoparticles to trimethylamine
(1) Synthesis of three mesoporous nanoparticle samples
Firstly, three mesoporous nano particles sequentially refer to: a. carboxyl functionalized mesoporous nanoparticles; b. sulfonic acid functionalized mesoporous nanoparticles; C. unmodified mesoporous nanoparticles
② the synthesis method of carboxyl functionalized mesoporous nano-particles is disclosed in patent application: a method for preparing carboxyl functionalized mesoporous nano-particles with spiral pore canals (patent application No. 201210306247.7).
③ the synthesis method of sulfonic acid functionalized mesoporous nanoparticles is as described in the patent application No. 201210306247.7, but the aqueous solution of trihydroxy silicon-based sodium acetate is replaced by 2- (4-chlorosulfonyl phenyl) ethyltrimethoxysilane (the name of England is 2- (4-chlorosulfonyl phenyl) ethyl trimethoxy silane,50wt% dichloromethane solution), and other reaction conditions are the same, the sulfonic acid functionalized mesoporous nanoparticles can be obtained.
The synthesis method of the unmodified mesoporous nano-particles is the same as that of the document (patent application number: 201210306247.7), but the unmodified mesoporous nano-particles can be obtained by using the same reagent trihydroxy silicon-based sodium acetate aqueous solution and the same other reaction conditions.
The tem photographs of the three mesoporous nanoparticles are shown in fig. 1 (a 1), (b 1), and (c 1);
(2) preparing a sample (loading mesoporous nano particles on the free end of the integrated piezoresistive silicon-based micro-cantilever to form a micro weighing sensor) and aging:
dispersing three mesoporous nano particles (the weight of each mesoporous nano particle is about 10 mg) in 1 ml of deionized water in advance to prepare dispersion liquid of the three mesoporous nano particles;
secondly, coating 1 microliter of mesoporous nano-particle dispersion liquid on the free end of the resonance type micro-cantilever by using a micro-operation system, and drying at 80 ℃ for later use;
placing the resonance type micro-cantilever coated with the mesoporous nano-particle material in a testing pool with a constant temperature function, and stably aging for 3 days under high-purity nitrogen airflow;
(3) test (taking carboxyl functionalized mesoporous nano-particles as an example)
Firstly, baseline test: under the condition of high-purity nitrogen gas flow, recording the frequency of a resonant micro-cantilever (the free end of which is loaded with carboxyl functionalized mesoporous nano particles) by using a commercial frequency meter;
testing a sensitive curve at the temperature of 298K (25 ℃): at the temperature of 298K, introducing 90ppb (ppb refers to the volume concentration of one part per billion) of trimethylamine gas, collecting the frequency of the resonant micro-cantilever in real time, introducing nitrogen gas after the frequency is kept unchanged, desorbing the carboxyl functionalized mesoporous nano-particles adsorbed with the trimethylamine gas, adjusting the concentration of the trimethylamine gas to 180ppb after the frequency of the resonant micro-cantilever is kept unchanged, and repeating the test to obtain the frequency data of the micro-cantilever in the gas atmosphere with the concentration; using this method, the concentration of trimethylamine gas was adjusted to 360ppb and 900ppb, respectively, and the frequency data of the resonant micro-cantilever at these two concentrations were measured, respectively. Thereby obtaining a real-time test curve of the frequency of the micro-cantilever beam along with the change of the trimethylamine gas concentration at the temperature of 298K (as shown in FIG. 1 (a 2));
regulating the temperature of the test cell to 318K, and obtaining another real-time test curve (shown in figure 1 (a 3)) of the frequency of the resonant micro-cantilever at 318K along with the change of the trimethylamine gas concentration according to the test process in the step II;
respectively fixing the temperatures of the test chambers to 298K and 318K by the same method, and correspondingly obtaining real-time test curves (shown as (b 2) and (b 3) in fig. 1) of the frequency of the sulfonic acid functionalized mesoporous nano particle loaded resonance type micro cantilever beam along with the change of the trimethylamine gas concentration;
fifthly, respectively fixing the temperatures of the test chambers to 298K and 318K by the same method, and correspondingly obtaining real-time test curves (as shown in (c 2) and (c 3) in the attached figure 1) of the frequency of the resonance type micro-cantilever beam loaded by the unmodified mesoporous nano-particles along with the change of the trimethylamine gas concentration;
(4) thermodynamic parameter calculation and adsorption characteristic evaluation
Drawing an isothermal curve: converting the test curves (shown in fig. 1 as (a 2) and (a 3), (b 2) and (b 3), (c 2) and (c 3) into adsorption isotherm curves (shown in fig. 1 as (a 4), (b 4) and (c 4), respectively) according to the mass sensitivity of the resonant micro-cantilever; the adsorption isotherm curve is a relation curve of trimethylamine gas adsorption amount and pressure at a constant temperature;
calculation of enthalpy change (Δ H °): arbitrarily making a horizontal line and intersecting with 2 adsorption isotherms, wherein 2 intersections are the partial pressure values of the trimethylamine under the same coverage. As shown in FIG. 1 (a 4), the partial pressure of trimethylamine at 298K is 18 mPa, the partial pressure of trimethylamine at 318K is 90 mPa, and the corresponding values of the partial pressure and temperature are substituted into the Clausius-Claburron equation
The adsorption enthalpy change delta H DEG of the carboxyl functionalized mesoporous nano particles to trimethylamine can be calculated to be-63.4 kJ/mol. By adopting the same method, the adsorption enthalpy change delta H DEG of the sulfonic acid functionalized mesoporous nano-particles to trimethylamine can be calculated to be-149.6 kJ/mol; the adsorption enthalpy change delta H DEG of the unmodified mesoporous nano particles to trimethylamine is-23.0 kJ/mol.
Calculating other thermodynamic parameters (entropy change, Gibbs free curve (energy change, adsorption/desorption equilibrium constant and coverage degree) of the carboxyl functionalized mesoporous nano-particles, namely transforming an adsorption isotherm into a relation of p/V and p, wherein p is the partial pressure of gas, and V is the volume of the adsorbed gas under the corresponding partial pressure p converted into the standard condition), and calculating the other thermodynamic parameters according to the Langmuir equation
p/V=p/V∞+(KV∞)-1，
The adsorption equilibrium constant K =63Pa was obtained from the intercept and the slope of the curve-1. Because the invention only relates to gas-solid two-phase adsorption reaction (in particular to a gaseous substance adsorbed on the surface of a solid substance and another solid substance with gas adsorbed on the surface of the solid substance), the standard equilibrium constant K DEG (= K multiplied by p DEG) (p DEG means standard pressure, namely p DEG (= 101325 Pa), and the approximate value is taken during actual calculationPa), i.e. K ° =63 × 105=6.3×106. Since the coverage of the material surface is different at different gas partial pressures before saturation adsorption is achieved, the coverage needs to be calculated at a given partial pressure. Equilibrium constant K =63Pa according to adsorption/desorption-1And specified partial pressure (e.g., p =9 × 10)-3Pa), and then by another form of the Lanmuir equation
θ=Kp/(1+Kp)，
The coverage θ =0.36 was obtained. According to the van T hoff equation Δ G ° = -RTlnK °, where the temperature T takes the temperature value 298K of the isotherm curve of fig. 1 (a 4), K ° =6.3 × 106Substitution, the change in Gibbs free energy Δ G ° = -38.8kJ · mol in the adsorption process can be calculated-1. Finally, the entropy change Δ S ° = -82.6J · K can be found from the Gibbs free energy change definition formula Δ G ° = Δ H ° -T Δ S °-1。
Evaluation of adsorption characteristics: physicochemical theories generally consider that adsorption enthalpy changes Δ H ° values with absolute values less than 40kJ/mol are attributed to physical adsorption, values greater than 80kJ/mol to chemical adsorption, and values in between are attributed to forces (such as hydrogen bonds, etc.) that are poorly defined. Therefore, according to the calculated adsorption enthalpy change Δ H ° value, the trimethylamine molecule is adsorbed on the surface of the carboxyl-functionalized mesoporous nanoparticles by means of hydrogen bonds, adsorbed on the surface of the sulfonic acid mesoporous nanoparticles by means of chemical adsorption, and adsorbed on the surface of the unmodified mesoporous nanoparticles by means of physical adsorption. The carboxyl functionalized mesoporous nanoparticles have certain selective adsorption on trimethylamine, can be desorbed and are suitable for being used as sensitive materials of amine gases; the sulfonic acid functionalized mesoporous nano-particles have a strong adsorption effect on trimethylamine, are difficult to desorb after adsorption, and are suitable for being used as an adsorbent for amine gas.
Example 2: the adsorption property of the functionalized hyperbranched polymer (the synthesis method is the same as chem. mater.2004,16,5357-5364, the molecular structure diagram of the functionalized hyperbranched polymer is shown in figure 2) on an organophosphorus simulator DMMP (dimethyl methylphosphonate) is evaluated:
(1) sample preparation (loading functional hyperbranched polymer on the free end of a resonance type micro-cantilever to form a micro-weighing sensor) and aging
Dispersing about 10 mg of functionalized hyperbranched polymer in 1 ml of tetrahydrofuran in advance;
secondly, coating 1 microliter of tetrahydrofuran dispersion liquid of the hyperbranched polymer on the free end of the resonance type micro-cantilever by using a micro-operation system, and drying at 80 ℃ for later use;
thirdly, the resonance type micro-cantilever beam coated with the functional material is placed in a testing pool with a constant temperature function, and is aged stably for 3 days under high-purity nitrogen gas flow.
(2) Testing
Firstly, baseline test: under the condition of high-purity nitrogen gas flow, recording the frequency of the resonant micro-cantilever by using a commercial frequency meter;
testing a sensitive curve at the temperature of 283K (10 ℃): under the temperature of 283K, 80ppb (ppb refers to the volume concentration of one billion) of DMMP gas is introduced, the frequency of the resonant micro-cantilever is collected in real time, and nitrogen flow is introduced to desorb the sensor adsorbing the gas after the frequency is kept unchanged; after the frequency of the micro-cantilever beam is kept unchanged, adjusting the concentration of DMMP gas to 160ppb, and repeatedly testing to obtain frequency data of the micro-cantilever beam under the gas atmosphere with the concentration; using this method, the DMMP gas concentration was readjusted to 270ppb and the resonant micro-cantilever was tested for frequency data at this concentration. Thus, a real-time test curve of the frequency of the micro-cantilever as a function of the DMMP gas concentration at a temperature of 283K was obtained (as shown in fig. 3 (a)).
And thirdly, adjusting the temperature of the test cell to 298K, and according to the step (ii), obtaining another real-time test curve (shown in figure 3 (b)) of the frequency of the micro-cantilever beam changing along with the concentration of the DMMP gas at the temperature.
(3) Thermodynamic parameter calculation and adsorption characteristic evaluation
Drawing an isothermal curve: converting the test curve (fig. 3 (a) and (b)) into an adsorption isotherm (i.e., DMMP gas adsorption versus pressure at constant temperature, as shown in fig. 3 (c)) according to the mass sensitivity of the resonant micro-cantilever;
calculation of enthalpy change (Δ H °): arbitrarily making a horizontal line and intersecting with 2 adsorption isotherms, wherein 2 intersection points are the partial pressure values of the DMMP under the same coverage degree (as shown in fig. 3 (c), the partial pressure of the DMMP under 283K is 8 millipascals, and the partial pressure of the DMMP under 298K is 19.5 millipascals), and substituting the corresponding partial pressure values and temperature values into a Clausius-Claburon equation to calculate that the adsorption enthalpy change delta H DEG is-41.6 kJ/mol;
evaluation of adsorption characteristics: physicochemical theories generally consider that adsorption enthalpy changes Δ H ° values with absolute values less than 40kJ/mol are attributed to physical adsorption, values greater than 80kJ/mol to chemical adsorption, and values in between are attributed to forces (such as hydrogen bonds, etc.) that are poorly defined. Therefore, according to the calculated adsorption enthalpy change delta H DEG value (-41.6 kJ/mol), the DMMP molecules are adsorbed on the surface of the functionalized hyperbranched polymer in a hydrogen bond mode, have certain selectivity, can be desorbed, and are suitable for being used as sensitive materials of organic phosphorus gases.
Claims (10)
1. A method for testing thermodynamic parameters of a functional material comprises the steps of using a resonant micro-cantilever as a micro-mass sensor, loading the functional material on the free end of the resonant micro-cantilever, testing the adsorption quantity of the functional material to gases with different concentrations at a specific temperature in real time to obtain an adsorption isotherm of the functional material, further calculating the thermodynamic parameters of the functional material, and evaluating the characteristics of the functional material according to the obtained thermodynamic parameters. .
2. The method for testing thermodynamic parameters of a functional material according to claim 1, wherein the functional material is selected from the group consisting of mesoporous materials, polymers, carbon nanotubes, and graphene.
3. The method according to claim 1, wherein the resonant micro-cantilever is an integrated piezoresistive silicon-based micro-cantilever.
4. The method of claim 1, wherein the mass sensitivity of the resonant micro-cantilever is 1.53 Hz/pg.
5. The method for testing the thermodynamic parameters of a functional material according to claim 1, comprising the following steps:
(1) coating: coating the dispersion liquid of the functional material on the free end of the resonant micro-cantilever by using a micro-operation system, and drying for later use;
(2) aging: placing the resonance type micro-cantilever coated with the functional material in a testing pool capable of stabilizing the temperature, and stably aging under high-purity nitrogen airflow;
(3) baseline testing was performed: fixing the flow of the introduced gas, continuously introducing high-purity nitrogen, and recording the frequency of the resonant micro-cantilever;
(4) and (3) sensitive curve testing: keeping the gas flow rate same as that in the step (3) at a constant temperature, continuously introducing mixed gas of adsorption gas with known concentration and nitrogen for adsorption, acquiring the frequency of the resonant micro-cantilever in real time, continuously introducing high-purity nitrogen with the same flow rate for purging and desorption after the frequency is kept unchanged, and acquiring the frequency of the resonant micro-cantilever in real time until the frequency is kept unchanged; then changing the concentration of the adsorbed gas in the introduced mixed gas, and repeating the test process; obtaining a sensitive curve of the frequency of the resonant micro-cantilever beam changing along with the concentration of the adsorbed gas at the temperature;
(5) adjusting the temperature of the test cell to another constant temperature, and repeating the step (4) to obtain another sensitive curve of the frequency of the resonant micro-cantilever beam changing along with the concentration of the adsorbed gas at another temperature;
(6) and (3) converting the sensitivity curve obtained in the steps (4) and (5) into an adsorption isothermal curve according to the mass sensitivity of the resonant micro-cantilever: namely a relation curve of gas adsorption quantity and pressure under constant temperature;
(7) calculating the change delta H degree of the adsorption enthalpy according to the adsorption isothermal curve and a Clausius-Klebsiella equation;
(8) any one adsorption isotherm is taken and is transformed into a relation curve of P/V and P, and an adsorption equilibrium constant K and a standard equilibrium constant K DEG are obtained according to the intercept and the slope of the curve;
(9) according to the value of K, calculating the coverage degree theta under specific adsorption gas partial pressure by a Langmuir equation;
(10) according to the K degrees and the test temperature of the isothermal curve obtained in the step (8), solving the Gibbs free energy change delta G degrees by a van Techf equation;
(11) and (3) according to the numerical values of the Gibbs free energy change delta G DEG and the adsorption enthalpy change delta H DEG, calculating the entropy change delta S DEG according to the definition formula of the Gibbs free energy change.
6. The method for testing the thermodynamic parameter of the functional material according to claim 5, wherein the concentration of the functional material in the dispersion of the functional material is 1-50 mg/mL; the coating weight at the free end of the resonance type micro-cantilever is 0.01-1 microliter; the solvent of the dispersion liquid of the functional material is selected from deionized water, ethanol and tetrahydrofuran.
7. The method for testing the thermodynamic parameter of a functional material according to claim 5, wherein in the step (2), the time for the stable aging is 1 to 5 days.
8. The method for testing the thermodynamic parameters of a functional material according to claim 5, wherein the frequency is collected by using a model 5313A frequency meter of Agilent USA.
9. The application of the resonant micro-cantilever in the thermodynamic parameter test of the functional material is characterized in that the resonant micro-cantilever is used as a micro-mass sensor, the functional material is loaded at the free end of the resonant micro-cantilever, the adsorption quantity of the functional material to gases with different pressures at a specific temperature is tested in real time, the adsorption isotherm of the functional material is obtained, and then the thermodynamic parameter of the functional material is further calculated; the functional material can then be characterized by the resulting thermodynamic parameters.
10. The application of the resonant micro-cantilever according to claim 8 in the thermodynamic parameter test of functional materials, comprising the following steps:
(1) coating: coating the dispersion liquid of the functional material on the free end of the resonant micro-cantilever by using a micro-operation system, and drying for later use;
(2) aging: placing the resonance type micro-cantilever coated with the functional material in a testing pool capable of stabilizing the temperature, and stably aging under high-purity nitrogen airflow;
(3) baseline testing was performed: fixing the flow of the introduced gas, continuously introducing high-purity nitrogen, and recording the frequency of the resonant micro-cantilever;
(4) and (3) sensitive curve testing: keeping the gas flow rate same as that in the step (3) at a constant temperature, continuously introducing mixed gas of adsorption gas with known concentration and nitrogen for adsorption, acquiring the frequency of the resonant micro-cantilever in real time, continuously introducing high-purity nitrogen with the same flow rate for purging and desorption after the frequency is kept unchanged, and acquiring the frequency of the resonant micro-cantilever in real time until the frequency is kept unchanged; then changing the concentration of the adsorbed gas in the introduced mixed gas, and repeating the test process; obtaining a sensitive curve of the frequency of the resonant micro-cantilever beam changing along with the concentration of the adsorbed gas at the temperature;
(5) adjusting the temperature of the test cell to another constant temperature, and repeating the step (4) to obtain another sensitive curve of the frequency of the resonant micro-cantilever beam changing along with the concentration of the adsorbed gas at another temperature;
(6) and (3) converting the sensitivity curve obtained in the steps (4) and (5) into an adsorption isothermal curve according to the mass sensitivity of the resonant micro-cantilever: namely a relation curve of gas adsorption quantity and pressure under constant temperature;
(7) calculating the change delta H degree of the adsorption enthalpy according to the adsorption isothermal curve and a Clausius-Klebsiella equation;
(8) any one adsorption isothermal curve is taken and transformed into a relation curve of p/V and p, and an adsorption equilibrium constant K and a standard equilibrium constant K DEG are obtained according to the intercept and the slope of the curve;
(9) according to the value of K, calculating the coverage degree theta under specific adsorption gas partial pressure by a Langmuir equation;
(10) according to the K degrees and the test temperature of the adsorption isothermal curve obtained in the step (8), solving the Gibbs free energy change delta G degrees by a Van't Hoff equation;
(11) and (3) according to the numerical values of the Gibbs free energy change delta G DEG and the adsorption enthalpy change delta H DEG, calculating the entropy change delta S DEG according to the definition formula of the Gibbs free energy change.
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