CN107247063A - A kind of in situ NMR test reactor and detection method - Google Patents
A kind of in situ NMR test reactor and detection method Download PDFInfo
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- CN107247063A CN107247063A CN201610318835.0A CN201610318835A CN107247063A CN 107247063 A CN107247063 A CN 107247063A CN 201610318835 A CN201610318835 A CN 201610318835A CN 107247063 A CN107247063 A CN 107247063A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
- G01N24/082—Measurement of solid, liquid or gas content
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Abstract
The present invention relates to a kind of in situ NMR test reactor and detection method, the tracking and detection of hydrogen-containing compound during true solid-liquid-gas light-catalyzed reaction can be realized.The situ reactor includes：It is fixedly connected with nuclear magnetic tube and optical fiber and the nuclear-magnetism cap of gas circuit；Sealing ring is covered on upper and lower perforate in the middle of nuclear-magnetism cap, hole, is connected respectively with nuclear magnetic tube with optical fiber；The top port is used to make customization optical fiber be deep into nuclear magnetic tube, and light is incided in heterogeneous solid-liquid suspension to be measured；Close to edge perforate above nuclear-magnetism cap, sealing ring is covered on hole, is connected with gas circuit；The port is used to gas being passed into nuclear magnetic tube.Using apparatus of the present invention, in situ the evolution process containing hydrogen reactant and its diffusion properties in a liquid during heterogeneous reaction, quantitative resolution reaction intermediate structural information can be followed the trail of, and then illustrate the influence factor and its mechanism of action of catalytic process.The method of testing can be studied and hydrocarbon related solid-liquid-gas catalytic field reactivity worth mechanism.The situ reactor is ingenious in design, simple to operate, and cost is low, is conducive to the popularization and application in other light reactions and heterogeneous catalytic reaction system.
Description
Technical field
The present invention relates to the in situ NMR test reactor under a kind of solid-liquid-gas reaction environment and detection method, the variation track tracking of hydrogen-containing compound and carbon compound in the courses of reaction such as photodissociation aquatic products hydrogen, fuel cell and carbon dioxide photo-reduction/photoelectric reduction is particularly suitable for use in, the reactor and method possess potential ability for research to hydrocarbon related solid-liquid-gas catalytic field reactivity worth mechanism.
Background technology
Energy shortage, environmental pollution and climatic issues are the global problems for 21 century restricting human society sustainable and healthy development.Compared with " the carbon economy " that traditional fossil energy is produced as representative, production hydrogen technology by driving force of solar energy has the advantages that calorific value height, no pollution, zero-emission, the problems such as energy, environment and weather can fundamentally being solved, while being also from traditional " carbon economy " to the future " hydrogen economy " more cleaned excessive important technical basis.Utilize conductor photocatalysis material system, by " artificial light compositing " process, extensive produce that hydrogen fuel is realized using water as raw material is to change energy general layout based on current fossil fuel, meet the important channel of future source of energy demand, and with great scientific meaning and society, economic value.The factors affects such as prepared by the design of catalysis material, the selection of co-catalyst and the matching of catalyst system and catalyzing overall photocatalytic water H2-producing capacity, and researcher is for further lifting that the scarcity that Reaction Mechanisms recognize is even more the exploitation and hydrogen generation efficiency that significantly limit high-performance optical catalysis material system.
Major part is studied at present and means of testing is observed under the ideal conditions such as low temperature, vacuum, but for the heterogeneous smooth decomposition water course of reaction of physical presence solid-liquid-gas multiphase, the linkage factor of influence in its course of reaction in multiple dimensioned aspect is ignored by most of hypothesis testing models.Therefore, seek can across yardstick tracking and the method that detects true solid-liquid-gas light-catalyzed reaction process, be the important thinking for breaking through the field study mechanism and development bottleneck at present, with very important scientific research value and practical significance.
The content of the invention
In view of problem above, the present invention proposes a kind of in situ NMR test reactor and method of testing, it can carry out in-situ tracking under illumination condition to the course of reaction under true solid-liquid-gas photocatalytic water reaction condition.The problem of solving the illumination normal temperature and pressure gas-liquid-solid experiment condition that congenic method under currently available technology can not be met.
The concrete technical scheme of the present invention is as follows：
A kind of in situ NMR test reactor, including：It is fixedly connected with nuclear magnetic tube and optical fiber and the nuclear-magnetism cap of gas circuit；Sealing ring is covered on upper and lower perforate in the middle of nuclear-magnetism cap, hole, is connected respectively with nuclear magnetic tube with optical fiber；The top port is used to make customization optical fiber be deep into nuclear magnetic tube, and light is incided in heterogeneous solid-liquid suspension to be measured；Close to edge perforate above nuclear-magnetism cap, sealing ring is covered on hole, is connected with gas circuit；The port is used to gas being passed into nuclear magnetic tube.
The invention also provides a kind of method of testing for realizing that hydrogen-containing compound is tracked in true solid-liquid-gas photocatalysis hydrogen production process using above-mentioned in situ NMR test reactor, its step includes：
1）Nuclear-magnetism cap is connected with optical fiber and gas circuit pipe, if not doing gas experiment, by the gas circuit seal of tube or can be opened wide；
2）Test sample is added in situ NMR test reactor, the nuclear-magnetism cap of even good optical fiber and gas circuit pipe is connected with installing the nuclear magnetic tube of test sample, the light source such as the optical fiber other end and xenon lamp is connected；
3）In situ NMR test reactor is positioned in nuclear magnetic resonance spectrometer cavity, xenon source is opened, nuclear magnetic resonance test experiments are carried out.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention is to realize tracking and detection containing hydrogen reactant in course of reaction under the true solid-liquid-gas reaction condition of photocatalytic water, and use can be directly connected to nuclear magnetic tube and optical fiber and the nuclear-magnetism cap of gas circuit, can realize illumination condition lasting in course of reaction；Nuclear-magnetism cap aperture gate material seal washer processing, it is ensured that the sealing of this device is excellent；In addition the situ reactor is ingenious in design, simple to operate, and cost is low, is conducive to the popularization and application in other light reactions and heterogeneous catalytic reaction system.
Brief description of the drawings
Fig. 1 and Fig. 2 are the structural representations of nuclear-magnetism cap in embodiment situ nmr response device, and wherein Fig. 1 is top view, and Fig. 2 is Fig. 1 midship sections A-A sectional view.
Fig. 3 is the structural representation of optical fiber in embodiment situ nmr response device；
Fig. 4 is the overall appearance schematic diagram of embodiment situ nmr response device；
Fig. 5 be in embodiment 1 heterogeneous solid-liquid system before illumination1H NMR spectras；
Fig. 6 is that heterogeneous solid-liquid system is changed over time in During Illumination in embodiment 11H NMR spectras；
Fig. 7 be in embodiment 2 sample A after illumination1H NMR spectras；
Fig. 8 be in embodiment 2 sample B after illumination1H NMR spectras.
Fig. 9 is sample A intermediate products after illumination in embodiment 21H NMR spectras.
Embodiment
Below, in order to facilitate the understanding of the purposes, features and advantages of the present invention, below by specific embodiments and the drawings, the present invention will be further described.
Fig. 1 and Fig. 2 are the structural representations of nuclear-magnetism cap in situ NMR reactor, and wherein Fig. 1 is top view, and Fig. 2 is Fig. 1 midship sections A-A sectional view.The nuclear-magnetism cap has the optical fiber entry port 1 being oppositely arranged and the nuclear magnetic tube connectivity port 3 being oppositely arranged, for making bare optical fiber part enter in nuclear magnetic tube and realizing the continuous light of testing sample in nuclear magnetic tube；The nuclear-magnetism cap further has the gas circuit entry port 2 being oppositely arranged, for providing the required atmosphere in reactor, if be able to need not open wide.The size of port 1 is according to depending on fiber size.A diameter of 8.2 mm of the present embodiment middle port 1.Sealing ring can be placed during connection, to carry out encapsulation process to the junction of optical fiber and nuclear-magnetism cap.Depending on the size of port 2 is according to the size of nuclear-magnetism pipe port.Sealing ring can be placed during connection, to carry out encapsulation process to the junction of nuclear magnetic tube and nuclear-magnetism cap.Depending on the size of port 3 is according to the size of gas circuit pipe.A diameter of 4 mm of the present embodiment middle port 3.
Shape, size and the material of the nuclear-magnetism cap can be set according to actual needs.In the present embodiment, the nuclear-magnetism cap is cylindric.The material of the nuclear-magnetism cap is polytetrafluoroethylmaterial material.
Fig. 3 is the structural representation of optical fiber in embodiment situ nmr response device.The fibre bundle that optical fiber is made up of 7 naked fibres used in the present embodiment.Afterbody is connected with light source needed for experiment.Light source is xenon source in the present embodiment.Can be by changing the illumination apparatus（Light source）Power and wave band there is provided the different light intensity needed for experiment.In the embodiment, in addition to naked fibre, remaining parcel optical fiber and illumination apparatus are arranged on the nuclear-magnetism containment portion.
Referring to Fig. 4, the measuring method studied using the in situ NMR reactor of the present invention is comprised the following steps：
Step 1：Fill sample sealing.
The testing sample is added in nuclear magnetic tube, testing sample can be liquid or the heterogeneous sample of solid-liquid.After addition can ultrasonic disperse it is uniform.The nuclear magnetic tube for carrying the testing sample is connected with nuclear-magnetism cap, if desired closed environment, can add sealing ring at nuclear-magnetism cap port 3.Connect connection customization optical fiber at the nuclear-magnetism cap port 1 of nuclear magnetic tube.Such as atmosphere is needed to test, gas circuit pipe needed for being connected at nuclear-magnetism cap 2 is not needed such as, salable or unlimited.
Step 2：Reactor is put into nuclear-magnetism intracavitary.
The in situ NMR reactor of the dress sample good seal is put into nuclear-magnetism cavity, height is adjusted, fiber outlet is connected with xenon source.
Step 3：Nuclear magnetic data initial acquisition.
Nuclear magnetic data initial acquisition is carried out to the in situ NMR reactor being put into nuclear-magnetism cavity, and sets up baseline.
Step 4：Introduce reaction condition.
Illumination or ventilation are carried out as needed, and illumination and aeration condition are either provided simultaneously or illumination and the switching of lucifuge condition is carried out.
Step 5：Signal acquisition.
Nuclear magnetic resonance map in the in situ NMR reactor of interval collection at regular intervals in liquid.
Step 6：Interpretation of result.
The gathered nuclear magnetic resonance map of processing, is analyzed experimental result.
The in situ NMR reactor and method of testing that the present invention is provided have the advantages that.Firstth, nuclear magnetic tube and optical fiber can be joined directly together by nuclear-magnetism cap, it is possible to achieve real-time online detection be carried out to the reactant in situ NMR reactor during illumination reaction, without separation product.Second, the gentle road of optical fiber can be incorporated into situ NMR reactor by nuclear-magnetism cap upper aperture 1 and hole 2 simultaneously, in situ NMR reactor is set to be combined together illumination condition and atmospheric condition, single illumination condition or atmospheric condition can be provided, illumination condition and atmospheric condition can be also provided simultaneously, the conversion between conversion and the illumination condition lucifuge condition between illumination condition and atmospheric condition can also be carried out, make being more widely applied in situ NMR reactor, be conducive to the popularization and application in other light reactions and heterogeneous catalytic reaction system, experimental procedure can also be simplified simultaneously, committed step mechanism in course of reaction is parsed.
In the present invention, if without particularly illustrating, all embodiments and preferred embodiment mentioned in this article can be combined with each other to form new technical scheme.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can be combined with each other to form new technical scheme.
The present invention is specifically described below in conjunction with specific embodiment is preferable to carry out method; it is to be understood that; those skilled in the art can be on the premise of the scope limited without departing substantially from claims; these embodiments are reasonably changed, improved and are mutually combined; so as to obtain new specific implementation method, these are also included within protection scope of the present invention by changing, improveing and being mutually combined the new embodiment of acquisition.
Specific embodiment 1：Study the generation process of hydrogen-containing gas in solution in photocatalytic water course of reaction
Step 1, the preparation of catalyst and dress calibration are standby
By appropriate PdCl2The aqueous solution is added to equipped with 100 mg TiO2Crucible in, 80oStirring and drying under the conditions of C；Crucible is put into Muffle furnace, with 5oMuffle furnace is warming up to 300 by C/min speedoC, constant temperature handles 1 h；Then, room temperature is naturally cooled to, crucible is taken out.Then, sample is taken out and be positioned in quartzy Noah's ark, and quartzy Noah's ark is pushed into tube furnace central thermal zone position, and seal up ring flange；By hydrogen and argon gas after spinner flowmeter is measured（Hydrogen flowing quantity is 20 % with argon flow amount ratio
H2/Ar）Enter tube furnace after being sufficiently mixed；With 5oTube furnace is warming up to 300 by C/min speedoC, constant temperature handles 1 h；Then, room temperature is naturally cooled to, sample is taken out, in case nuclear magnetic resonance test is used.
By 1 mg Pd/TiO2Catalyst, 300 μ L CD3OD、300 μL H2O and 5 μ L D2O（Contain 1 %
DSS internal standards）It is added in nuclear magnetic tube, ultrasonic disperse is uniform.Then nuclear magnetic tube is connected with optical fiber with gas circuit pipe by nuclear-magnetism cap, nitrogen or argon gas are passed through into nuclear magnetic tube by gas circuit pipe before reaction, to exclude the air in nuclear magnetic tube.
Sample carrying in situ NMR reactor is put into nuclear magnetic resonance cavity, fiber outlet is connected with xenon source.
Step 2, in situ NMR test
Under conditions of lucifuge, the sample carried in step 1 in situ NMR reactor is carried out in situ1H NMR are tested.Nuclear magnetic resonance apparatus in embodiment is 700 MHz Agilent nuclear magnetic resonance apparatus.Xenon source is then turned on, in During Illumination, in the in situ NMR reactor of interval collection at regular intervals in liquid1H signal.Reference picture 5, to the liquid collected in situ NMR reactor before reaction1H signal analysis is visible, in the heterogeneous system1H species signals are high-visible.Reference picture 6, to the liquid collected in situ NMR reactor after illumination1H signal analysis is visible, with the increase of light application time, H2Peak gradually increases, and illustrates that catalyst constantly produces H during illumination2And discharge in a liquid.Preferably, peak shape differentiates clear to the in situ NMR reactor data signal under test intensity, can realize the detection of hydrogeneous intermediate product under the conditions of true illumination solid-liquid reaction.
Specific embodiment 2：Study H2O/CD3OD and D2O/CH3The generation of hydrogen-containing gas and intermediate product in OH systems
Pd/TiO2The synthetic method of catalyst is similar to Example 1.By 2 mg Pd/TiO2Catalyst, 20 μ L CH3OH and 500 μ L D2O（Sample A）And 2 mg Pd/TiO2Catalyst, 20 μ L H2O and 500 μ L CD3OD（Sample B）It is added in different nuclear magnetic tubes, ultrasonic disperse is uniform.Subsequent dress calibration is standby similar with implementing 1.
Under conditions of lucifuge, the sample in carrying in situ NMR reactor is carried out in situ1H NMR are tested.Nuclear magnetic resonance apparatus in embodiment is 700 MHz Agilent nuclear magnetic resonance apparatus.Xenon source is then turned on, in liquid in situ NMR reactor after illumination certain time1H signal is acquired.Reference picture 7 and Fig. 8, to the liquid collected in situ NMR reactor after illumination1H signal analysis is visible, and faint HD gas peak is occurred in that in sample A nuclear magnetic spectrogram, and occurs in that H in sample B nuclear magnetic spectrum2With HD gas peak.Reference picture 9, in sample A, CH is occurred in that in the signal after illumination2DOD intermediate products, and resolution ratio is clear.This represents that the in situ NMR reactor can realize the online observation in situ of the different solid system under actual response environment.
Presently preferred embodiments of the present invention is the foregoing is only, those skilled in the art can modify or equivalent substitution in spirit of the invention, all changes done according to spirit of the invention should all belong to covering scope claimed of the invention.
Claims (7)
1. a kind of in situ NMR test reactor, it is characterised in that including：It is fixedly connected with nuclear magnetic tube and optical fiber and the nuclear-magnetism cap of gas circuit；Sealing ring is covered on upper and lower perforate in the middle of nuclear-magnetism cap, hole, is connected respectively with nuclear magnetic tube with optical fiber；The top port is used to make customization optical fiber be deep into nuclear magnetic tube, and light is incided in heterogeneous solid-liquid suspension to be measured；Close to edge perforate above nuclear-magnetism cap, sealing ring is covered on hole, is connected with gas circuit；The port is used to gas being passed into nuclear magnetic tube.
2. in situ NMR test reactor as claimed in claim 1, it is characterised in that：Sealed between optical fiber and nuclear-magnetism cap, gas circuit pipe and nuclear-magnetism cap, nuclear-magnetism cap and nuclear magnetic tube.
3. in situ NMR test reactor as claimed in claim 1, it is characterised in that：A diameter of 5~10 mm of nuclear-magnetism cap intelligent acess mouthful, gas circuit mouthful access a diameter of 3~6 mm, a diameter of 3~6 mm of nuclear magnetic tube access port.
4. in situ NMR test reactor as claimed in claim 1, it is characterised in that：A diameter of 20~30 mm of nuclear-magnetism cap.
5. in situ NMR test reactor as claimed in claim 1, it is characterised in that：It carries out real-time online detection during can realizing light-catalyzed reaction to the reactant in situ NMR reactor, and without separation product.
6. in situ NMR test reactor as claimed in claim 1, it is characterised in that：The gentle road of optical fiber can be incorporated into situ NMR reactor by nuclear-magnetism cap upper aperture 1 and hole 2 simultaneously, in situ NMR reactor is set to be combined together illumination condition and atmospheric condition, single illumination condition or atmospheric condition can be provided, also illumination condition and atmospheric condition can be provided simultaneously, moreover it is possible to carry out the conversion between conversion and the illumination condition lucifuge condition between illumination condition and atmospheric condition.
7. in situ NMR test reactor described in a kind of use claim 1 realizes the method for testing that hydrogen-containing compound is tracked in true solid-liquid-gas photocatalysis hydrogen production process, its step includes：
1）Nuclear-magnetism cap is connected with optical fiber and gas circuit pipe, if not doing gas experiment, by the gas circuit seal of tube or can be opened wide；
2）Test sample is added in situ NMR test reactor, the nuclear-magnetism cap of even good optical fiber and gas circuit pipe is connected with installing the nuclear magnetic tube of test sample, the light source such as the optical fiber other end and xenon lamp is connected；
3）In situ NMR test reactor is positioned in nuclear magnetic resonance spectrometer cavity, xenon source is opened, nuclear magnetic resonance test experiments are carried out.
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Cited By (2)
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| CN111122638A (en) * | 2020-03-31 | 2020-05-08 | 南京昊绿生物科技有限公司 | Nuclear magnetic testing device and method for monitoring reaction process in real time on line |
| CN113740369A (en) * | 2020-05-29 | 2021-12-03 | 华东师范大学 | Reduction method for detecting heavy metal ions based on in-situ low-field nuclear magnetic resonance relaxation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111122638A (en) * | 2020-03-31 | 2020-05-08 | 南京昊绿生物科技有限公司 | Nuclear magnetic testing device and method for monitoring reaction process in real time on line |
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| CN113740369A (en) * | 2020-05-29 | 2021-12-03 | 华东师范大学 | Reduction method for detecting heavy metal ions based on in-situ low-field nuclear magnetic resonance relaxation method |
| CN113740369B (en) * | 2020-05-29 | 2024-03-12 | 华东师范大学 | Reduction method for detecting heavy metal ions based on in-situ low-field nuclear magnetic resonance relaxation method |
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