CN218674741U

CN218674741U - LIBS-EC integrated detection device

Info

Publication number: CN218674741U
Application number: CN202222371923.0U
Authority: CN
Inventors: 杨远帆; 马明俊; 戚功美; 陈石华; 杨猛; 赵南京; 黄行九
Original assignee: Hefei Institutes of Physical Science of CAS
Current assignee: Hefei Institutes of Physical Science of CAS
Priority date: 2022-09-06
Filing date: 2022-09-06
Publication date: 2023-03-21
Anticipated expiration: 2032-09-06

Abstract

The utility model discloses a LIBS-EC integrated detection device, which comprises a shell, wherein a longitudinal clapboard is fixedly arranged in the shell and divides the inner space of the shell into an operation space and a storage space, and a spectrometer, a laser and an electrochemical workstation are arranged in the storage space; a reaction tank and a PC industrial personal computer are arranged in the operation space; electrodes are arranged in the reaction tank and electrically connected with the electrochemical workstation; the laser output end of the laser is focused on the surface of an electrode in the reaction cell through a laser transposition head; the plasma receiver is arranged at the bottom end of the laser transposition head, and the plasma receiver is connected with the spectrometer through an optical fiber; the spectrometer and the electrochemical workstation are electrically connected with a PC industrial personal computer. The LIBS detection can be realized by the enrichment effect of the electrochemical workstation on the heavy metals, and the LIBS-EC cooperative detection under a solution and the anti-interference detection of the heavy metals in the complex water body are realized.

Description

LIBS-EC integrated detection device

Technical Field

The utility model relates to a nano-material technique and heavy metal pollutant detection area specifically are an integrative detection device of LIBS-EC.

Background

At present, the problem of water environment pollution is increasingly prominent, particularly heavy metal pollution, and a plurality of methods for detecting the heavy metal pollutants in the water body are used at home and abroad. Common detection methods include Atomic Absorption Spectroscopy (AAS), inductively coupled plasma-emission spectroscopy (ICP-AES), inductively coupled plasma-atomic fluorescence spectroscopy (ICP-AFS), atomic Fluorescence Spectroscopy (AFS), mass Spectrometry (MS) and electrochemical analysis (electrochemical analysis), wherein the electrochemical analysis has a wide application range due to the advantages of simple equipment, convenience in operation, high sensitivity, easiness in miniaturization and the like.

The development of the nano modified electrode greatly improves the detection sensitivity and selectivity of an electrochemical method for heavy metal pollutants, but when multi-component heavy metals coexist under a complex background, the detection accuracy and the anti-interference performance are still the bottleneck of the electrochemical analysis method. Research shows that a large number of inorganic ions and organic molecules in the actual water environment directly influence the electrochemical detection analysis result.

Compared with other element analysis technologies, the Laser Induced Breakdown Spectroscopy (LIBS) technology can perform all-element analysis and real-time analysis, and has the advantages that samples do not need to be pretreated, the forms of the samples are not limited, and the like. The method is also gradually applied to analysis of liquid samples in recent years, but the LIBS has relatively poor detection limit on the liquid samples, and analysis of the forms of heavy metal pollutants in water environments cannot be directly realized.

SUMMERY OF THE UTILITY MODEL

In view of this, the utility model provides a LIBS-EC normal position detecting instrument, establish the analytic mode of normal position LIBS-EC under a solution promptly through LIBS-EC all-in-one, the electrochemical deposition-the process of dissolving out of the metal contamination on real-time dynamic detection electrochemical electrode surface reveals the mutual interference mechanism between the heavy metal contamination and realizes anti-interference detection.

In order to achieve the above object, the utility model provides a following technical scheme:

a LIBS-EC integrated detection device comprises a shell, wherein a longitudinal partition plate is fixedly arranged in the shell and divides the inner space of the shell into an operation space and a storage space, and a spectrometer, a laser and an electrochemical workstation are arranged in the storage space; a reaction tank and a PC industrial personal computer are arranged in the operation space; electrodes are arranged in the reaction tank and electrically connected with the electrochemical workstation; the laser output end of the laser is focused on the surface of an electrode in the reaction cell through a laser transposition head; the plasma receiver is arranged at the bottom end of the laser transposition head, and the plasma receiver is connected with the spectrometer through an optical fiber; the spectrometer and the electrochemical workstation are electrically connected with a PC industrial personal computer.

In a further scheme, a magnetic stirrer is arranged at the bottom end of the reaction tank.

According to a further scheme, a micro peristaltic pump is arranged in the operation space and communicated with the reaction tank through a pipeline to be used for leading in or discharging a sample to be detected in the reaction tank.

Preferably, the laser transposition head penetrates through a longitudinal partition plate through a connecting pipe to be fixedly connected with the laser, and switches respectively used for controlling the magnetic stirrer, the electrochemical workstation and the PC industrial personal computer are respectively installed on the longitudinal partition plate; and the longitudinal partition plate is provided with a through hole for the optical fiber to pass through.

In a further scheme, a power supply end of the electrochemical workstation is connected with an electrochemical workstation power supply, a three-phase power socket is mounted on a shell positioned at the power supply end of the electrochemical workstation, and the three-phase power socket is electrically connected with an outer end power supply and is used for providing working power supplies of the electrochemical workstation power supply, the magnetic stirrer, the PC industrial personal computer, the micro peristaltic pump and the spectrometer.

In a further scheme, a transverse partition plate is arranged in the storage space in a horizontal frame, the laser and the electrochemical workstation are fixedly arranged on the top end face of the transverse partition plate, and the spectrometer and the electrochemical workstation power supply are fixedly arranged on a shell positioned below the transverse partition plate.

In the further scheme, a display window is arranged on a shell positioned on the front side of the PC industrial personal computer.

In a further scheme, a water-cooling power supply machine is externally connected with the laser for supplying electric energy and cooling the laser. The water-cooling power supply machine is a known commercially available product, and the power supply water-cooling machine in the application is an ultra power supply water-cooling machine produced by a manufacturer quantel.

The utility model discloses integrate electrochemistry detection device and LIBS detection device organic as an organic whole, can real-time dynamic monitoring electrochemistry deposition-the process of dissolving out of the heavy metal contamination on electrochemistry electrode surface, be expected to reveal the mutual interference mechanism of heavy metal contamination between the effect mechanism and the heavy metal contamination of heavy metal contamination on electrode surface. Therefore, the problems of low accuracy and interference in electrochemical detection are solved, and the defect that LIBS detection cannot be used for detecting and analyzing a liquid sample is overcome.

The method has the advantages that heavy metal in a sample to be detected is enriched on an electrode through the enrichment effect of the heavy metal in the electrochemical detection process; after liquid is emptied, LIBS detection can be realized, the sensitivity of LIBS for detecting heavy metal pollutants in the solution can be further improved, and the anti-interference detection of heavy metals in complex water bodies can be realized.

Drawings

FIG. 1 is a schematic view of the structure of the present invention,

figure 2 is a schematic left-hand view of the internal structure of the present invention,

fig. 3 is a right-hand schematic view of the internal structure of the present invention.

In the figure: 1-shell, 11-display window, 12-transverse clapboard, 13-longitudinal clapboard and 14-three-phase power socket; 2-PC industrial personal computer, 3-flip, 31-buckle, 4-spectrometer, 41-plasma receiver, 5-laser, 51-laser transposition head, 6-reaction tank, 7-stirrer, 8-electrochemical workstation, 81-electrochemical workstation power supply, 9-micro peristaltic pump.

Detailed Description

To facilitate an understanding of the present invention, the present invention will be described more fully with reference to the following specific embodiments. The invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

As shown in fig. 1-3, an LIBS-EC integrated detecting device comprises a housing 1, wherein a longitudinal partition 13 is fixedly arranged inside the housing 1 and divides the internal space of the housing into an operating space and a storage space, for convenience of operation, a movable flip 3 is arranged above the operating space, and a buckle 31 for connecting the flip 3 with the housing 1 is arranged on the flip 3. When not in work, the flip cover 3 is used for buckling and protecting the internal instrument, and when in work, the flip cover 3 is opened, so that the internal switch is convenient to operate.

A spectrometer 4, a laser 5 and an electrochemical workstation 8 are arranged in the storage space; specifically, the laser 5 and the electrochemical workstation 8 are fixedly arranged on the top end surface of the diaphragm 12, and the spectrometer 4 and the electrochemical workstation power supply 81 are fixedly arranged on a shell positioned below the diaphragm 12. Thus, the whole space is reasonably arranged and the space is saved

A reaction tank 6 and a PC industrial personal computer 2 are arranged in the operation space; the reaction tank 6 is an electrochemical electrolytic tank in an electrochemical workstation, an electrode is arranged in the reaction tank 6, and the electrode is electrically connected with the electrochemical workstation 8; the laser output end of the laser 5 is focused on the surface of the electrode in the reaction tank 6 through a laser transposition head 51; that is, the laser transposing head 51 converts the laser light in the horizontal direction into the vertical direction so that it is focused just on the electrode surface. The plasma receiver 41 is installed at the bottom end of the laser transposing head 51, and the plasma receiver 41 is connected with the spectrometer 4 through an optical fiber; the plasma signal captured by the plasma receiver 41 is fed back to the spectrometer for spectral analysis. The spectrometer 4 and the electrochemical workstation 8 are electrically connected with the PC industrial personal computer 2 for signal transmission.

In the embodiment, the PC industrial personal computer and the spectrometer are known commercial products, wherein the PC industrial personal computer can be an AIBAOTU and 10.4-inch industrial control all-in-one machine; the spectrometer is of the AVANTES type (WLS 2048-3-USB 2), and the plasma receiver is connected with the spectrometer through optical fibers.

Further scheme, the bottom of reaction tank 6 is equipped with magnetic stirrers 7, and magnetic stirrers 7 during operation stirs through the sample that awaits measuring that magnetic action made in the reaction tank 6, improves the accuracy that detects. A micro peristaltic pump 9 is arranged in the operation space, and the micro peristaltic pump 9 is communicated with the reaction tank 6 through a pipeline and used for leading in or discharging a sample to be detected in the reaction tank. Namely, the micro peristaltic pump 9 guides the sample to be detected into the reaction tank 6 during electrochemical detection, so that heavy metal in the sample to be detected is enriched on the electrode, thereby being beneficial to subsequent LIBS detection. When the LIBS is detected, a micro peristaltic pump 9 is used to discharge a sample to be detected from the reaction tank, and heavy metals enriched on the electrode are directly detected.

The laser transposition head 51 penetrates through the longitudinal partition plate 13 through a connecting pipe to be fixedly connected with a laser, and switches respectively used for controlling the magnetic stirrer, the electrochemical workstation and the PC industrial personal computer are respectively installed on the longitudinal partition plate 13; the longitudinal partition 13 is provided with a through hole for passing an optical fiber.

In a further scheme, a power end of the electrochemical workstation 8 is connected with an electrochemical workstation power supply 81 for supplying power to the electrochemical workstation 8; a three-phase power socket 14 is installed on the shell 1 at the end of the power supply 81 of the electrochemical workstation, and the three-phase power socket 14 is electrically connected with an external power supply and is used for providing a working power supply of the power supply 81 of the electrochemical workstation, a magnetic stirrer, a PC industrial personal computer and a micro peristaltic pump. And the power supply for the laser is external.

Further scheme has seted up display window 11 on being located 2 front sides of PC industrial computer's casing 1, conveniently operates the PC industrial computer.

In a further scheme, a power water cooler is externally connected to the laser 5 and used for providing electric energy and cooling the laser. In the embodiment, the power water cooler manufactured by quantel and having an ultra model is selected. When the device is used, the device is connected with a three-phase power socket through a power line to be powered on, then a switch of an electrochemical workstation, a switch of a PC industrial personal computer and a switch of a magnetic stirrer are sequentially turned on, and then power supplies of a laser and a spectrometer are turned on. Electrically connecting an electrode arranged in a reaction tank with an electrochemical workstation, then opening a micro peristaltic pump to lead a sample to be detected (the sample to be detected is a buffer solution plus heavy metal/actual water sample) into the reaction tank through a sample introduction pipeline, and simultaneously working a magnetic stirrer to stir the sample to be detected in the reaction tank through the action of magnetic force; the electrochemical workstation starts to work to carry out square wave voltammetry testing, and a detection result is fed back to a PC industrial personal computer to complete electrochemical detection; and simultaneously, the heavy metals in the sample to be detected are all enriched on the electrode.

And during or after the electrochemical detection is finished, emptying a sample to be detected in the electrochemical reaction tank by using a sample discharge pipeline of the micro peristaltic pump, driving laser to the surface of an electrode through a laser transposition head by using a laser to generate plasma, feeding the plasma to a spectrometer through an optical fiber after the plasma is received by a plasma receiver, and feeding the plasma to a PC industrial personal computer after the plasma is analyzed by the spectrometer to finish laser-induced breakdown spectroscopy, wherein the whole LIBS-EC combined detection process is finished, and the electrochemical detection and the laser spectrum detection are finished simultaneously.

The electrochemical workstation (Ec) is a short for electrochemical measurement system in the application, and is a commonly used measurement device for electrochemical research and teaching. An electrochemical workstation is an electronic instrument that controls the potential difference between a working electrode and a reference electrode. Wherein the working electrode, the counter electrode and the reference electrode are all components in the electrochemical electrolytic cell. The electrochemical workstation controls the potential difference between the working electrode and the reference electrode by injecting a current into the electrodes. In this example, chenghua 760E was selected as the electrochemical workstation.

The basic principle of the magnetic stirrer is that magnetic stirring arms arranged in a container are pushed by a magnetic field to perform circumferential operation by utilizing the principle that like poles repel and opposite poles attract of the magnetic field, so that the aim of stirring liquid is fulfilled.

The Laser Induced Breakdown Spectroscopy (LIBS) technique focuses ultrashort pulses on the surface of a sample to form plasma, and then analyzes the plasma emission spectrum to determine the material composition and content of the sample. The energy density of the ultra-short pulse laser is higher after the ultra-short pulse laser is focused, and the ultra-short pulse laser can excite a sample in any state (solid, liquid or gas) to form plasma.

Although the present description is described in terms of embodiments, not every embodiment includes only a single embodiment, and such description is for clarity only, and those skilled in the art should be able to integrate the description as a whole, and the embodiments can be appropriately combined to form other embodiments as will be understood by those skilled in the art.

Therefore, the above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application; all changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims

1. An LIBS-EC integrated detection device, comprising a housing (1), characterized in that: a longitudinal partition plate (13) is fixedly arranged in the shell (1) and divides the inner space of the shell into an operation space and a storage space, and a spectrometer (4), a laser (5) and an electrochemical workstation (8) are arranged in the storage space; a reaction tank (6) and a PC industrial personal computer (2) are arranged in the operation space; an electrode is arranged in the reaction tank (6) and is electrically connected with the electrochemical workstation (8); the laser output end of the laser (5) is focused on the surface of an electrode in the reaction tank (6) through a laser transposition head (51); the bottom end of the laser transposition head (51) is provided with a plasma receiver (41), and the plasma receiver (41) is connected with the spectrometer (4) through an optical fiber; the spectrometer (4) and the electrochemical workstation (8) are electrically connected with the PC industrial personal computer (2).

2. The LIBS-EC integrated detecting device according to claim 1, characterized in that: and a magnetic stirrer (7) is arranged at the bottom end of the reaction tank (6).

3. The LIBS-EC integrated detecting device according to claim 2, wherein: a micro peristaltic pump (9) is arranged in the operation space, and the micro peristaltic pump (9) is communicated with the reaction tank (6) through a pipeline and is used for leading in or discharging a sample to be detected in the reaction tank.

4. The LIBS-EC integrated detection device of claim 3, wherein: the laser transposition head (51) penetrates through a longitudinal partition plate (13) through a connecting pipe to be fixedly connected with a laser, and switches respectively used for controlling the magnetic stirrer, the electrochemical workstation and the PC industrial personal computer are respectively installed on the longitudinal partition plate (13); and the longitudinal partition plate (13) is provided with a through hole for passing an optical fiber.

5. The LIBS-EC integrated detection device of claim 3, wherein: the power end of the electrochemical workstation (8) is connected with an electrochemical workstation power supply (81); install three-phase supply socket (14) on casing (1) that is located electrochemistry workstation power (81) end, three-phase supply socket (14) are connected with the outer end power and are used for providing the working power supply of electrochemistry workstation power (81), magnetic stirrers, PC industrial computer, miniature peristaltic pump and spectrum appearance.

6. The LIBS-EC integrated detecting device according to claim 1, characterized in that: a transverse partition plate (12) is horizontally erected in the storage space, the laser (5) and the electrochemical workstation (8) are fixedly arranged on the top end face of the transverse partition plate (12), and the spectrometer (4) and the electrochemical workstation power supply (81) are fixedly arranged on a shell located below the transverse partition plate (12).

7. The LIBS-EC integrated detecting device according to claim 1, characterized in that: a display window (11) is arranged on the shell (1) positioned at the front side of the PC industrial personal computer (2).

8. The LIBS-EC integrated detecting device according to claim 1, characterized in that: the laser (5) is externally connected with a water-cooling power supply machine for providing electric energy and cooling the laser.