CN118209612A - Planar optical waveguide in-situ monitoring device and monitoring method for electrocatalytic hydrogen production - Google Patents
Planar optical waveguide in-situ monitoring device and monitoring method for electrocatalytic hydrogen production Download PDFInfo
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Abstract
The invention provides a planar optical waveguide in-situ monitoring device for electrocatalytic hydrogen production and a monitoring method thereof, wherein the planar optical waveguide in-situ monitoring device comprises a broadband light source, an in-situ electrolytic cell, a loss mode resonance sensor, an electrochemical workstation and a spectrometer, wherein the broadband light source, the loss mode resonance sensor and the spectrometer are mutually connected through an optical fiber transmission module; the invention analyzes the influence of the change of the electrocatalytic hydrolysis hydrogen production reaction medium and the dynamic behavior of bubbles generated on the surface of the electrocatalytic film on the catalytic hydrogen production efficiency by monitoring the change of the electrocatalytic hydrolysis hydrogen production reaction medium in real time, and solves the technical problem of difficult in-situ monitoring of the electrocatalytic hydrogen production process in the prior art.
Description
Technical Field
The invention relates to the field of electrocatalytic characterization, in particular to a planar optical waveguide in-situ monitoring device and a monitoring method for electrocatalytic hydrogen production.
Background
Hydrogen energy is an ideal green clean energy source, and the production of hydrogen is closely related to catalytic reaction. Extensive research into catalytic processes can promote synthesis of high-efficiency catalysts and optimization of catalytic reaction systems. In recent years, research on "catalysis and surface interface chemistry" has focused on "surface interface", and in-situ measurement and quantitative analysis of adsorption, activation, reaction, and change of chemical molecules and mass transfer of catalyst surface interface have become an indispensable part. However, the catalytic environment and the physicochemical process of the surface interface in the hydrogen production process exemplified by the electrolysis water and the photolysis water are very complicated, and it is difficult to accurately analyze the entire process, particularly the microscopic process of the surface interface. Therefore, developing advanced methods for in-situ and real-time online characterization of surfaces is of great theoretical and practical significance for understanding complex processes and relationships between surfaces and catalysts.
With the continuous development of the heterogeneous electrocatalytic hydrogen production technology, the mechanism research work is gradually in depth, researchers adopt methods (such as electrochemical detection, mass spectrum, chromatography, electron microscope and the like) to examine the physical and chemical change process of a catalyst surface interface, and key factors and microscopic mechanisms affecting the efficiency are revealed by researching the surface interface reaction process, so that the research has become a hot spot and a difficult point in the field of interface catalysis. The definition of the three-phase surface interface dynamic process and the microcosmic mechanism in the electrocatalytic hydrogen production system and the disclosure of the structure-activity relationship of the catalytic materials are key to further improve the hydrogen production efficiency of the electrocatalytic hydrogen production system, and are critical to the development of the hydrogen production industry. However, the various complex processes associated with gas evolution produce associated electrical signals, and therefore their effects should be determined separately. In particular, changes in the electrolytic environment can adjust the performance of the electrode, causing erroneous decisions.
In recent years, the dynamics of bubble evolution in the process of producing electrolytic gas have been studied by methods such as atomic force microscopy, transmission electron microscopy, dark field microscopy, high-speed microscopy photography, particle image processing, and the like, and particularly, the single bubble evolution has been studied. However, bulky, inefficient, and costly equipment is commonly used. In addition, ex-situ detection results in large measurement errors, which are severely dependent on the resolution and response speed of the device itself. In addition, in industrial production, the evolution speed of bubbles is high, and great difficulty is brought to real-time monitoring.
Disclosure of Invention
The invention aims to provide a planar optical waveguide in-situ monitoring device and a planar optical waveguide in-situ monitoring method for electrocatalytic hydrogen production, which are used for solving the technical problem that in-situ monitoring of an electrocatalytic hydrogen production process is difficult in the prior art. In order to solve the technical problems, the invention firstly provides a planar optical waveguide in-situ monitoring device for electrocatalytic hydrogen production, which comprises a broadband light source, an in-situ electrolytic cell, a loss mode resonance sensor, an electrochemical workstation and a spectrometer, wherein the broadband light source, the loss mode resonance sensor and the spectrometer are connected with each other through an optical fiber transmission module, the loss mode resonance sensor is positioned in the in-situ electrolytic cell, and the electrochemical workstation is electrically connected with an electrode assembly of the in-situ electrolytic cell;
When the in-situ electrolytic cell is monitored for electrocatalytic hydrogen production, the loss mode resonance sensor is placed under the laser emitted by the broadband light source, and the laser generates loss mode resonance on the surface of the loss mode resonance sensor.
Preferably, the loss mode resonance sensor includes a planar waveguide layer, a semiconductor layer, and a catalytic metal layer stacked from bottom to top, and the orthographic projection area of the semiconductor layer on the planar waveguide layer is smaller than the cross-sectional area of the planar waveguide layer.
Preferably, the planar waveguide layer is a cover glass, the semiconductor layer is an ITO material, and the catalytic metal layer is Pt particles.
Preferably, the electrode assembly in the in-situ electrolytic cell comprises a working electrode, a reference electrode and a counter electrode, and the electrode clamps of the electrochemical workstation clamp the working electrode, the reference electrode and the counter electrode respectively.
Preferably, the electrolyte in the in-situ electrolytic cell is dilute sulfuric acid solution, the semiconductor layer is multiplexed as a working electrode, the reference electrode is Ag/AgCl material, and the counter electrode is Pt coil wire.
Preferably, the optical fiber transmission module is a multimode optical fiber, and the core layer diameter of the multimode optical fiber is 100-300 μm.
Preferably, a linear polarizer is provided between the broadband light source and the loss mode resonance sensor, the linear polarizer being used to separate TE light and TM light in loss mode resonance.
Preferably, the in-situ electrolytic cell is also provided with a three-dimensional displacement table, the loss mode resonance sensor is fixed on the three-dimensional displacement table, and the three-dimensional displacement table is used for adjusting the height between the loss mode resonance sensor and the ground so as to enable the laser to generate loss mode resonance on the surface of the loss mode resonance sensor.
Correspondingly, the invention also provides a planar optical waveguide in-situ monitoring method for electrocatalytic hydrogen production, which comprises the following steps:
s10, sequentially depositing a semiconductor layer and a catalytic metal layer on the surface of a planar waveguide layer to form a loss mode resonance sensor;
s20, connecting a broadband light source, a loss mode resonance sensor and a spectrometer through a multimode fiber, and performing coupling alignment on the multimode fiber;
S30, fixing the loss mode resonance sensor on a three-dimensional displacement table, and adjusting the height of the loss mode resonance sensor through the three-dimensional displacement table so as to enable laser emitted by the broadband light source to generate loss mode resonance on the surface of the loss mode resonance sensor;
s40, separating TE light and TM light in loss mode resonance by adjusting a linear polarizer;
S50, placing the loss mode resonance sensor and the three-dimensional displacement table in an in-situ electrolytic cell filled with electrolyte, respectively clamping a plurality of electrodes in the in-situ electrolytic cell by electrode clamps of an electrochemical workstation, and adjusting the electrodes among the plurality of electrodes through the electrochemical workstation so as to perform electrocatalytic hydrogen production in the in-situ electrolytic cell;
S60, monitoring the electric signal change in the hydrogen bubble separation process under the constant potential condition through an electrochemical workstation, recording the optical signal change acquired by a spectrometer in the electrocatalytic hydrogen production process, and analyzing the electric signal and the optical signal through a data recording computer so as to realize real-time in-situ monitoring of electrocatalytic hydrogen production.
Preferably, after performing step S30 and before performing step S40, the method further includes:
And removing the loss mode resonance sensor from the three-dimensional displacement table, fixing the planar waveguide layer without the semiconductor layer on the three-dimensional displacement table, and placing the planar waveguide layer and the planar waveguide layer together in an in-situ electrolytic cell filled with electrolyte for correcting the spectrum baseline.
The beneficial effects of the invention are as follows: compared with the prior art, the invention provides a planar optical waveguide in-situ monitoring device and a monitoring method thereof for electrocatalytic hydrogen production, wherein the planar optical waveguide in-situ monitoring device comprises a broadband light source, an in-situ electrolytic cell, a loss mode resonance sensor, an electrochemical workstation and a spectrometer, wherein the broadband light source, the loss mode resonance sensor and the spectrometer are mutually connected through an optical fiber transmission module; when the electrocatalytic hydrogen production is carried out on the surface of the loss mode resonance sensor, the laser emitted by the broadband light source generates loss mode resonance on the surface of the loss mode resonance sensor, the spectrometer can quantitatively reveal the hydrogen production quantity in the electrocatalytic hydrogen production process according to the resonance wavelength drift of the loss mode resonance so as to sense the growth process of bubbles at the stage, and meanwhile, the electrochemical workstation monitors the hydrogen bubble separation process in the electrocatalytic hydrogen production process according to the current change among a plurality of electrodes in the in-situ electrolytic cell under the constant potential condition, so that the influence on the catalytic hydrogen production efficiency is analyzed by researching the bubble behaviors, the dynamics mechanism of a three-phase interface of the catalytic hydrogen production system is further known in depth from a microscopic level, the structural effect relationship of the catalytic surface is clarified, and the improvement of the catalytic hydrogen production efficiency of the electrocatalytic hydrogen production industry is further facilitated.
Drawings
FIG. 1 is a block diagram of a planar optical waveguide in-situ monitoring device for electrocatalytic hydrogen production, provided by an embodiment of the invention;
FIG. 2 is a block diagram of an electrochemical loss mode resonance platform in a planar optical waveguide in-situ monitoring device for electrocatalytic hydrogen production according to an embodiment of the present invention;
FIG. 3 is a flow chart of a method for in-situ monitoring of planar optical waveguides for electrocatalytic hydrogen production, provided by an embodiment of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Electrocatalytic hydrogen production involves a complex reaction process that can be divided into two stages, pre-bubble generation and post-bubble generation. In the discharge reaction process before bubble generation, active hydrogen is first generated and adsorbed on the active sites on the catalyst surface, and the liquid phase reactant on the catalyst surface is also changed.
Thus, the present invention can be understood by monitoring the refractive index changes of the solid and liquid media at the catalyst surface for the reaction process at this stage, including the formation of active hydrogen and the change in the liquid reaction media at the catalyst surface, followed by the bubble formation, growth and detachment stages. The change in film thickness is already substantially stable before bubble formation, so that the behavior of the bubbles at this stage causes a significant change in the refractive index of the catalyst surface. Meanwhile, the invention can sense the growth and detachment process of bubbles at this stage through the loss mode resonance sensor 9, and analyze the influence of the bubbles on the catalytic hydrogen production efficiency by researching the behavior of the bubbles. In contrast, the electrochemical loss mode resonance platform can be used for online in-situ monitoring of the hydrogen production reaction process, and has the advantages of quick response, corrosion resistance and small volume. Meanwhile, the accuracy of the monitoring result can be mutually verified by combining the data acquired by optical and electrical synchronization.
Aiming at the difficulty in-situ monitoring of the electrocatalytic hydrogen production process in the prior art, the invention provides a planar optical waveguide in-situ monitoring device and a monitoring method thereof for electrocatalytic hydrogen production. The invention aims to provide a new technical implementation method for the research of the catalytic hydrogen production process by monitoring the change of an electrocatalytic hydrolysis hydrogen production reaction medium and the dynamic behavior of bubbles generated on the surface of an electrocatalytic film in real time. The method can be used for deeply knowing the dynamic mechanism of the three-phase interface of the catalytic hydrogen production system from a microscopic level, and defining the structural effect relationship of the catalytic surface, thereby providing the planar optical waveguide in-situ monitoring device capable of in-situ monitoring the electrocatalytic hydrogen production process.
Specifically, referring to fig. 1 to 2, fig. 1 is a block diagram of a planar optical waveguide in-situ monitoring device for electrocatalytic hydrogen production according to an embodiment of the present invention; FIG. 2 is a block diagram of an electrochemical loss mode resonance platform in a planar optical waveguide in-situ monitoring device for electrocatalytic hydrogen production according to an embodiment of the present invention; the invention provides a planar optical waveguide in-situ monitoring device for electrocatalytic hydrogen production, which at least comprises a broadband light source 1, an in-situ electrolytic cell, a loss mode resonance sensor 9, an electrochemical workstation 5 and a spectrometer 6 (Avants spectrometer);
Wherein, broadband light source 1, loss mode resonance sensor 9 and spectrometer 6 are connected with each other through fiber optic transmission module 10, and loss mode resonance sensor 9 is located in the normal position electrolytic cell, and electrochemical workstation 5 is connected with the electrode subassembly of normal position electrolytic cell electricity.
Specifically, when the in-situ electrolytic cell is monitored for electrocatalytic hydrogen production, the loss mode resonance sensor 9 is placed under the laser emitted by the broadband light source 1, the laser generates loss mode resonance on the surface of the loss mode resonance sensor 9, the spectrometer 6 is used for quantitatively revealing the hydrogen production amount according to the resonance wavelength drift of the loss mode resonance, and the electrochemical workstation 5 is used for monitoring the hydrogen bubble separation process according to current change under constant potential conditions.
In the embodiment of the present invention, the loss mode resonance sensor 9 includes a plane waveguide layer, a semiconductor layer and a catalytic metal layer, which are stacked from bottom to top, and the orthographic projection area of the semiconductor layer on the plane waveguide layer is smaller than the cross-sectional area of the plane waveguide layer.
In particular, the loss mode resonance sensor 9 is capable of performing both electrochemical and optical measurements, in particular Loss Mode Resonance (LMR), to monitor the growth of hydrogen on the working electrode 2.
Further, loss Mode Resonance (LMR) is a resonance generated by the mutual coupling between evanescent waves and detuned modes within a conductive metal oxide, which can be excited by Transverse Electric (TE) or Transverse Magnetic (TM) polarized light. Such resonance may cause the intensity of light transmitted in the optical waveguide to decrease drastically, thereby forming a resonance trough. The LMR effect is sensitive to the external refractive index, and when the external refractive index changes, the resonance trough of the LMR also changes correspondingly to reflect the refractive index change of the external substance, so that the refractive index conversion can be used for obtaining the to-be-measured value.
Preferably, the plane waveguide layer is a cover glass, the semiconductor layer is made of ITO material, and the catalytic metal layer is Pt particles; wherein, the cover glass can be used as a planar waveguide, the semiconductor layer can be multiplexed into a working electrode 2 in an in-situ electrolytic cell for electrocatalytic hydrogen production, and the catalytic metal layer is used as a catalyst for electrocatalytic hydrogen production.
In the embodiment of the invention, the electrode assembly in the in-situ electrolytic cell comprises a working electrode 2, a reference electrode 3 and a counter electrode 4, and the electrode clamps of the electrochemical workstation 5 clamp the working electrode 2, the reference electrode 3 and the counter electrode 4 respectively.
Wherein, electrolyte in the in-situ electrolytic cell is dilute sulfuric acid solution, the working electrode 2 is ITO material, the reference electrode 3 is Ag/AgCl material, and the counter electrode 4 is Pt coil wire.
Referring to fig. 1 and 2, a broadband light source 1, a loss mode resonance sensor 9 and a spectrometer 6 are connected with each other through an optical fiber transmission module 10, wherein the optical fiber transmission module 10 is a multimode optical fiber, and the diameter of a core layer of the multimode optical fiber is 100-300 μm; the laser (visible light wave band) emitted by the broadband light source 1 generates loss mode resonance on the surface of the loss mode resonance sensor 9, the spectrometer 6 receives an optical signal generated by the loss mode resonance through the multimode optical fiber, and transmits the optical signal to the data recording computer 7 to analyze the optical signal, so as to realize real-time in-situ monitoring of electrocatalytic hydrogen production.
Specifically, after the electrochemical loss mode resonance platform shown in fig. 2 is prepared, the visible light emitted from the broadband light source 1 is guided in the plane waveguide layer in the loss mode resonance sensor 9, and when the mode guided in the plane waveguide layer is subjected to transition, the LMR resonance phenomenon can be observed when guided in the semiconductor layer covered on the plane waveguide layer.
When electrochemical hydrogen evolution occurs on the surface of the semiconductor layer of the loss mode resonance sensor 9, the refractive index of the periphery of the semiconductor layer is changed, so that the LMR resonance wavelength shifts, the bubble dynamics behavior in the hydrogen production process can be monitored in situ on line by analyzing the wavelength shift signal, meanwhile, the analysis can be performed according to the LMR resonance wavelength, and the hydrogen production quantity can be quantitatively disclosed through the shift of the resonance wavelength. While the electrochemical workstation 5 can monitor the hydrogen bubble separation process according to the current change under the constant potential condition.
In the embodiment of the present invention, a linear polarizer 8 is disposed between the broadband light source 1 and the loss mode resonance sensor 9, and the linear polarizer 8 is used to separate TE light and TM light in the loss mode resonance, thereby increasing the visibility of the LMR, and maximum visibility can be achieved by adjusting the linear polarizer 8 in such a manner that the electric field axis is parallel or perpendicular to the surface of the semiconductor layer.
In the embodiment of the invention, a three-dimensional displacement table 12 is further arranged in the in-situ electrolytic cell, the loss mode resonance sensor 9 is fixed on the three-dimensional displacement table 12, and the three-dimensional displacement table 12 is used for adjusting the height between the loss mode resonance sensor 9 and the ground so as to enable laser to generate loss mode resonance on the surface of the loss mode resonance sensor 9.
Correspondingly, referring to fig. 3, the invention also provides a planar optical waveguide in-situ monitoring method for electrocatalytic hydrogen production, which comprises the following steps:
s10, depositing a semiconductor layer and a catalytic metal layer on the surface of a plane waveguide layer in sequence to form the loss mode resonance sensor 9.
Specifically, S10 further includes:
Firstly, ITO is deposited on a cover glass with the thickness of 150 micrometers by utilizing a magnetron sputtering mode, and the size of the cover glass is 18mm x 18mm, and the specific process is as follows: using In 2O3：SnO2 = 90:10wt% of ITO target with the purity of 99.99 percent, and depositing a semiconductor film (7 mm 16 mm) of ITO material on the surface of a cover glass under the conditions of Ar partial pressure of 0.1Pa and current intensity of 150mA, wherein the deposition rate is 0.06nm per second, and the deposition rate is 100 nm.
Wherein the semiconductor layer is not deposited over the whole area of the cover slip to avoid interference of the transmission spectrum due to deposition of the lateral faces of the waveguide. And after the ITO film is deposited on the cover glass, pt particles are deposited on the surface of the ITO film by utilizing a magnetron sputtering mode so as to form a catalytic metal layer.
S20, the broadband light source 1, the loss mode resonance sensor 9 and the spectrometer 6 are connected through multimode optical fibers, and the multimode optical fibers are coupled and aligned.
Specifically, S20 further includes:
Referring to fig. 2, the optical fiber fixing frame 11 is first mounted on the optical bread board 13, and the optical bread board 13 with a positioning groove is selected in the present invention, and the bottom of the optical fiber fixing frame 11 has a matching tongue, which can be tightly assembled into the positioning groove of the optical bread board 13 to realize the coupling alignment of the optical fibers.
Thereafter, a multimode optical fiber having a core diameter of 200 μm was used to connect the broadband light source 1, the loss-mode resonance sensor 9, and the spectrometer 6.
Further, a linear polarizer 8 is placed in front of the fiber holder 11 near the side of the broadband light source 1, and the linear polarizer 8 can help separate TE light and TM light in the loss mode resonance, thereby increasing the visibility of the LMR. Maximum visibility can be achieved by adjusting the polarizer in such a way that the electric field axis is parallel or perpendicular to the film surface.
S30, fixing the loss mode resonance sensor 9 on the three-dimensional displacement table 12, and adjusting the height of the loss mode resonance sensor 9 by the three-dimensional displacement table 12 so that the laser light emitted from the broadband light source 1 generates loss mode resonance on the surface of the loss mode resonance sensor 9.
Specifically, S30 further includes:
After the optical fiber coupling alignment, the spectrum baseline correction is directly carried out, then the prepared loss mode resonance sensor 9 with the ITO film is adjusted in height in the air through the three-dimensional displacement table 12, and when the LMR resonance occurs in the observation spectrum, the height of the cover glass can enable the light transmitted by the multimode optical fiber to be guided through the cover glass, so that the laser emitted by the broadband light source 1 generates loss mode resonance on the surface of the loss mode resonance sensor 9.
Then, the loss mode resonance sensor 9 is removed from the three-dimensional displacement table 12, and the planar waveguide layer without the semiconductor layer is fixed on the three-dimensional displacement table 12 and placed in an in-situ electrolytic cell filled with electrolyte together for spectral baseline correction, and the specific process is as follows:
The cover glass without the ITO film is fixed on a three-dimensional displacement table 12 by a mechanical fixing mode, and then is placed into a cube glass container electrolytic cell (in-situ electrolytic cell) with the dimensions of 10cm multiplied by 10cm and filled with dilute sulfuric acid solution serving as electrolyte solution together with the three-dimensional displacement table 12 to carry out spectrum baseline correction.
S40, TE light and TM light in the loss mode resonance are separated by adjusting the linear polarizer 8.
Specifically, S40 further includes:
After correction of the spectral baseline, the prepared cover glass with the ITO film is fixed on a three-dimensional displacement table 12 in a mechanical fixing mode, and TE mode and TM mode in LMR resonance are separated by adjusting a linear polarizer 8.
And S50, placing the loss mode resonance sensor 9 together with the three-dimensional displacement table 12 in an in-situ electrolytic cell filled with electrolyte, respectively clamping a plurality of electrodes in the in-situ electrolytic cell by electrode clamps of the electrochemical workstation 5, and adjusting the electrodes among the plurality of electrodes by the electrochemical workstation 5 so as to perform electrocatalytic hydrogen production in the in-situ electrolytic cell.
Specifically, S50 further includes:
The electrochemical catalytic hydrogen production process was carried out in an in situ cell (conventional three electrode system) using a cube glass container of dimensions 10cm x 10 cm. A cover glass (100 nm film) with an ITO film deposited thereon was used as the working electrode 2, the cover glass area was 7mm×16mm, ag/AgCl was used as the reference electrode 3 (providing a stable standard potential as a reference point for potential measurement), platinum (Pt) coil wires (10 coils with a diameter of 0.5mm and a diameter of 8 mm) were used as the counter electrode 4, and the electrolyte solution was a dilute sulfuric acid solution. The working electrode 2, the reference electrode 3 and the counter electrode 4 are respectively connected to an electrochemical workstation 5 by copper strips, and the electrochemical workstation 5 adjusts the voltage to the voltage (1.6V-2V) for generating hydrogen for electrocatalytic hydrogen generation.
S60, monitoring the electric signal change in the hydrogen bubble separation process under the constant potential condition through the electrochemical workstation 5, recording the optical signal change acquired by the spectrometer 6 in the electrocatalytic hydrogen production process, and analyzing the electric signal and the optical signal through the data recording computer 7 so as to realize real-time in-situ monitoring of electrocatalytic hydrogen production.
Specifically, S60 further includes:
electrolysis is carried out for 120s under the constant potential condition of the electrochemical workstation 5, the sampling frequency is 100Hz, the current change in the hydrogen bubble separation process is monitored, and meanwhile, the change of the optical signal collected by the spectrometer 6 in the electrolytic catalysis hydrogen production process is recorded. By analyzing the wavelength shift during the electrolytic catalytic hydrogen production and the electrical signal in the electrochemical workstation 5, the electrocatalytic hydrogen production can be monitored in situ in real time.
Compared with the prior art, the invention has the following beneficial effects:
The electrochemical loss mode resonance platform is used as a monitoring device, so that the electrocatalytic hydrogen production process can be monitored in situ in real time, and the electrochemical loss mode resonance platform can monitor the electrocatalytic hydrogen production process in situ in real time by optical monitoring of optical signals of wavelength drift caused by the change of the surrounding refractive index and analysis of electrical signals of the electrochemical workstation 5 in the catalysis process. The invention can effectively solve the problem of difficult monitoring of the electrochemical hydrogen production process in the prior art by the planar waveguide sensing and real-time monitoring system, provides a novel in-situ real-time monitoring method for hydrogen production process research, qualitatively and quantitatively reveals the catalytic hydrogen production three-phase surface dynamic reaction process and microcosmic mechanism from micro-nano scale, establishes a microcosmic to macroscopic bridge, and builds a novel evaluation method for hydrogen production system efficiency evaluation.
In summary, unlike the prior art, the invention provides a planar optical waveguide in-situ monitoring device and a monitoring method thereof for electrocatalytic hydrogen production, wherein the planar optical waveguide in-situ monitoring device at least comprises a broadband light source 1, an in-situ electrolytic cell, a loss mode resonance sensor 9, an electrochemical workstation 5 and a spectrometer 6, wherein when the electrocatalytic hydrogen production is monitored in the in-situ electrolytic cell, the loss mode resonance sensor 9 is placed under the laser emitted by the broadband light source 1, the laser generates loss mode resonance on the surface of the loss mode resonance sensor 9, the spectrometer 6 is used for quantitatively revealing the hydrogen production amount according to the resonance wavelength drift of the loss mode resonance, and the electrochemical workstation 5 is used for monitoring the hydrogen bubble separation process according to current change under constant potential conditions; when the electrocatalytic hydrogen production is carried out on the surface of the loss mode resonance sensor 9, the laser emitted by the broadband light source 1 generates loss mode resonance on the surface of the loss mode resonance sensor 9, the spectrometer 6 can quantitatively reveal the hydrogen production amount in the electrocatalytic hydrogen production process according to the resonance wavelength drift of the loss mode resonance so as to sense the growth process of bubbles in the stage, meanwhile, the electrochemical workstation 5 monitors the hydrogen bubble separation process in the electrocatalytic hydrogen production process according to the current change among a plurality of electrodes in the in-situ electrolytic cell under the constant potential condition, and further analyzes the influence on the catalytic hydrogen production efficiency by researching the bubble behaviors, further deeply knows the dynamic mechanism of a three-phase interface of the catalytic hydrogen production system from the microscopic level, and clearly determines the structural effect relation of the catalytic surface, thereby being further beneficial to the improvement of the catalytic hydrogen production efficiency of the electrocatalytic hydrogen production industry.
The foregoing examples merely illustrate embodiments of the invention and are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The planar optical waveguide in-situ monitoring device for electrocatalytic hydrogen production is characterized by comprising a broadband light source, an in-situ electrolytic cell, a loss mode resonance sensor, an electrochemical workstation and a spectrometer, wherein the broadband light source, the loss mode resonance sensor and the spectrometer are mutually connected through an optical fiber transmission module, the loss mode resonance sensor is positioned in the in-situ electrolytic cell, and the electrochemical workstation is electrically connected with an electrode assembly of the in-situ electrolytic cell;
When the in-situ electrolytic cell is monitored for electrocatalytic hydrogen production, the loss mode resonance sensor is placed under laser emitted by the broadband light source, and loss mode resonance is generated on the surface of the loss mode resonance sensor by the laser.
2. The device of claim 1, wherein the loss mode resonance sensor comprises a planar waveguide layer, a semiconductor layer and a catalytic metal layer stacked from bottom to top, and the orthographic projection area of the semiconductor layer on the planar waveguide layer is smaller than the cross-sectional area of the planar waveguide layer.
3. The electrocatalytic hydrogen generating planar optical waveguide in-situ monitoring device as set forth in claim 2, wherein the planar waveguide layer is a cover slip, the semiconductor layer is an ITO material, and the catalytic metal layer is Pt particles.
4. The planar lightwave circuit of claim 2, wherein the electrode assembly comprises a working electrode, a reference electrode, and a counter electrode, and wherein the electrode clamps of the electrochemical workstation clamp the working electrode, the reference electrode, and the counter electrode, respectively.
5. The device for in-situ monitoring of planar lightwave circuit of hydrogen production by electrocatalysis according to claim 4, wherein electrolyte in the in-situ electrolytic cell is dilute sulfuric acid solution, the semiconductor layer is multiplexed to the working electrode, the reference electrode is Ag/AgCl material, and the counter electrode is Pt coil wire.
6. The device of claim 1, wherein the fiber transmission module is a multimode fiber, and the diameter of the core layer of the multimode fiber is 100-300 μm.
7. The device of claim 6, wherein a linear polarizer is disposed between the broadband light source and the loss mode resonance sensor, the linear polarizer being configured to separate TE light and TM light in the loss mode resonance.
8. The device for in-situ monitoring of planar lightwave circuit of claim 6, wherein the in-situ cell is further provided with a three-dimensional displacement stage, the loss mode resonance sensor is fixed on the three-dimensional displacement stage, and the three-dimensional displacement stage is used for adjusting the height between the loss mode resonance sensor and the ground so as to generate loss mode resonance on the surface of the loss mode resonance sensor.
9. A method of monitoring a planar lightwave circuit in-situ monitoring device as claimed in any of claims 1 to 8, the method comprising:
s10, sequentially depositing a semiconductor layer and a catalytic metal layer on the surface of a planar waveguide layer to form a loss mode resonance sensor;
s20, connecting a broadband light source, the loss mode resonance sensor and a spectrometer through a multimode optical fiber, and carrying out coupling alignment on the multimode optical fiber;
S30, fixing the loss mode resonance sensor on a three-dimensional displacement table, and adjusting the height of the loss mode resonance sensor through the three-dimensional displacement table so as to enable the laser emitted by the broadband light source to generate loss mode resonance on the surface of the loss mode resonance sensor;
S40, separating TE light and TM light in the loss mode resonance by adjusting the linear polarizer;
S50, placing the loss mode resonance sensor and the three-dimensional displacement table in an in-situ electrolytic cell filled with electrolyte, respectively clamping a plurality of electrodes in the in-situ electrolytic cell by electrode clamps of an electrochemical workstation, and adjusting the electrodes among the plurality of electrodes by the electrochemical workstation so as to perform electrocatalytic hydrogen production in the in-situ electrolytic cell;
S60, monitoring the electric signal change in the hydrogen bubble separation process under the constant potential condition through the electrochemical workstation, recording the optical signal change acquired by the spectrometer in the electrocatalytic hydrogen production process, and analyzing the electric signal and the optical signal through a data recording computer so as to realize real-time in-situ monitoring of electrocatalytic hydrogen production.
10. The method of claim 9, further comprising, after step S30 and before step S40:
and removing the loss mode resonance sensor from the three-dimensional displacement table, fixing the plane waveguide layer which is not plated with the semiconductor layer on the three-dimensional displacement table, and placing the plane waveguide layer and the plane waveguide layer together in an in-situ electrolytic cell filled with electrolyte for correcting the spectrum baseline.
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