CN113373472B - Polypyrrole/rhodium nanoparticle composite flexible electrode and preparation method and application thereof - Google Patents
Polypyrrole/rhodium nanoparticle composite flexible electrode and preparation method and application thereof Download PDFInfo
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Abstract
The utility model belongs to the technical field of electrode materials, in particular to a polypyrrole/rhodium nanoparticle composite flexible electrode, a preparation method and application thereof.
Description
Technical Field
The utility model belongs to the technical field of electrode materials, and particularly relates to a polypyrrole/rhodium nanoparticle composite flexible electrode, and a preparation method and application thereof.
Background
Electrochemical hydrogen production is critical to many renewable energy systems, especially water splitting to produce hydrogen, whereas in water splitting, the ideal electrode is a flexible self-supporting catalytic material because: the self-supporting electrode has larger surface area, is also beneficial to timely discharging bubbles generated by catalysis in the catalysis process, and is beneficial to the continuous occurrence of the reaction.
The catalysts commonly used in the prior art are nano inorganic materials, and although the catalysts have good catalytic performance, the catalysts cannot be used as independent flexible electrodes, so that the application of the catalysts in water splitting is limited.
The electrodes commonly used at present mainly comprise a glassy carbon electrode, carbon Cloth (CC) and the like, and the glassy carbon electrode is high in price and easy to pollute in the use process and is not suitable for being used in water splitting; the carbon cloth has the characteristic of flexibility, but the carbon cloth is expensive, and complicated pretreatment steps are required before the carbon cloth is used, and the carbon cloth has certain limitation in practical application, so that the preparation of a self-supporting and flexible electrode becomes a new direction for researching the electrocatalyst; in recent years, a literature reports that a polymer is combined with an inorganic material and is widely applied to various flexible instruments such as batteries, electric detection and capacitors, so that the defect of the inorganic nano material can be overcome by the good mechanical property of the polymer, and a flexible self-supporting electrode with good catalytic property is obtained.
Conductive polymers such as poly 3, 4-ethylenedioxythiophene monomers: polystyrene sulfonate (PEDOT-PSS), polyaniline (PANI), polypyrrole (PPy) and the like, because the conductive polymer has good mechanical property and conductive property, the conductive polymer is widely applied to the electrochemical field, in particular polypyrrole, and the conductive polymer is widely focused as a polymer material which has the advantages of cheap raw materials, simple preparation method, good conductivity and easy film formation; polypyrrole is generally synthesized by adopting two modes of a chemical oxidation method or an electrodeposition method, wherein the chemical oxidation method generally obtains powdery PPy, and the electrodeposition method can obtain a flexible independent PPy film; PPy, however, while having good mechanical properties, does not possess a rich electrocatalytically active site in itself, and when applied in electrochemical materials, particularly in electrocatalytic processes, it is difficult to overcome the slow kinetics of hydrogen and oxygen evolution.
Pt and Pt-based materials are currently known to be the best hydrogen generating materials in electrochemical hydrogen evolution, however Pt scarcity limits its further development; it is therefore particularly critical to find an alternative catalytic material. In recent years, reports on Rh-based materials have also shown that Rh has excellent HER catalytic performance and stability enough to be comparable to Pt, whereas its poor mechanical properties as an inorganic material further limit its development in electrocatalytic water splitting.
Disclosure of Invention
Aiming at the technical defects, the utility model provides a polypyrrole/rhodium nanoparticle composite flexible electrode, a preparation method and application thereof.
In order to solve the technical problems, the utility model adopts the following technical scheme:
the preparation method of the polypyrrole/rhodium nanoparticle composite flexible electrode comprises the following steps:
(1) Cleaning ITO conductive glass and cutting;
(2) Preparation of polypyrrole/rhodium nanoparticle composite flexible electrode:
s1, dissolving rhodium trichloride monohydrate in deionized water to prepare a solution of 0.01-0.05mol/L, and then adding sulfuric acid and pyrrole to prepare a mixed solution;
wherein the mass ratio of the rhodium trichloride monohydrate to the sulfuric acid to the pyrrole is 1:1:2-5;
s2, taking an Ag/AgCl electrode as a reference electrode, a platinum wire electrode as a counter electrode and ITO conductive glass as a working electrode to form a three-electrode system, taking the mixed solution in the step S1 as a deposition solution, and adopting a multi-potential alternative deposition method to deposit pyrrole and rhodium on the surface of the working electrode to prepare the polypyrrole/rhodium nanoparticle composite flexible electrode;
the multi-potential alternating deposition method comprises the following specific steps: the working electrode is alternately placed under the potential condition of 0.8-1V for depositing for 20s, -0.6-0.4V for depositing for 10s, and the alternate depositing operation is carried out for 150-500s.
Preferably, the total deposition time of the step S2 is 300-400S.
Preferably, the specific steps of the multi-potential alternating deposition method in step S2 are as follows: the working electrode was deposited at a potential of 0.8V for 20s and then continued at a potential of-0.5V for 10s, alternately operated in the above deposition order, and co-deposited for 350s.
Preferably, the cleaning treatment method of the ITO conductive glass in the step (1) includes: sequentially adopting 70% of H by mass 2 SO 4 Washing ITO glass with deionized water and acetone for 10-20min, and drying.
Preferably, the step (1) cuts the cleaned ITO conductive glass to (1-3) X (2-3) cm 2 。
The utility model also protects the polypyrrole/rhodium nanoparticle composite flexible electrode prepared by the preparation method.
The utility model also protects the application of the polypyrrole/rhodium nanoparticle composite flexible electrode in preparing the electrolytic water catalytic electrode.
Preferably, the method for the electrolytic water catalytic reaction comprises the following steps: and (3) using an Ag/AgCl electrode containing saturated potassium chloride as a reference electrode, a platinum wire electrode as a counter electrode and a polypyrrole/rhodium nanoparticle composite flexible electrode as a working electrode to form a three-electrode system, connecting the three-electrode system to electrochemical detection equipment, and carrying out electrolysis by using a sulfuric acid solution with the pH of 0.2-1 as an electrolyte.
Compared with the prior art, the utility model has the beneficial effects that:
1. the utility model prepares polypyrrole (PPy) by oxidizing pyrrole under 0.8-1V by an electrodeposition method, reduces Rh under-0.6-0.4V 3+ Rh is obtained, and an electrode material which effectively combines the high catalytic activity of rhodium with the mechanical property of polypyrrole is provided.
2. The utility model adopts a multi-potential alternating deposition method (multi-potential steps) to prepare the PPy/Rh composite material, and obtains the optimal deposition time after optimizing the deposition time of Rh and PPy; and further, the electron transfer condition between Rh and PPy is researched through a characterization test, and a large number of electron delocalization centers can be generated after the Rh and the PPy are compounded, and the electron delocalization centers can be used as sites for generating rich catalytic activity in the electrocatalytic process.
3. Electrochemical tests have shown that PPy/Rh is formed in an acidic electrolyte at a deposition time of 350s 350 Only 59.5mV is needed to reach 10mA cm of HER -2 And has a low tafel slope (58.78 mV.dec -1 ) In addition, the temperature was 10 mA.cm -2 And 20mA cm -2 I-t testing for up to 24h at constant current also demonstrated excellent stability.
4. Compared with the traditional catalytic material, the polypyrrole/rhodium nanoparticle composite flexible electrode has the advantages that the preparation method is simple and quick, the preparation of the electrode can be completed within a few minutes, the performance is superior and stable, the noble metal Rh loading amount is extremely low, and the raw material is saved to the greatest extent; at the same time, such a flexible electrode is still capable of maintaining electrochemical properties before bending after bending folding, which provides a good starting point for its application in chemical devices.
Drawings
FIG. 1 is a schematic illustration of the preparation process of polypyrrole/rhodium nanoparticle composite flexible electrodes of examples 1-7 of the present utility model;
FIG. 2 shows Rh/PPy obtained in example 1 of the present utility model 350 An i-t curve of the deposition process;
FIG. 3 shows the Rh/PPy of example 1 after soaking in hot water 350 Optical pictures of the film;
FIG. 4 shows Rh/PPy obtained in example 1 of the present utility model 350 Is a gel permeation chromatogram of (2);
FIG. 5 shows Rh prepared in comparative example 3, PPy prepared in comparative example 2 and Rh/PPy prepared in example 1 350 Scanning electron microscope SEM images of (a);
in fig. 5, a is an SEM image of Rh prepared in comparative example 3; b is an SEM image of the PPy film prepared in comparative example 2; c is Rh/PPy prepared in example 1 350s SEM images of (a);
FIG. 6 is an SEM topography of polypyrrole/rhodium nanoparticle composite flexible electrodes at various deposition times for examples 4-7;
in FIG. 6, a is Rh/PPy of example 4 55 A figure; b is Rh/PPy of example 5 150 A figure; c is Rh/PPy of example 6 240 The method comprises the steps of carrying out a first treatment on the surface of the d is Rh/PPy of example 7 500 ；
FIG. 7 shows Rh prepared in comparative example 3 and Rh prepared in example 1Rh/PPy 350s XRD contrast pattern of (b);
FIG. 8 is an XRD spectrum of PPy prepared in comparative example 2;
FIG. 9 shows the PPy obtained in comparative example 2 and the Rh/PPy obtained in example 1 350s Raman contrast plot of (c);
FIG. 10 is a Raman spectrum of Rh/PPy at different deposition times;
FIG. 11 is an XPS spectrum of Rh 3 d;
in FIG. 11, a is Rh prepared in comparative example 3 and Rh/PPy prepared in example 1 350s Rh 3d narrow spectrum in (b); b is Rh 3d narrow spectrum of Rh/PPy with different deposition times prepared in example 1 and examples 4-7; c is PPy prepared in comparative example 2 and Rh/PPy prepared in example 1 350s N1s narrow spectrum of (a); d is the N1s narrow spectrum of Rh/PPy with different deposition times prepared in example 1 and examples 4-7;
FIG. 12a is the Rh/PPy obtained in example 1 350s Rh prepared in comparative example 3, pt/C in comparative example 1 at 0.5mol H 2 SO 4 HER polarization curve in (a); b is a Tafil slope diagram corresponding to a;
FIG. 13A is a graph showing that the Rh/PPy obtained in the different deposition times obtained in example 1 and examples 4 to 7 was 0.5mol H 2 SO 4 HER polarization curve in (a); b is a Tafil slope diagram corresponding to a;
FIG. 14A is a sample of Rh/PPy obtained in example 1 350s Electrochemical impedance spectra of Rh prepared in comparative example 3 and Pt/C of comparative example 1; b is the electrochemical impedance spectrum of Rh/PPy with different deposition times prepared in the example 1 and the examples 4-7;
FIG. 15 shows the different materials vs. 0.5mol H 2 SO 4 Contact angle test patterns of (2);
in fig. 15, a is PPy of comparative example 2; b is Rh/PPy of example 4 55s The method comprises the steps of carrying out a first treatment on the surface of the c is Rh/PPy of example 5 150s The method comprises the steps of carrying out a first treatment on the surface of the d is Rh/PPy of example 6 240s The method comprises the steps of carrying out a first treatment on the surface of the e is Rh/PPy of example 1 350s The method comprises the steps of carrying out a first treatment on the surface of the f is Rh/PPy of example 7 500s ；
In FIG. 16, a is a current density of 10mA cm respectively -2 And 20mA cm -2 Rh/PPy below 350s I-t test curve of (2)A wire; b is Rh/PPy 350s The small plots inserted in b are CV control plots for the first and 5000 th cycles of the cycle, for the LSV curve comparison plots before and after 5000 cyclic voltammetry scans;
in FIG. 17, a is Rh/PPy 350s //RuO 2 And Pt// RuO 2 A polarization curve comparison of water splitting; b is Rh/PPy// RuO 2 The current density of the two-electrode system is 10mA cm -2 The following i-t test plot;
in fig. 18, it is bent by a; b, curling; rh/PPy prepared in example 1 under c-twist and d-fold 350s A physical diagram;
in FIG. 19, a is Rh/PPy before and after bending 350s HER polarization curve control for the film; b is a Tafil slope diagram corresponding to a.
Detailed Description
The following detailed description of specific embodiments of the utility model is, but it should be understood that the utility model is not limited to specific embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the utility model without making any inventive effort, are intended to be within the scope of the utility model. The experimental methods described in the examples of the present utility model are conventional methods unless otherwise specified.
Table 1 laboratory apparatus
| Experimental instrument | Model number | Manufacturing factories |
| Electronic analytical balance | AR224CN | Shanghai Ox instruments Co Ltd |
| Vacuum drying oven | DHG-9076A | Shanghai precision macro laboratory Equipment Co.Ltd |
| Ultrasonic cleaner | KQ-100E | KUNSHAN ULTRASONIC INSTRUMENTS Co.,Ltd. |
| Centrifugal machine | TG16-WS | HUNAN XIANGYI LABORATORY INSTRUMENTS DEVELOPMENT Co.,Ltd. |
| Fourier infrared spectrometer | TENSOR27 | Bruker，German |
| X-ray powder diffractometer | D8 ADVANCE | Bruker，German |
| Raman (Raman) | |
Hormonal，USA |
| X-ray photoelectron spectroscopy | 5000VersaProbe | PHI，Japan |
| Scanning electron microscope | SU-8010 | HITACHICo.Ltd.，Japan |
| Electrochemical workstation | CHI660E | Shanghai Chenhua instruments Inc |
The main reagents required for the experiment are shown in Table 2:
table 2 experimental reagents
| Chemical reagent | Specification of specification | Manufacturing factories |
| Rhodium trichloride monohydrate | 99％ | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Concentrated sulfuric acid | Analytical grade | Tianjin chemical reagent Co.Ltd |
| Pyrrole compounds | 0.968-0.971g/mL,≥98％ | Shanghai King industries Co., ltd |
| Acetone (acetone) | ≥99.5％ | Tianjin Li Anlong Bohua pharmaceutical chemical Co., ltd |
| Nickel acetate | Analytical grade | Shanghai exhibition cloud chemical industry Co.Ltd |
| Absolute ethyl alcohol | Analytical grade | Tianjin chemical reagent Co.Ltd |
| Ultrapure water | Milli-Q pure water purification system | Millipore, USA |
Example 1
The preparation method of the polypyrrole/rhodium nanoparticle composite flexible electrode comprises the following steps:
(1) Cleaning ITO conductive glass and cutting;
sequentially adopting 70% of H by mass 2 SO 4 Washing ITO glass with the solution, deionized water and acetone for 20min, and drying; cutting the cleaned ITO conductive glass to 1cm multiplied by 2cm;
(2) Preparation of polypyrrole/rhodium nanoparticle composite flexible electrode:
s1, dissolving rhodium trichloride monohydrate in deionized water to prepare a solution of 0.01mol/L, and then adding 0.01mol of sulfuric acid and 0.02mol of pyrrole to prepare a mixed solution;
s2, taking an Ag/AgCl electrode as a reference electrode, a platinum wire electrode as a counter electrode and ITO conductive glass as a working electrode to form a three-electrode system, taking the mixed solution in the step S1 as a deposition solution, and adopting a multi-potential alternative deposition method to deposit pyrrole and rhodium on the surface of the working electrode to prepare the polypyrrole/rhodium nanoparticle composite flexible electrode;
the multi-potential alternating deposition method comprises the following specific steps: the working electrode was deposited at a potential of 0.8V for 20s and then electricallyContinuously depositing for 10s under the condition of-0.5V, alternately operating according to the deposition sequence, and co-depositing for 350s to obtain the polypyrrole/rhodium nanoparticle composite flexible electrode (PPy/Rh) 350s )。
The method for the electrolytic water catalytic reaction comprises the following steps:
and (3) using an Ag/AgCl electrode containing saturated potassium chloride as a reference electrode, a platinum wire electrode as a counter electrode, and a three-electrode system formed by using the prepared polypyrrole/rhodium nanoparticle composite flexible electrode as a working electrode, connecting the three-electrode system to electrochemical detection equipment, using a sulfuric acid solution of 0.5mol as an electrolyte, and drawing a working curve by adopting a cyclic voltammetry and a linear scanning voltammetry.
Example 2
The preparation method of the polypyrrole/rhodium nanoparticle composite flexible electrode comprises the following steps:
(1) Cleaning ITO conductive glass and cutting;
sequentially adopting 70% of H by mass 2 SO 4 Washing ITO glass with the solution, deionized water and acetone for 10min, and drying; cutting the cleaned ITO conductive glass to 2cm multiplied by 2cm;
(2) Preparation of polypyrrole/rhodium nanoparticle composite flexible electrode:
s1, dissolving rhodium trichloride monohydrate in deionized water to prepare a solution of 0.03mol/L, and then adding 0.03mol of sulfuric acid and 0.1mol of pyrrole to prepare a mixed solution;
s2, taking an Ag/AgCl electrode as a reference electrode, a platinum wire electrode as a counter electrode and ITO conductive glass as a working electrode to form a three-electrode system, taking the mixed solution in the step S1 as a deposition solution, and adopting a multi-potential alternative deposition method to deposit pyrrole and rhodium on the surface of the working electrode to prepare the polypyrrole/rhodium nanoparticle composite flexible electrode;
the multi-potential alternating deposition method comprises the following specific steps: the working electrode is deposited for 20s under the condition of 0.9V potential, then is continuously deposited for 10s under the condition of-0.4V potential, and is alternately operated according to the deposition sequence to obtain the polypyrrole/rhodium nanoparticle composite flexible electrode by co-depositing for 500s.
Example 3
The preparation method of the polypyrrole/rhodium nanoparticle composite flexible electrode comprises the following steps:
(1) Cleaning ITO conductive glass and cutting;
sequentially adopting 70% of H by mass 2 SO 4 Washing ITO glass with the solution, deionized water and acetone for 20min, and drying; cutting the cleaned ITO conductive glass to 3cm multiplied by 3cm;
(2) Preparation of polypyrrole/rhodium nanoparticle composite flexible electrode:
s1, dissolving rhodium trichloride monohydrate in deionized water to prepare a solution of 0.05mol/L, and then adding 0.05mol of sulfuric acid and 0.25mol of pyrrole to prepare a mixed solution;
s2, taking an Ag/AgCl electrode as a reference electrode, a platinum wire electrode as a counter electrode and ITO conductive glass as a working electrode to form a three-electrode system, taking the mixed solution in the step S1 as a deposition solution, and adopting a multi-potential alternative deposition method to deposit pyrrole and rhodium on the surface of the working electrode to prepare the polypyrrole/rhodium nanoparticle composite flexible electrode;
the multi-potential alternating deposition method comprises the following specific steps: the working electrode is deposited for 20s under the condition of the potential of 1.0V, then is continuously deposited for 10s under the condition of the potential of-0.6V, and is alternately operated according to the deposition sequence to be co-deposited for 350s, so as to prepare the polypyrrole/rhodium nanoparticle composite flexible electrode.
Example 4
The same procedure as in example 1 was followed except that the co-deposition time was changed from 350s to 55s to obtain polypyrrole/rhodium nanoparticle composite flexible electrode (PPy/Rh) 55s )。
The method for the electrolytic water catalytic reaction comprises the following steps:
the same procedure as in example 1 was followed except that PPy/Rh prepared in example 1 was used 350s Replaced by PPy/Rh 55s As a working electrode.
Example 5
The same procedure as in example 1 was followed except that the co-deposition time was replaced with 150s (PPy/Rh) from 350s 150s )。
The method for the electrolytic water catalytic reaction comprises the following steps:
the same procedure as in example 1 was followed except that PPy/Rh prepared in example 1 was used 350s Replaced by PPy/Rh 150s As a working electrode.
Example 6
The same procedure as in example 1 was followed except that the co-deposition time was replaced with 240s (PPy/Rh) from 350s 240s ) As a working electrode.
The method for the electrolytic water catalytic reaction comprises the following steps:
the same procedure as in example 1 was followed except that PPy/Rh prepared in example 1 was used 350s Replaced by PPy/Rh 240s As a working electrode.
Example 7
The same procedure as in example 1 was followed except that the co-deposition time was replaced with 500s (PPy/Rh) from 350s 500s ) As a working electrode.
The method for the electrolytic water catalytic reaction comprises the following steps:
the same procedure as in example 1 was followed except that PPy/Rh prepared in example 1 was used 350s Replaced by PPy/Rh 500s As a working electrode.
The polypyrrole/rhodium nanoparticle composite flexible electrode with excellent catalytic performance is prepared in each of the embodiments 1-7, the polypyrrole/rhodium nanoparticle composite flexible electrode prepared in the embodiment 1 and the embodiment 4-7 is taken as an example for research, and the polypyrrole/rhodium nanoparticle composite flexible electrode prepared in the embodiment 1 and the embodiment 4-7 is respectively taken as a working electrode, and specific research methods and research results are as follows:
comparative example 1
The working electrode was replaced with an industrialized Pt/C electrode from the polypyrrole/rhodium nanoparticle composite flexible electrode prepared in example 1, and a working curve was drawn by cyclic voltammetry and linear sweep voltammetry.
Comparative example 2
Preparation of PPy:
(1) Cleaning ITO conductive glass and cutting;
sequentially adopting 70% of H by mass 2 SO 4 Washing ITO glass with the solution, deionized water and acetone for 20min, and drying; cutting the cleaned ITO conductive glass to 1cm multiplied by 2cm;
(2) Preparation of polypyrrole:
s1, dissolving rhodium trichloride monohydrate in deionized water to prepare a solution of 0.01mol/L, and then adding 0.01mol of sulfuric acid and 0.02mol of pyrrole to prepare a mixed solution;
s2, taking an Ag/AgCl electrode as a reference electrode, a platinum wire electrode as a counter electrode and ITO conductive glass as a working electrode to form a three-electrode system, taking the mixed solution prepared in the step 2 as a deposition solution, depositing for 100 seconds under the condition that the potential is 0.8V, placing the working electrode in hot water, and stripping polypyrrole from the ITO conductive glass to prepare the polypyrrole (PPy).
The method for the electrolytic water catalytic reaction comprises the following steps:
the same procedure as in example 1 was followed except that PPy/Rh prepared in example 1 was used 350s PPy is substituted as the working electrode.
Comparative example 3
Preparation of Rh:
(1) Cleaning ITO conductive glass and cutting;
sequentially adopting 70% of H by mass 2 SO 4 Washing ITO glass with the solution, deionized water and acetone for 20min, and drying; cutting the cleaned ITO conductive glass to 1cm multiplied by 2cm;
(2) Preparation of rhodium:
s1, dissolving rhodium trichloride monohydrate in deionized water to prepare a solution of 0.01mol/L, and then adding 0.01mol of sulfuric acid and 0.02mol of pyrrole to prepare a mixed solution;
s2, taking an Ag/AgCl electrode as a reference electrode, a platinum wire electrode as a counter electrode and ITO conductive glass as a working electrode to form a three-electrode system, taking the mixed solution prepared in the step 2 as a deposition solution, depositing for 100 seconds under the condition that the potential is-0.5V, placing the working electrode in hot water, and stripping rhodium from the ITO conductive glass to prepare Rh.
The method for the electrolytic water catalytic reaction comprises the following steps:
the same procedure as in example 1 was followed except that PPy/Rh prepared in example 1 was used 350s Rh is substituted as the working electrode.
Results of studies on electrochemical characterization of the electrodes during different modifications:
as shown in FIG. 1, polypyrrole and rhodium are simultaneously deposited on the pretreated ITO conductive glass by a multi-potential alternating deposition method (multi-potential steps), in the electro-deposition process, a positive potential value is firstly given to a working electrode, and Py molecules start to be accumulated and polymerized on the surface of the electrode so as to form a PPy film; next, rh was present in the solution while continuing to apply a negative voltage to the working electrode 3+ Ions are reduced into Rh simple substance and are embedded into the PPy film; and repeatedly continuing to supply negative potential and positive potential to the electrode, and repeating the two deposition processes until the thickness capable of stripping is reached, and soaking the electrode in hot water for 3-5min to obtain the polypyrrole/rhodium nanoparticle composite flexible electrode (PPy/Rh film). The PPy/Rh film is shown in FIG. 3;
as shown in FIG. 4, gel Permeation Chromatography (GPC) showed that PPy obtained at a deposition potential of 0.8V had a weight average molecular weight of about 10082 and a degree of polymerization of about 144, indicating successful polymerization of PPy.
For the appearance structure of the depolymerized pyrrole/rhodium nanoparticle composite flexible electrode, SEM electron microscope scanning is carried out on the depolymerized pyrrole/rhodium nanoparticle composite flexible electrode, and meanwhile, SEM electron microscope scanning is carried out on deposited Rh particles and polypyrrole, and comparison research is carried out; as shown in fig. 5a, rh particles obtained by deposition are clustered in clusters of small particles having a size of about 80-100 nm; PPy in fig. 5b is a planar structure stacked by uniform hemispheres of about 100nm in diameter; the morphology shown in FIG. 5c is obtained when Rh and PPy are deposited by multi-potential steps for 350s. It can be seen that the gray particles in the figure are particles of Rh, which are uniformly dispersed on the surface of the PPy film, and at the same time, compared with fig. 5a, the aggregation state of Rh is significantly improved, and the uniformly distributed state is favorable for charge transfer between Rh and PPy and exposure of active sites.
The present utility model also performed SEM characterization on the composite material deposited at different times, as shown in fig. 6, it can be seen that when the deposition time is only 55s, the film structure is basically not seen, and as the deposition time increases, dense Rh particles can be seen to be uniformly deposited on the surface of PPy after 150s, 240s, and 500s, and as the deposition time increases, the particle size gradually decreases. Since the size of the nanomaterial has a close relationship with its specific surface area, the specific surface area increases correspondingly as the size decreases. Therefore, the reduction of the particle size is beneficial to increasing the specific surface area, so that more active sites are exposed, and the further improvement of the catalytic performance is facilitated.
Knowing the interaction between Rh and PPy, the present utility model also performed XRD testing as shown in FIG. 7, combined with the XRD peak positions of PPy in FIG. 8, rh/PPy 350s The XRD of (C) indicates successful binding of PPy to Rh. At the same time Rh/PPy 350s The 111 crystal plane of Rh is significantly broadened relative to Rh, which means that the crystal structure is damaged to some extent, which is related to the combination with PPy, and at the same time, the combination with PPy also results in the weakening or even disappearance of the other crystal plane of Rh, which is related to the strong amorphous state of PPy.
The utility model further adopts Raman scattering spectrum characterization to study the carbon peak emergence condition of PPy. As can be seen from FIG. 9 and FIG. 10, PPy is 1579cm -1 The peak at which represents the C=C vibration peak, and at 1368cm -1 The peak at this point is the peak of the C-N single bond.
When the deposition times of Rh and PPy are 55s, 150s, 240s, 350s and 500s, respectively, the Raman shifts of the C=C and C-N bonds are shown in Table 3, it can be seen that the C=C peak is red shifted to different degrees, the C-N peak is blue shifted to different degrees, and Rh/PPy 350s Is the most displaced, indicating that after Rh incorporation into PPy, the transfer of electrons inside PPy occurs from c=c double bonds to c—n bonds. And Rh/PPy 350s The electron shift phenomenon of (2) is most obvious, thereby leading to the following Rh/PPy 350s In the imbalance of electrons that will be most generated inside the materialAnd (5) a heart.
Table 3 raman shift tables for c=c and C-N for different catalysts
| Material | C＝C(cm -1 ) | C-N(cm -1 ) |
| Rh/PPy 55s | 1588 | 1335 |
| Rh/PPy 150s | 1590 | 1333 |
| Rh/PPy 240s | 1594 | 1328 |
| Rh/PPy 350s | 1596 | 1318 |
| Rh/PPy 500s | 1580 | 1361 |
The XPS characterization further demonstrates this result as well, as shown in FIG. 11a, the narrow spectrum of Rh 3d splits into 4 peaks altogether, located at 307.4eV and 312.0eV of Rh 3d 5/2 And 3d 3/2 Peak at 308.7 and 313.6eV is Rh 3+ 3d of (2) 5/2 And 3d 3/2 This oxidation state is likely to occur due to oxidation of a small amount of Rh caused by the material being placed in air. Rh 3d, as shown in FIG. 11b, can be clearly seen for Rh/PPy at different deposition times 350s The synthesis of (2) results in a different degree of forward movement of Rh and exhibits a maximum forward movement at a deposition time of 350s, indicating that Rh is the electron-withdrawing party and that Rh/PPy 350s The material with the greatest Rh electron loss. In both fig. 11c and 11d, narrow spectra of N1s are shown, at 398.2eV, 399.7eV and 400.8eV, respectively represented by-n=, -NH-and-NH-, respectively + Three N bonding modes. Meanwhile, when Rh and PPy are deposited for different times, it can be seen that the incorporation of Rh makes the peak of N significantly blue-shifted relative to PPy, indicating that N is one party to the electrons. In combination with raman, rh 3d and N1s analysis, rh acts as one electron donating side in the Rh/PPy complex, transferring electrons to the N site in PPy, and at the same time c=c double bond in PPy transfers electrons to the N site, so that Rh/PPy contains rich electron imbalance sites, and rich active sites are generated in Rh/PPy, which further becomes a good catalytic material.
Based on the analysis, respectively performing electrochemical tests on the Rh/PPy obtained; first, as shown in FIG. 12a, at 0.5mol H 2 SO 4 Rh/PPy in the electrolyte of (C) 350s At 10mA cm -2 Only 59.5mV of overpotential is required compared to Rh/ITO (122.5 mV) and significantly reduced compared to Pt/C (81.5 mV) already industrialised at the same loading.
ICP data shows the Rh content of the resulting composite films at different deposition times, as shown in table 4:
TABLE 4 ICP test of Rh in Rh/PPy films at different deposition times
| Rh/PPy 55s | Rh/PPy 150s | Rh/PPy 240s | Rh/PPy 350s | Rh/PPy 500s | |
| Rh-carrying capacity (mgcm) -2 ) | / | 0.00192 | 0.01024 | 0.01576 | 0.02424 |
The utility model also tested the HER catalytic performance of Rh/PPy composites obtained at different deposition times, as shown in FIG. 13a, with corresponding overpotential of 225.5mV (55 s), 188.5mV (150 s), 129.5mV (240 s) and 101.5mV (500 s), respectively, where Rh/PPy 55s ，Rh/PPy 150s And Rh/PPy 240s Is not thick enough to obtain an independent membrane electrode, and Rh/PPy 500s Performance of (C) and Rh/PPy 350s There is no obvious advantage in performance compared with the prior art, and the Rh loading is also higher than Rh/PPy 350s Much larger (shown in Table 4) results in waste of raw materials, and thus Rh/PPy 350s Is the optimal catalyst.
To further investigate the reaction kinetics of the above catalysts, tafil slope diagrams (FIG. 12b and FIG. 13 b) were obtained from the polarization curves shown in FIG. 12 and FIG. 13, and a catalyst was obtained by 350s depositionThe Tafil slope of the chemical agent is only 50.78mV dec -1 While the Tafil slope of Rh/PPy at other deposition times was 117.16mV dec, respectively -1 (55s)，90.14mV dec -1 (150s)，86.14mV dec -1 (240s)，62.21mV dec -1 (500 s) and Rh has a Tafil slope of 103.05mV dec -1 Pt/C Tafil slope of 52.11mV dec -1 . The tafel slope is a parameter characterizing the kinetics of the catalyst reaction, and a low tafel slope indicates that the catalyst has faster kinetics during electrocatalysis, consistent with the trend toward HER catalytic performance exhibited by it.
Electrochemical Impedance Spectroscopy (EIS) as shown in fig. 14, by fitting it, impedance values of different materials can be obtained, and the interfacial electron transfer ability of the catalyst can be further evaluated. As can be seen from the graph, the resistance value at a Rh/PPy deposition time of 350s was 7.15Ω, which is superior to 27.51Ω (Rh), and 12.43Ω (Pt/C). While the other deposition times have impedance values of 78.32 Ω (55 s), 33.43 Ω (150 s), 22.61 Ω (240 s), 17.93 Ω (500 s), respectively, it was found from comparison with the impedance values of Rh that the composite material exhibited the lowest impedance value when the deposition time was 350s, further indicating that the deposition time was the optimal deposition time, which resulted in a material having the fastest interfacial electron transfer capability, consistent with the results obtained from the polarization curve and tafel slope. This suggests that the conductive structure of PPy can provide a fulcrum for Rh, further enhancing the conductivity of the catalyst.
The material being more acidic (0.5 mol H 2 SO 4 ) Also studied by contact angle testing, the results are shown in FIG. 15, rh/PPy 350s The best affinity is shown, which facilitates sufficient contact with the electrolyte during the electrocatalytic process, thus facilitating the onset of water splitting.
Similarly, the ability of the catalyst to maintain substantially constant performance over a prolonged period of electrocatalysis is also an important indicator for evaluation of its performance, and thus the stability test was carried out herein, as shown in FIG. 16a, at 10mA cm -2 And 20mA cm -2 The catalyst can still maintain the performance for at least 24 hours. At the same time, FIG. 16b showsShowing that there is still only a slight shift after a 5000cycles cycle. This shows that the catalyst has very good stability.
Since the material shows good HER catalytic performance, the water splitting performance of the material is further explored, and the material is suitable for PPy/Rh 350s //RuO 2 The two-electrode water splitting system of (1) takes Rh/PPy as a negative electrode and RuO 2 As a positive electrode, 0.5mol H 2 SO 4 As an electrolyte to an electrochemical workstation; pt/C// RuO 2 The two-electrode water splitting system of (1) takes Pt/C as a cathode and RuO 2 As a positive electrode, 0.5mol H 2 SO 4 As electrolyte connected to the electrochemical workstation, the polarization curves were all tested between 1-2V; ruO with the same loading of both 2 As a positive electrode for water splitting, a water splitting test was performed using Rh/PPy as a negative electrode (FIG. 17 a), and when the potential value reached 1.66V, it was able to reach 10mA cm -2 Is used for the current density of the battery. At the same time, the material can maintain stability for at least 24h at 1.66V (fig. 17 b), and in the process, the generation of bubbles can be clearly observed. This indicates that the material has good water splitting ability.
The Rh/PPy film deposited by taking ITO as a substrate can be easily peeled off after being soaked in hot water for 3-5 minutes, and the obtained independent film has good flexibility. As shown in fig. 18 a-d, the film can be bent, curled and even folded into the shape of a kite, which shows that the resulting composite film has good flexibility. Further electrochemical tests investigated the HER catalytic performance of the composite membrane before and after bending.
As shown in fig. 19, the polarization curves of HER catalytic processes before and after bending the composite film are shown, and the inset is a physical diagram of the composite film as an independent electrode for testing; it can be seen that there is no significant change in the polarization curves before and after bending, indicating that bending has no effect on the catalytic performance of the film. At the same time, the tafel slope also has a negligible change.
In summary, the utility model successfully prepares the polymer/nanoparticle composite film (Rh/PPy) with independent self-support through a one-step electrodeposition method; substrate of PPy film enablesThe Rh particles are more dispersed, so that the specific surface area of Rh/PPy is increased, the further full exposure of active sites is promoted, meanwhile, electrons are transferred due to the tight combination between PPy and Rh, and an electron imbalance center is generated, so that the catalysis performance of HER is enhanced. Electrochemical tests prove that Rh/PPy 350s Can reach 10mA cm under the low overpotential of 59.5mV -2 At the same time, its Tafil slope is only 50.78mV dec -1 It was further demonstrated by the i-t and CV cycles that they have better stability. Moreover, the independent electrode can be bent into any shape thanks to the excellent mechanical properties of PPy, and the electrocatalytic properties are basically consistent before and after bending. The utility model provides a new thought for compounding the polymer and the inorganic nano material and also provides a new strategy for researching the independent self-supporting working electrode.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present utility model without departing from the spirit or scope of the utility model. Thus, it is intended that the present utility model also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof. The above-described embodiments are merely preferred embodiments for fully explaining the present utility model, and the scope of protection is not limited thereto. Equivalent substitutions and modifications are intended to be within the scope of the present utility model, as will be apparent to those skilled in the art based upon the present disclosure.
Claims (7)
1. The preparation method of the polypyrrole/rhodium nanoparticle composite flexible electrode is characterized by comprising the following steps of:
(1) Cleaning ITO conductive glass and cutting;
(2) Preparation of polypyrrole/rhodium nanoparticle composite flexible electrode:
s1, dissolving rhodium trichloride monohydrate in deionized water to prepare a solution of 0.01-0.05mol/L, and then adding sulfuric acid and pyrrole to prepare a mixed solution;
wherein the ratio of the amounts of rhodium trichloride monohydrate, sulfuric acid and pyrrole is 1:1:2-5;
s2, taking an Ag/AgCl electrode as a reference electrode, a platinum wire electrode as a counter electrode and ITO conductive glass as a working electrode to form a three-electrode system, taking the mixed solution in the step S1 as a deposition solution, and adopting a multi-potential alternative deposition method to deposit pyrrole and rhodium on the surface of the working electrode to prepare the polypyrrole/rhodium nanoparticle composite flexible electrode;
the multi-potential alternating deposition method comprises the following specific steps: alternately placing the working electrodes under the potential condition of 0.8-1V for depositing 20s and the potential condition of minus 0.6 to minus 0.4V for depositing 10s, alternately depositing, and co-depositing for 150-500s; the total deposition time of the step S2 is 300-400S.
2. The method for preparing the polypyrrole/rhodium nanoparticle composite flexible electrode according to claim 1, wherein the specific steps of the multi-potential alternate deposition method in step S2 are as follows: the working electrodes are alternately placed under the potential condition of 0.8-1V for depositing 20s and the potential condition of-0.6 to-0.4V for 10s, and the alternate depositing operation and the total depositing operation are carried out for 350s.
3. The method for preparing the polypyrrole/rhodium nanoparticle composite flexible electrode according to claim 1, wherein the method for cleaning the ITO conductive glass in the step (1) is as follows: sequentially adopting 70% of H by mass 2 SO 4 And washing the ITO glass with the solution, deionized water and acetone for 10-20min, and drying.
4. The method for preparing the polypyrrole/rhodium nanoparticle composite flexible electrode according to claim 1, wherein the step (1) is to cut the cleaned ITO conductive glass to (1-3) x (2-3) cm 2 。
5. The polypyrrole/rhodium nanoparticle composite flexible electrode made by the method of any one of claims 1-4.
6. The use of the polypyrrole/rhodium nanoparticle composite flexible electrode of claim 5 in the preparation of an electrolyzed water catalytic electrode.
7. The application of the polypyrrole/rhodium nanoparticle composite flexible electrode in preparing an electrolyzed water catalytic electrode according to claim 6, wherein the method for catalyzing the reaction by the electrolyzed water is as follows: and (3) using an Ag/AgCl electrode containing saturated potassium chloride as a reference electrode, a platinum wire electrode as a counter electrode and a polypyrrole/rhodium nanoparticle composite flexible electrode as a working electrode to form a three-electrode system, connecting the three-electrode system to electrochemical detection equipment, and carrying out electrolysis by using a sulfuric acid solution with the pH of 0.2-1 as an electrolyte.
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