CN115414930B - Ru(bpy) 32+ Anode or cathode coreactant and method for producing same - Google Patents
Ru(bpy) 32+ Anode or cathode coreactant and method for producing same Download PDFInfo
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- CN115414930B CN115414930B CN202211033508.2A CN202211033508A CN115414930B CN 115414930 B CN115414930 B CN 115414930B CN 202211033508 A CN202211033508 A CN 202211033508A CN 115414930 B CN115414930 B CN 115414930B
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01J35/393—
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- B01J35/40—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/301—Reference electrodes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Abstract
The invention discloses Ru (bpy) 3 2+ The anode or cathode coreactant and the preparation method thereof are both Au-rGO complexes, and the particle size of Au nano particles in the anode coreactant is 10-15nm; the particle size of Au nano-particles in the cathode coreactant is 2-4nm. The prepared anode coreactant has better OER reaction catalyzing performance and can promote the anode luminescence of terpyridyl ruthenium; the cathode coreactant has better ORR reaction catalyzing performance and can promote the cathode luminescence of terpyridyl ruthenium.
Description
Technical Field
The invention belongs to Ru (bpy) 3 2+ The technical field of anode or cathode coreactants, in particular to Ru (bpy) 3 2+ Anode or cathode coreactants and methods for their preparation.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
In recent years, development of sensitive and specific tumor marker detection means is a hot spot of research. Among them, electrochemiluminescence is receiving a great deal of attention due to its advantages of high sensitivity, good stability, and the like. Electrochemiluminescence refers to the generation of excited state substances by potential excitation and a series of oxidation-reduction reactions of luminophores in a system when a certain voltage or current is applied, whichWhen the transition is made back to the ground state, the light emits energy. Wherein, noble metal complex terpyridyl ruthenium (II) (Ru (bpy) 3 2+ ) The derivative thereof is a luminous body with high luminous efficiency, good stability and recycling. The light-emitting material can be used as a light-emitting body of a single-light-emitting body multi-coreactant system, and can display potential-resolved light-emitting performance when promoted by different corresponding coreactants, namely, can generate electrochemiluminescence under the action of different potentials.
However, most ECL analysis systems are typically based on a single signal ("signal on" or "signal off" mode), with disadvantages in terms of detection: the stability, accuracy and efficiency of signal output are not facilitated, and the integration and miniaturization of the biosensor are not facilitated.
The ECL detection system with multiple signal outputs can avoid most defects of the ECL system with single signal, and is more flexible, convenient and accurate in detection. The multi-signal ECL output typically relies on the introduction of a distinguishable signal output probe or the construction of multi-channel detection. In the resolved ECL strategy, the potential resolved ECL has the advantages of low instrument requirement, shortened detection time, improved sample flux and the like, but a large number of potential resolved multi-signal ECL systems mostly use double luminophores, two potential resolved complex luminophores and co-reactant combinations, are plagued by limited potential resolved luminescence pairs, troublesome assembly steps, complex labeling processes, and unavoidable mutual crosstalk between co-reactant and luminophores, between co-reactants and between luminophores, and greatly limit the development of the ratio ECL detection system.
In the related research of the dual-signal ratio ECL strategy of a single luminophor, the selection of the coreactants is very critical, the current research on the coreactants under different potentials of the luminophor is relatively less, most of the coreactants are complex to synthesize and difficult to prepare, and researchers try to synthesize the cathode coreactants and the anode coreactants together or introduce the coreactants into an electrolysis reaction in situ to generate the coreactants so as to achieve the purposes of simplifying the processes of preparing, adding the coreactants and the like. However, none of these studies have essentially solved the relative lack of problems of co-reactant studies, and the synthesis of cathode-anode co-reactant complexes is equally complex, with systems that generate co-reactants in situ being extremely susceptible to environmental interference.
Disclosure of Invention
In view of the deficiencies of the prior art, an object of the present invention is to provide Ru (bpy) 3 2+ The prepared anode coreactant has better OER reaction catalyzing performance and can promote the anode luminescence of terpyridyl ruthenium; the cathode coreactant has better ORR reaction catalyzing performance and can promote the cathode luminescence of terpyridyl ruthenium.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides Ru (bpy) 3 2+ The anode or cathode coreactants are Au-rGO complexes, and the particle size of Au nano particles in the anode coreactants is 10-15nm; the particle size of Au nano-particles in the cathode coreactant is 2-4nm.
In a second aspect, the present invention provides the Ru (bpy) 3 2+ The preparation method of the anode or cathode coreactant comprises the following steps:
HAuCl 4 Mixing the aqueous solution with the r-GO suspension in proportion, and performing ultrasonic dispersion to obtain a mixture I;
adding NaBH to mixture one 4 Mixing, adding sodium citrate, and mixing;
after the reaction is finished, separating and washing a solid product, and then redispersing the solid product to obtain a resuspension solution;
centrifuging the heavy suspension at 11000-12500rpm for 10-30min, and collecting non-precipitated components.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
the transformation of the terpyridyl ruthenium anode-cathode co-reactant is realized by adjusting the size of the gold nanoparticle loaded on the reduced graphene oxide. Cross talk between cathode and anode coreactants is greatly reduced in a single-illuminant multi-signal output system;
by designing the ORR and OER catalysts with proper catalytic capability as cathode and anode coreactants of ruthenium, the accurate design of the cathode and anode coreactants of terpyridyl ruthenium is realized.
The change of the ruthenium anode-cathode co-reactant is achieved by adjusting the catalytic capability of ORR and OER through changing the particle size of Au-gamma GO.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
In fig. 1, (a) is a large-scale Transmission Electron Microscope (TEM) of Au-rGO, (b) is an annular dark field SEM of Au-rGO, (c) is a scanning electron microscope SEM image of Au-rGO;
FIG. 2 is a graph of Au/rGO of different sizes grown on a rGO substrate in an embodiment of the invention, wherein A is a transmission electron microscope image and B is a corresponding size histogram of Au/rGO-1; c is the corresponding size histogram of Au/rGO-2, D is the corresponding size histogram of Au/rGO-3, and E is the corresponding size histogram of Au/rGO-4.
FIG. 3 is a graph of DPV test of Au/rGO-2 showing that the electrolyte is ruthenium terpyridyl with pH=6 in the example of the present invention;
FIG. 4 is an EDS map image of Au-rGO, where A is an SEM image of Au-rGO at 100nm scale, in an embodiment of the present invention; b is an EDS mapping image of carbon elements of Au-rGO under the scale of 100 nm; c is an EDS mapping image of nitrogen element of Au-rGO under the scale of 100 nm; d is an EDS mapping image of an oxygen element of Au-rGO under the scale of 100 nm; e is an EDS mapping image of gold elements of Au-rGO under the scale of 100 nm; f is an EDS mapping image of carbon, nitrogen, oxygen and gold elements of Au-rGO under the scale of 100 nm; g is an element content analysis chart obtained by EDS mapping of Au-rGO under the scale of 100 nm;
FIG. 5 is an XRD pattern for Au/rGO in an embodiment of the invention;
FIG. 6 is an ultraviolet-visible absorption spectrum image of Au/rGO in an embodiment of the invention, wherein A is the ultraviolet-visible absorption spectrum of GO film and AuNPs/rGO nanocomposite film; b is the ultraviolet-visible absorption spectrum of Au/rGO with different reduction times of rGO. Wherein Au/rGO-A, B, C respectively represents that the reduction events of rGO are 3h, 6h and 12h;
FIG. 7 is a Zeta potential image of Au/rGO in an embodiment of the present invention;
in fig. 8, a) XPS investigation spectra of the original graphene oxide thin film and AuNPsrGO nanocomposite thin film after Ar plasma treatment for 15 min; b) High resolution C1 deconvolution spectra of graphene oxide films and C) AuNPsrGO films; d) Au4f XPS spectrum of AuNPsrGO;
FIG. 9 is a Raman spectrum of Au/rGO in an embodiment of the invention;
FIG. 10 shows ECL and CV performance of AuNPs-rGO at different AuNPs particle sizes, where A is the Au/rGO versus Ru (bpy) of the AuNPs particle sizes in accordance with an embodiment of the present invention 3 2+ ECL manifestations of action; b is CV performance of Au/rGO with different particle sizes of AuNPs; c is a cathode co-reactant Au/rGO-2 and the bare electrode are respectively arranged on Ru (bpy) 3 2+ CV performance in PBS; d is an anodic coreactant Au/rGO-3 and the bare electrode are respectively arranged on Ru (bpy) 3 2+ CV performance in PBS;
FIG. 11 shows the results of the embodiment of the invention where Au-rGO of different particle sizes is represented by A) N 2 CV performance under atmosphere, B) under air atmosphere, C) under oxygen atmosphere; d) LSV images of Au-rGO-2 at different rotation speeds; e) Cathodic coreactant and F) anodic coreactant ECL behavior under argon atmosphere.
FIG. 12 is an ECL effect diagram of different metal/reduced graphene oxide hybrids, wherein A is the different metal/reduced graphene oxide hybrid pair Ru (bpy), in an embodiment of the invention 3 2+ An ECL image of the effect; b is LSV image of different metal/reduced graphene oxide hybrids;
FIG. 13 is an ECL effect of Au-rGO-2 and Au-rGO-3 on ruthenium terpyridyl under different atmospheres, wherein A is the ECL performance of the cathode co-reactant Au-rGO-2 on Ru (bpy) 32+ under nitrogen, air, oxygen atmosphere, in an embodiment of the invention; b is ECL performance of an anode co-reactant Au-rGO-3 on Ru (bpy) 32+ under the atmosphere of nitrogen, air and oxygen;
in FIG. 14, A) cathode coreactant Au/r after addition of superoxide anion inhibitorGO-2 pair Ru (bpy) 3 2+ ECL manifestations of action; b) After addition of the hydroxyl radical inhibitor, the anodic coreactant Au/rGO-3 pair Ru (bpy) 3 2+ ECL manifestations of action;
in FIG. 15, ru (bpy) 3 2+ Eliminating all of the O involved under an Ar atmosphere of acetonitrile solution 2 A comparison of the promotion of cathodoluminescence by A) Au-rGO-2 and the promotion of cathodoluminescence by B) Au-rGO-3 during the ORR and OER processes of dissolved oxygen and oxygen atoms;
FIG. 16 is a graph showing the ECL characterization of the sub-material of Au-rGO in an embodiment of the invention;
FIG. 17 is a graph showing the change of Ic/Ia with reduction time in an embodiment of the present invention.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. 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 inventors have sought to innovatively use ruthenium terpyridyl (Ru (bpy) without introducing excessive amounts of reactants 3 2+ ) As a single luminophore, a similar co-reactant is found to achieve opposite potential separation of signal changes by taking advantage of its property of both anode and cathode emission under the action of the corresponding co-reactant.
The inventor finds Ru (bpy) through related research 3 2+ The cathodic process of (2) is associated with an Oxygen Reduction Reaction (ORR), and the production of Reactive Oxygen Species (ROS), an intermediate of the ORR reaction, can significantly enhance luminescence. The anodic process of ruthenium terpyridyl can be modified by O 2 Quenching, and enhancement by OH, are the end product and intermediate product of the OER process (reverse reaction of ORR), respectively. Since Au and its related alloy clusters have catalytic capabilities of ORR and OER, and by varying the adjustable catalytic properties of AuNPs particle size, it becomes Ru (bpy) 3 2+ Is an ideal reagent for anode and cathode luminescence conversion.
In a first aspect, the invention provides Ru (bpy) 3 2+ The anode or cathode coreactants are Au-rGO complexes, and the particle size of Au nano particles in the anode coreactants is 10-15nm; the particle size of Au nano-particles in the cathode coreactant is 2-4nm.
Experiments have found that AuNPs and rGO alone do not significantly catalyze Ru (bpy) 3 2+ Anode or cathode emission of (a); auNPs with smaller particle size have better cathode promotion effect. This is because smaller sized Au particles have greater electrocatalytic activity towards Oxygen Reduction Reactions (ORR) than larger sized AuNPs, a significant portion of the surface atoms may absorb and activate oxygen molecules.
In some embodiments, the reduction of rGO in the anode co-reactant is to a degree of reduction of 5.5 to 6.5 hours in hydrazine hydrate vapor.
Graphene oxide has certain anodic stimulation characteristics, and reducing graphene oxide by hydrazine hydrate changes the anodic stimulation characteristics, so that the cathode luminescence promoting capability of the graphene oxide is higher than that of the graphene oxide.
Incomplete reduction reactions of defective graphene substrate formation can accelerate charge transfer from AuNPs to O 2 By destabilizing ORR intermediate species and reducing O 2 The dissociated activation energy of (2) reduces the energy barrier of the rate limiting step resulting in more reactive oxygen species production.
In some embodiments, the reduction of rGO in the cathode co-reactant is to a degree of reduction of 5.5 to 6.5 hours in hydrazine hydrate vapor.
In a second aspect, the present invention provides the Ru (bpy) 3 2+ The preparation method of the anode or cathode coreactant comprises the following steps:
HAuCl 4 Mixing the aqueous solution with the r-GO suspension in proportion, and performing ultrasonic dispersion to obtain a mixture I;
adding NaBH to mixture one 4 Mixing, adding sodium citrate, and mixing;
after the reaction is finished, separating and washing a solid product, and then redispersing the solid product to obtain a resuspension solution;
centrifuging the heavy suspension at 11000-12500rpm for 10-30min, and collecting non-precipitated components.
NaBH 4 Is used for the HAuCl 4 Reduced to Jin Shanzhi, thereby forming gold nanoparticles.
The effect of adding sodium citrate is to further reduce the gold nanoparticles.
Because the particle sizes of the gold nanoparticles in the solution are not uniform and have large difference before the step, the heavy suspension solution is centrifuged at 11000-12500rpm for 10-30min, and in the process, the gold nanoparticles with large particle sizes and the undesirable products such as the complex of the gold nanoparticles and the reduced graphene oxide are removed by centrifugation. And removing gold nanoparticles with larger particle size in the precipitate by adopting a method of taking supernatant after centrifuging at a proper rotating speed for a proper time.
In some embodiments, the method further comprises the step of preparing reduced graphene oxide by reducing graphene oxide with hydrazine hydrate vapor, specifically: and respectively placing the suspension of graphene oxide and hydrazine hydrate in two containers, placing the two containers in the same closed space, and stirring for reaction.
In some embodiments, HAuCl is present during the preparation of the anode co-reactant 4 、r-GO、NaBH 4 HAuCl in the mixed reaction system of sodium citrate 4 The concentration of (2) is 18-22mg/ml;
the concentration of r-GO is 1.8-2.2mg/ml;
NaBH 4 the concentration of (2) is 0.005-0.015M;
the concentration of sodium citrate is 0.005-0.015M.
In some embodiments, HAuCl is present during the preparation of the cathode coreactant 4 、r-GO、NaBH 4 HAuCl in the mixed reaction system of sodium citrate 4 The concentration of (2) is 18-22mg/ml;
the concentration of r-GO is 1.8-2.2mg/ml;
NaBH 4 the concentration of (2) is 0.005-0.015M;
the concentration of sodium citrate is 0.005-0.015M.
In some embodiments, after the reaction is completed, in the step of separating and washing the solid product, the separation is a centrifugation at 14500-15500rpm for 30-60min.
The centrifugal separation is carried out at a relatively high rotational speed and for a relatively long period of time, so that the residual reducing agent (NaBH 4 Sodium citrate) is completely separated from AuNPs/rGO, avoiding the influence of the residual reducing agent on AuNPs/rGO.
In some embodiments, HAuCl is used 4 The aqueous solution and the r-GO suspension are mixed in proportion, and then the steps of ultrasonic treatment and stirring are included, wherein the ultrasonic treatment time is 5-15min, and the stirring time is 1.5-2.5h. Ultrasonic agitation to HAuCl 4 Fully and uniformly mixing with r-GO. The ultrasonic power was 200w.
Preferably, for HAuCl 4 The process of ultrasonic treatment and stirring of the mixed solution of the aqueous solution and the r-GO suspension is repeated for 2 to 4 times. Repeated ultrasonic agitation to HAuCl 4 Fully mixing with r-GO and uniformly dispersing.
In some embodiments, to HAuCl 4 Adding NaBH into the mixed solution of the aqueous solution and the r-GO suspension 4 Then, after preliminary stirring, carrying out ultrasonic treatment; the time of preliminary stirring is 10-20min, and the time of ultrasonic treatment is 5-15min. Stirring is used for uniform mixing, and ultrasound is used for dispersing particle size. The ultrasonic power was 200w.
In some embodiments, after adding sodium citrate to the mixture, after preliminary stirring, sonicating; the time of preliminary stirring is 20-40min, and the time of ultrasonic treatment is 5-15min. Stirring is used for uniform mixing, and ultrasound is used for dispersing particle size. The ultrasonic power was 200w.
The invention is further illustrated below with reference to examples.
Experimental materials
Tetrachloroauric acid (HAuCl) 4 ) Silver nitrate (AgNO) 3 ) And sodium citrate from biological engineering (Shanghai) stock, inc.;
terpyridine (2, 2' -bipyridine) ruthenium (II) (Ru (bpy) 3 2+ ) Purchased from nape technologies, su zhou;
natural graphite powder (325 mesh) was purchased from nanjing first-come nanomaterial technologies limited;
sodium borohydride (NaBH) 4 ) Ethanethiol, ascorbic Acid (AA) and isopropanol were purchased from national pharmaceutical chemicals limited.
Adding 0.1M KCl into KH with proper proportion 2 PO 4 And Na (Na) 2 HPO 4 In the mixed solution, phosphate buffer (PBS, 0.1M pH 7.4) was obtained for ECL detection. All other chemicals were analytical grade chemicals and no further purification was required for use. All aqueous solutions were freshly prepared and diluted with ultrapure water (. Gtoreq.18 M.OMEGA., milli-Q, millipore).
Instrument and equipment
ECL measurements were performed on an MPI-E multifunctional electrochemiluminescence analyzer (sienna rest mai analyzer, inc.). Three electrode ECL cell with working electrode composed of modified glassy carbonAn Ag/AgCl (saturated KCl) electrode was used as a reference electrode, and a platinum wire was used as a counter electrode. Photomultiplier tubes (PMTs) are biased at 600V. The scanning voltage is 1.5 to-2V, and the scanning speed is 100mV/s.
Ultraviolet-visible light (UV-vis) absorption spectra and fluorescence spectra were obtained using a spectrophotometer (Model UV2450, shimadzu, japan) and a spectrophotometer (Model F-7000, hitachi, japan), respectively.
X-ray photoelectron spectroscopy (XPS) characterization was measured by VG Multilab 2000X X ray photoelectron spectroscopy (american thermo-electric company, usa).
Fourier transform Infrared Spectroscopy (FT-IR) was observed on an infrared spectrometer (ALPHA, bruker, germany).
Transmission Electron Microscope (TEM) images were obtained using a JEM-2010 transmission electron microscope (JEOL, japan).
Cyclic Voltammograms (CVs) and Electrochemical Impedance Spectroscopy (EIS) were obtained by an electrochemical workstation (Ivium, netherlands).
CVs are found in 5mM K containing 0.1M KCL 3 (CN) 6 ]/K 4 (CN) 6 ]In the solution, between-0.2V and +0.6V, the scanning rate was 100mV/s.
EIS measurements were performed by applying a voltage of 5mV amplitude over a frequency range of 0.01Hz to 106 Hz.
Inductively coupled plasma mass spectrometry (ICP-MS, icapp Q, thermo Fisher, america) was used to analyze real samples.
The preparation method comprises the following steps:
1) And (3) GO synthesis:
and synthesizing graphene oxide from the oxidized natural graphite powder by a Hummer method. Graphite powder (3.0 g) was added to concentrated sulfuric acid (70 mL) while vigorously stirring in an ice bath. Then, potassium permanganate (9.0 g) was gently added to maintain the suspension at a temperature below 20 ℃. The reaction system was transferred to a 40 ℃ oil bath in sequence and stirred actively for about 30 minutes. Then, 150mL of water was added and the solution was stirred at 95℃for 15 minutes. 500mL of water was added, followed by a steady addition of 15mL of hydrogen peroxide (30%) to change the color of the solution from dark brown to yellow.
To remove metal ions, the post-reaction mixture was first treated with 250ml 1: the 10 hydrochloric acid and water mixed solution was filtered and washed, and then the synthesized solid was dried in air, diluted with water to 600mL to form an oxidized graphite ink dispersion. Next, a molecular weight of 8000 to 14,000g mol is used -1 Dialysis membrane (from Beijing Chemical Reagent co., china) was subjected to dialysis purification for one week to eliminate residual metals.
The dispersion of the metal ion-removed graphite oxide ink solution was diluted to 1.2L, stirred overnight, sonicated for 30 minutes, and exfoliated to graphene oxide. Finally, the graphene oxide dispersion was centrifuged at 3000rpm for 40 minutes to remove non-exfoliated graphite.
2) Synthesis of reduced graphene oxide r-GO
2mg of graphene oxide was dissolved in 2ml of ultrapure water; the resulting 2mg/ml graphene oxide and 2ml hydrazine hydrate were placed in two clean small beakers, respectively, while one large beaker was covered on both beakers. After 6 hours of stirring, the color of the graphene oxide fabric changed from light brown to black, indicating the formation of reduced graphene oxide.
3) Synthesis of cathode coreactant Au-rGO-2 and anode coreactant Au-rGO-3 of terpyridyl ruthenium
HAuCl 4 (2.5. Mu.l of 2% HAuCl for Au-rGO-2) 4 Diluting to 10 μl with ultrapure water; for Au-rGO-3, 10. Mu.l of 2% HAuCl 4 Undiluted) 2ml r-GO was added and the solution stirred, followed by sonication for 10 minutes, then stirring at room temperature for 2 hours, and the procedure was repeated three times.
After 10 minutes of ultrasonic inspection, 25. Mu.l of freshly prepared NaBH 0.01M was added rapidly 4 Stirring for 15 minutes, and then carrying out ultrasonic treatment for 10 minutes;
then 10 μl of 0.01M sodium citrate was added to the solution, stirred for 25 minutes, then sonicated for 10 minutes.
After that, the mixture was centrifuged at 15,000rpm for 45 minutes to remove the excess NaBH 4 And sodium citrate, thoroughly washed with water, and finally redispersed in 2mL of ultrapure water. The resuspended solution was then centrifuged at 12,000rpm for 20 minutes to collect the non-precipitated components of the solution for further use and characterization.
Synthetic characterization
Electron microscope and particle size analysis
The nanostructure of the composite material can be verified by morphological analysis. Large-scale Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM) images showed typical fold texture of Au-rGO films, illustrating the presence of flexible ultrathin rGO flakes (as shown in fig. 1). In addition, clearly visible spherical AuNPs particles, namely black dots in TEM images and bright dots in SEM images, also appear on the background reduced graphene oxide flakes, verifying the in-situ growth of AuNPs on reduced graphene oxide flakes. TEM images (FIG. 1 b) show that AuNPs are uniformly spread on the surface of rGO sheets, with no loose clusters formed on the outside. The inset of fig. 1b shows that the AuNPs have a diameter on Au/rGO of about 3.8nm, which is smaller than the size of a single AuNPs, indicating that the electrostatic or pi-pi stacking interactions between the AuNPs and rGO surfaces are relatively strong.
According to the Plieth equation:
wherein Ebulk is the oxidation potential of the bulk metal (taken as 1.15V), gamma is the surface tension (1880 erg cm -2 )，V m Is the molar volume (10.21 cm) 3 mol -1 ) Z is the electron number (1), F is the Faraday constant, and d is the NP diameter (3.4 nm).
Thus, the peak oxidation potential of AuNPs (E AuNPs) (Au (0) to Au (I)) in Au/rGO-2 was calculated to be 0.92V (compared to SHE). E AuNPs and Ag/AgCl electrodes were transformed according to the Nernst equation:
E°vs Ag/AgCl＝E°vs SHE-E° Ag/AgCl -(RT/(zF·lge))pH；
wherein, E DEG vs SHE of AuNPs is 0.92V, E DEG Ag/AgCl Is 0.22V vs SHE. The pH of the system was 6.
Thus, the comparison of E.degree AuNPs with Ag/AgCl was calculated to be 0.35eV, which is consistent with the CV peak at 0.37V for AuNPs (Au (0) to Au (I)) when 2mol/L Au/rGO-2 is supported on the electrode (FIG. 3).
EDS
Analysis of chemical composition was performed by EDS mapping. The presence of AuNPs on rGO was further confirmed by EDS mapping of Au-rGO composites, which showed characteristic peaks of C, N, O and Au, consistent with the chemical composition of graphene and AuNPs. The presence of an oxygen characteristic peak in the EDS spectrum indicates that the oxygen-containing groups on the graphene oxide are not fully reduced (as shown in fig. 3).
XRD
The crystalline phase composition of Au/rGO was analyzed using XRD (fig. 5). As GO decreases, the diffraction peak of GO at 10.2 (0.2) disappears (fig. 5, dark blue curve) and appears as a new peak at 29.0 (0.0 2) (fig. 5, light blue curve) for rGO generation. Characteristic diffraction peaks of rGO also appear in the diffraction spectrum Au/rGO, which have a significant characteristic diffraction peak at 38.3℃and two peaks of poor intensity at 44.5℃and 82.4℃respectively, corresponding to Au (1 1), au (2 0) and Au (2 22 2), respectively, due to the recombination of face-centered cubic (fcc) structures of AuNPs on rGO.
Ultraviolet-visible absorption spectrum
To further confirm the dual reduction effect, the uv-visible absorption spectrum of Au-rGO composite films was also recorded, as shown in fig. 6a, rGO spectra exhibited characteristic absorption peaks at 227nm and shoulder peaks at 315nm, corresponding to pi-pi transitions of aromatic Csingle bonds C and n-pi transitions of Csingle bonds O bonds, respectively. In the Au-rGO spectrum, the peak at 227nm was red shifted to 258nm and the peak at 315nm disappeared, demonstrating the presence of rGO. Furthermore, a new absorption peak at 535nm appears in the Au-rGO spectrum, which is due to surface plasmon resonance in Au and confirms the formation of Au.
In FIG. 6B, au/rGO-A, au/rGO-B and Au/rGO-C refer to the reduction degree of rGO in Au/rGO, respectively, as follows: reducing for 3h, 6h and 12h in hydrazine hydrate steam. The red shift of the characteristic peak of rGO indicates an increase in rGO reduction time.
zeta potential
Zeta potential measurements were performed on GO, rGO and Au/rGO to detect surface charge characteristics. The average zeta potential of GO is about-44 mV, derived from oxygen-containing functional groups, such as carboxyl and epoxy groups, with negative charges on the GO surface. After the reduction process, the 23.5mV value of RGO becomes more negative, probably because functionalization of RGO during partial reduction results in a higher surface negative charge density compared to GO. This results in stable dispersion of RGOs in an aqueous solution by electrostatic repulsive force with water molecules. The estimated Zeta potential of Au/rGO NCs was found to be 7.95mV. The reduced negative charge of Au/rGO NCs compared to rGO suggests successful synthesis of Au NPs on rGO, as shown in fig. 7.
XPS
The chemical structure of rGO and Au/rGO was further confirmed by X-ray photoelectron spectroscopy (XPS). As is apparent from FIG. 8A, carbon (C) and oxygen (O) are the main components of RGO, and Au-RGO is composed of C, O and gold (Au). The nitrogen (N) is very small in the rGO and Au-RGO. The high resolution C1s deconvolution spectrum of Au-rGO is shown in fig. 8B, which can be divided into four peaks centered at 284.6 eV (C-C/c=c in the aromatic ring), 286.3eV (C-O), 287.2eV (c=o) and 288.4eV (O-c=o), with the relatively higher c=o peaks indicating that rGO is not completely reduced. The high resolution N1 s spectrum of C in fig. 8 can be deconvolved into three gaussian-lorentzian peaks with binding energies of 398.6eV (sp 2 bonded nitrogen in the N-containing aromatic ring (C-n=c)), 399.7eV (tertiary nitrogen N- (C) 3 group) and 400.7eV (amino (C-N-H)), confirming the presence of amino groups on Au/rGO.
High resolution Au4f spectra obtained from Au-RGO samples, as shown in FIG. 8D, in the binding energy scale of Au (I), more pronounced Au4f 7/2 and Au4f 5/2 spin-orbital gemini were found at 88.3eV and 84.5eV, and weaker Au4f 5/2 and Au4f 7/2 at 87.2V and 83.4eV due to Au (0). Thus, the chemistry of gold in Au-rGO has been determined as a combination of metal-Au (0) and Au (I) present in Au-N bonds. The slightly negative shift (0.4 eV) exhibited by the Au4f spin-orbit duplex region relative to the conventional reference position of metal-Au means that there is a strong interaction between Au and the RGO framework.
Raman spectrum
Raman spectroscopy tests were performed on Au/rGO and rGO. Given the nearly identical raman spectra between Au/rGO and rGO (fig. 9), it can reasonably be assumed that the formation of AuNPs has little effect on the in-plane sp2 domain size of graphene, probably because the low loading volume of AuNPs (0.01 atomic%) seems to be insufficient to structurally damage rGO.
ECL characterization
For research and demonstration, a series of Au-rGO (Au-rGO-1, au-rGO-2, au-rGO-3 and Au-rGO-4) with particle sizes of 3.1, 3.4, 13.5 and 30.6nm respectively are synthesized.
Ru (bpy) is shown in FIG. 10A 3 2+ And the corresponding ECL behavior of the prepared Au/rGO. As co-reactant Au/rGO-1, stronger Ru (bpy) was observed at-1.7V 3 2+ Cathode luminescence (red line) (5123 a.u). Au/rGO-2 is Ru (bpy) under the condition of-1.7V (blue line) 3 2+ Has super strong cathode luminescence (14488 a. U), which is stronger than the corresponding peak value of Au/rGO-1. Au/rGO-3 and Au/rGO-4 both exhibit poor cathode catalytic performance with the lowest cathode peak being lower than bare GCE. Thus, ECLThe results demonstrate that Au/rGO can exhibit Ru (bpy) at medium-small AuNPs particle sizes 3 2+ Is a strong cathodic co-reaction characteristic of (c).
Mechanism for
Cathodic coreactant of ruthenium with ORR reaction
The cathode co-reactant of ruthenium terpyridyl is an ORR catalyst that is strong enough to produce sufficient ROS, yet avoid excessive water production from the complete reaction. Au/rGO has adjustable catalytic properties, which can be enhanced by shrinking AuNPs and vice versa. Furthermore, according to d-band theory, as the size of the Au nanocluster core decreases, the d-band narrows and shifts toward the fermi level, indicating that smaller Au clusters are energetically more favorable to O 2 Is adsorbed by the adsorbent. Therefore, based on the theory, the Au/reduction graphene oxide pair Ru (bpy) with medium particle size 3 2+ The promotion effect of cathodoluminescence is greatest.
A series of Au-rGO (Au-rGO-1, au-rGO-2, au-rGO-3 and Au-rGO-4) with the particle sizes of 3.1, 3.4, 13.5 and 30.6nm are synthesized. ECL results demonstrate that Au/rGO can exhibit Ru (bpy) at medium-small AuNPs particle sizes 3 2+ Is shown in fig. 10 a.
Cyclic Voltammograms (CVs) show the addition of Ru (bpy) 3 2+ Reversible peaks of redox reaction (at 1.13V and +1.05V respectively) and Ru (bpy) 3 2+ In PBS and Ru (bpy) outside the reduction oxidation reactions (at-1.65V and-1.60V, respectively) (FIG. 10B) 3 2+ A small peak of-0.65V observed on GCE of PBS was attributed to the Oxygen Reduction Reaction (ORR). The peak at-0.65V increased significantly after modification of Au/rGO-2 on GCE, indicating its catalytic performance during ORR (FIG. 10C).
By O at room temperature 2 Or N 2 Cyclic voltammetry was performed in a saturated 0.1M aqueous KOH solution and the catalytic performance of a series of Au/rGO was compared. As shown in FIG. 11B, the ORR initiation potential was about-0.08V (vs. Ag/AgCl), and the reduction peak was about-0.22V (vs. Ag/AgCl). Inhibition and enhancement of the reduction peaks in nitrogen and oxygen atmospheres indicates oxygenThe reaction was participated, which demonstrates the ORR process (fig. 11A-C). The adjustable catalytic performance of Au/RGO was demonstrated by varying the particle size of Au/RGO under the same atmosphere. Among them, the Au/rGO-1 catalyst with the smallest particle size has the best ORR catalytic performance, and the catalytic performance is reduced with the increase of the particle size. These findings indicate that Au/rGO-2 with moderate ORR catalytic capability will have superior cathodic coreactant performance.
At O 2 The number of electron transfer during catalysis was calculated using Linear Sweep Voltammetry (LSV) in saturated 0.1M KOH solution at different rotational speeds (ω) of Rotating Disk Electrode (RDE) 225rpm to 3600rpm (fig. 11D). The initial ORR potential of the Au/rGO-2 modified electrode at 1600rpm was about-0.20V (vs Ag/AgCl) and the ORR current density at 0.8V (vs Ag/AgCl) was about 0.28mA/cm 2 . FIG. 11D is an inset depicting the Koutesky-Levich equation (J-1 vs. omega. -1/2) at different electrode potentials (from 0.5V to 0.7 vsAg/AgCl). According to the K-L equation, the number of electrons transferred (N) per oxygen molecule catalyzed by Au/rGO-2 is 1.2-1.7 in the potential range of-0.5 to-0.7V (vs Ag/AgCl).
The catalytic activity of Au/rGO, and different metal/reduced graphene oxide hybrids at different AuNPs particle sizes was characterized by recording the RDE curve (1600 rpm) corresponding to ORR. As shown in FIG. 11, the ORR onset potential of Au/rGO-2 (-0.20V) is more positive than that of Au/rGO-3 (-0.25V), but more negative than that of Au/rGO-1 (-0.18V). In addition, au/RGO-2 (0.28 mA/cm) 2 ) The ORR current density (e.g., at-0.8V vsAg/AgCl.) is significantly greater than that of Au/RGO-3 (0.18 MA/cm) 2 ) But lower than Au/rGO-1 (0.38 MA/cm 2).
The ORR onset potential of Au/rGO-2 (-0.20V) is more negative than Ag/rGO (-0.15V), cu/rGO, and Pt/rGO (-0.10V) as shown in FIG. 12B. These metal nanoparticles/graphene were compared as Ru (bpy) 3 2+ Electrochemiluminescence properties of the co-reactant of (a) (fig. 12A). The superior cathodic coreactant performance of Au/rGO-2 can also be explained by the moderate ORR catalytic activity.
Anode coreactant of ruthenium terpyridate with OER reaction
OH. InPromotion Ru (bpy) 3 2+ Plays an important role in anodic oxidation, and oxygen is toxic to anodic luminescence. Thus, au/rGOs acts as a controlled Ru (bpy) 3 2+ The cathode or anode promoter has the advantage that it exhibits an increase in OER catalytic performance with decreasing particle size. Suitable anode promoters should therefore not only catalyze H 2 O loses one electron to generate a large amount of OH. Excessive O should also be avoided 2 . Thus, weaker OER reaction catalysts are required to shift the reaction to reaction (equation 2-1) rather than reaction (equation 2-2), while also taking into account d-band theory, so that larger particle size Au-rGO has better anodic co-reactant properties of ruthenium.
H 2 O-e→HO ˙ +H + (2-1)
O2 ˙ --e→O 2 (2-2)
As shown in FIG. 10A, ru (bpy) when Au/RGO-3, au/RGO-4 having a large size (13 Nm) and a largest size (30 Nm) in AuNPs is loaded on the electrode 3 2+ The anode luminescence at 1.1V was greatly amplified. Whereas Au/rGO-1 and Au/rGO-2 with small particle size of AuNPs are only compatible with Ru (bpy) 3 2+ Generating weak fluorescence, weaker than bare GCE, probably due to O generated by OER 2 Quenching effect of (2). Ru (bpy) 3 2+ The electroluminescence over the Au/rGO-3 catalyst is superior to Au/RGO-4 because Au/RGO-4 catalysts with too large AuNPs particle size are too weak for OER catalysis to produce enough OH. This is demonstrated by cyclic voltammograms.
In Ru (bpy) 3 2+ Under anodic scanning of bare GCE in solution, due to Ru (bpy) 3 2+ The current rises at +1.0v background current and then increases faster due to oxidation of water and peaks at +1.3v. Peak current at +1.3v can be used as a marker for OER level, cyclic voltammetry was used to evaluate the OER catalytic performance of a series of synthetic Au/rGO, and fig. 10B shows gradual decline of OER catalytic ability of Au/rGO-1 to Au/rGO-4. The result also proves that the anode accelerator Au/rGO-3 with weak OER catalytic performance can slow down the OER reaction, thereby prolonging the catalytic reaction of the product OHResidence time of the surface of the chemical agent. In addition, the larger AuNPs particle size may make OH numbers more prone to desorb from Au/rGO-3, resulting in a large amount of OH numbers to accumulate near the electrode, which favors strong ECL luminescence.
The enhancement of ECL luminescence by the cathodic and anodic Au/rGOs under nitrogen and oxygen atmospheres was characterized.
In a nitrogen environment, a cathode accelerator Au/rGO-2 (dark blue line) is used for preparing Ru (bpy) 3 2+ The promotion of cathodoluminescence is reduced because the nitrogen in the system removes dissolved oxygen, thereby inhibiting the occurrence of ORR reactions. While the enhancement of the anode luminescence is due to the dissolved oxygen to Ru (bpy) 3 2+* The quenching effect of (2) is lost. In contrast, ORR process is at O 2 Stimulated in the environment (light blue line), resulting in Ru (bpy) 3 2+ The cathode luminescence is enhanced.
FIG. 13B shows the anode promoter Au/rGO-3 vs Ru (bpy) under different atmospheres 3 2+ Influence of luminescence. Ru (bpy) under nitrogen atmosphere (dark blue line) 3 2+ The anodic luminescence of (2) is significantly enhanced. This is probably due to the fact that the Au/rGO-3 catalyzed OER reaction produces an intermediate OH and other reactive oxygen species that promote anodic luminescence, while by-product O 2 And dissolved oxygen is removed by a nitrogen stream. Introduction of O 2 After that, ru (bpy) 3 2+ The anodic luminescence of (2) is obviously reduced, and the cathodic luminescence is not obviously enhanced. This is because Au/rGO-3 lacks strong ORR catalytic ability, and the increase of dissolved oxygen in the electrolyte has strong quenching effect on anode luminescence.
The above results indicate that the ORR catalytic capability of Au/rGO-2 can promote Ru (bpy) 3 2+ And O generated by OER reaction of dissolved oxygen in the solution and the electrode surface 2 Ru (bpy) can be suppressed 3 2+ Is provided.
Thus, OH inhibitors-superoxide dismutase SOD and isopropanol, and O2-inhibitor Benzoquinone (BQ) were introduced to reflect the various catalytically active oxygen components independently versus Ru (bpy) 3 2+ Specific effects of cathode and anode luminescence.
As shown in fig. 14, SOD, isopropanol, benzoquinone (BQ) all significantly reduced Au/rGO-2 promoted cathodoluminescence, indicating that Au/rGO-2 promoted cathodoluminescence mainly by catalyzing the reduction of oxygen to O2- (fig. 14A).
For the anode promoter Au/rGO-3, ru (bpy) when Benzoquinone (BQ), SOD and isopropanol were added respectively 3 2+ This demonstrates that Au/rGO-3 was successfully prepared as a weak OER catalyst, demonstrating that OH-is generated at the electrode surface as the main OER product to promote anodic emission (fig. 14B).
Ru (bpy) 3 2+ Luminescence under Ar atmosphere of acetonitrile solution, eliminating all related O 2 ORR and OER processes of dissolved oxygen and oxygen atoms to examine Au/rGO and Ru (bpy) 3 2+ Is a direct effect of (a).
As a result, FIG. 15A shows that Au/rGO-2 modified electrode pair Ru (bpy) is compared to bare GCE 3 2+ The promotion effect of cathodoluminescence is weaker, and Au/rGO-3 can obviously promote Ru (bpy) 3 2+ Anodic emission (FIG. 15B), demonstrating that Au/rGO can not only indirectly promote Ru (bpy) by catalyzing OER or ORR reactions 3 2+ Emitting, and can also be directly connected with Ru (bpy) 3 2+ The reduction-reduction oxidation reaction and the oxidation-reduction reaction are carried out, and the luminescence is directly enhanced.
Ru (bpy) is detected 3 2+ Co-reaction characteristics of AuNPs, graphene oxide, reduced graphene oxide, and various combinations thereof, separated in solution. As shown in fig. 16, auNPs and rGO alone were found not to significantly catalyze either the anode or cathode emission of Ru (bpy) 32+. This is probably because, in previous studies, both experimental results and Density Function Theory (DFT) calculations indicate that none of them exhibit significant ORR or OER catalytic performance. In addition, we also changed the particle size of AuNPs, as shown in fig. 16A, auNPs with smaller particle size had better cathode promotion effect. This is because smaller sized Au particles have greater electrocatalytic activity towards Oxygen Reduction Reactions (ORR) than larger sized AuNPs, a significant portion of the surface atoms may absorb and activate oxygen molecules. In addition, reduced graphene oxideThe degree of reduction also has a certain effect on the nature of its coreactants. As can be seen from fig. 16C, graphene oxide has a certain anodic stimulation property, and reduction of graphene oxide by hydrazine hydrate changes the anodic stimulation property, and its cathodoluminescence promoting ability is greater than that of graphene oxide. From the element ratio of XPS and the amino ratio (5% of N) lower than the oxygen-containing functional group exhibited by infrared spectroscopy, it is presumed that it is possible that the relatively weak anodic co-reaction property of reduced graphene oxide is due to the anodic promotion function of the amino group on reduced graphene oxide failing to counteract the decrease in anodic luminescence caused by the decrease in the oxygen-containing functional group.
The reduction degree of the reduced graphene oxide has a certain influence on the property of a coreactant, and the reduction time of the reduced graphene oxide is measured to reduce Au/rGO and Ru (bpy) 3 2+ The effect of the reduction degree of the reduced graphene oxide on the Au/rGO co-reaction performance was further measured by the ratio of the cathode to anode luminescence (Ic/Ia) of the co-reaction. The red shift of uv-vis spectrum shows that Ic/Ia reaches maximum at 6h reduction time when the reduction degree of graphene oxide increases, and then decreases with increasing reduction time (see fig. 17). Ru (bpy) 3 2+ The optimal Ic/Ia for Au/rGO catalytic reduction from partially reduced graphene can be attributed to the fact that: incomplete reduction reactions of defective graphene substrate formation can accelerate charge transfer from AuNPs to O 2 By destabilizing ORR intermediate species and reducing O 2 The dissociated activation energy of (2) reduces the energy barrier of the rate limiting step resulting in more reactive oxygen species production.
It is speculated that the relatively weak anodic co-reaction properties of reduced graphene oxide are due to the inability of the anodic promotion function of the amino groups on reduced graphene oxide to counteract the reduced anodic luminescence caused by the reduced oxygen-containing functional groups. As can be seen from fig. 16C, graphene oxide has a certain anodic stimulation property, and reduction of graphene oxide by hydrazine hydrate changes the anodic stimulation property, and its cathodoluminescence promoting ability is greater than that of graphene oxide. This is because incomplete reduction reactions due to defective graphene substrate formation can accelerate charge transfer from AuNPs to O 2 By destabilizing ORRInter species and reduction of O 2 The dissociated activation energy of (2) reduces the energy barrier of the rate limiting step resulting in more reactive oxygen species production.
Equation of reaction
The principle of cathodoluminescence is shown in fig. 16. First, ru (bpy) 3 2+ And water are simultaneously reduced and converted to Ru (bpy) at a negative potential 3 + And. O 2 H. Then, highly oxidized O 2 H can directly bond Ru (bpy) 3 + Oxidation to Ru (bpy) 3 2+* Or oxidation of Au/rGO to form [ Au/rGO ]] ox Then indirectly oxidize Ru (bpy) 3 + . In this process, O 2 H can be reduced to hydrogen peroxide, which has a strong oxidizing property, and then further reduced to OH. Also, OH can oxidize Ru (bpy) 3 2+ Form high-energy Ru (bpy) 3 2+* Thereby triggering cathode luminescence. In addition, O due to the high oxidation potential of ROS 2 H and OH can directly oxidize Ru (bpy) 3 2+ Ru (bpy) is generated 3 3+ Then with Ru (bpy) 3 + The reaction releases light by annihilation reaction.
The reaction equation for Au-rGO-2 to promote ruthenium terpyridyl cathode luminescence is shown below:
Ru(bpy) 3 2+ +e - →Ru(bpy) 3 + (1)
Primary Pathway：
Pathway 1：
O 2 +e - +H + →·O 2 H (2)
Ru(bpy) 3 + +·O 2 H+H + →Ru(bpy) 3 2+* +H 2 O 2 (3)
Pathway 2：
Au/rGO+·O 2 H→[Au/rGO] ox · +H 2 O 2 (4)
Ru(bpy) 3 + +[Au/rGO] ox · →Ru(bpy) 3 2+* +[Au/rGO] ox · +Au/rGO (5)
Secondary Pathway：
Pathway 3：
H 2 O 2 +H + +e - →H 2 O+·OH (6)
Ru(bpy) 3 + +·OH+H + →Ru(bpy) 3 2+* +H 2 O (7)
Pathway 4：
Au/rGO+·OH→[Au/rGO] ox · +H 2 O (8)
Ru(bpy) 3 + +[Au/rGO] ox · →Ru(bpy) 3 2+* +[Au/rGO] ox ·+Au/rGO (5)
Pathway 5：
Ru(bpy) 3 2+ +·O 2 H+H + →Ru(bpy) 3 3+ +H 2 O 2 (9)
Ru(bpy) 3 2+ +·OH+H + →Ru(bpy) 3 3+ +H 2 O 2 (10)
Ru(bpy) 3 + +Ru(bpy) 3 3+ →Ru(bpy) 3 2+* +Ru(bpy) 3 2+ (11)
for anodic reactions, au/rGO-3 can be used as a co-reactant and OER catalyst to promote Ru (bpy) 3 2+ Is provided. Au/rGO-3 and Ru (bpy) 3 2+ The reaction of (2) mainly comprises Ru (bpy) through oxygen group (carboxyl, hydroxyl) and amino group on the surface 3 2+ Converted to an excited state. In addition, au/rGO-3 acts as a weak catalyst for the OER process, catalyzing the oxidation of water to form OH. Then, OH can enhance the decarboxylation process of Au/rGO-COO to Au/rGO, which can transfer electrons to Ru (bpy) 3 3+ Ru (bpy) is generated 3 2+* . In addition, small amounts of OH and Au/rGO-COO - May interact to produce CO with reducibility 2 -· Thereby Ru (bpy) 3 2+ LoweringIs Ru (bpy) 3 + Then with Ru (bpy) 3 3+ Interaction. The specific equation is as follows:
Ru(bpy) 3 2+ -e - →Ru(bpy) 3 3+ (1)
Pathway 1：
Au/rGO(ArCHOHR)-e - →[Au/rGO(ArCHOHR)] +· →[Au/rGO(ArCOHR)] · (2)
[Au/rGO(ArCOHR)] · +Ru(bpy) 3 3+ →Ru(bpy) 3 2+* +Au/rGO(ArCOR) (3)
Pathway 2：
Au/rGO(ArNCH 2 R)-e - →[Au/rGO(ArNCH 2 R)] +· (4)
[Au/rGO(ArNCH 2 R)] +· -H + →[Au/rGO(ArNCH 2 R)] · +H 2 O (5)
[Au/rGO(ArNCH 2 R)] · +Ru(bpy) 3 3+ →Ru(bpy) 3 2+ +[Au/rGO(ArN＝CHR)] + (6)
[Au/rGO(ArN＝CHR)] + +H 2 O→Au/rGO-NH 2 +Au/rGO-CHO (7)
Pathway 3：
H 2 O-e - →H + +·OH (8)
Au/rGO-COO - +·OH+H + →Au/rGO-COO·+H 2 O→Au/rGO · +CO 2 +H 2 O (9)
Ru(bpy) 3 2+ -e - →Ru(bpy) 3 3+ (10)
Au/rGO · +Ru(bpy) 3 3+ →Au/rGO + +Ru(bpy) 3 2+* →Ru(bpy) 3 2+ +hv (11)
the above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Au-rGO complex as Ru (bpy) 3 2+ Use of an anode and cathode co-reactant characterized by: ru (bpy) 3 2+ The anode and cathode coreactants are Au-rGO complex, and the particle size of Au nano particles in the anode coreactant is 10-15nm; the particle size of Au nano particles in the cathode coreactant is 2-4nm;
Ru(bpy) 3 2+ the anode coreactant and the cathode coreactant form a single-illuminant multi-signal output system, ru (bpy) 3 2+ As a single luminophor, the anode and the cathode have the property of enhancing ECL luminescence under the action of the anode and the cathode coreactant.
2. The use according to claim 1, characterized in that: in the anode coreactant, the reduction degree of rGO is reduced for 5.5-6.5h in hydrazine hydrate steam;
in the cathode coreactant, the reduction degree of rGO is reduced in hydrazine hydrate steam for 5.5-6.5h.
3. The use according to claim 1, characterized in that: ru (bpy) 3 2+ The preparation method of the anode and cathode coreactants comprises the following steps:
HAuCl 4 Mixing the aqueous solution with the rGO suspension in proportion, and performing ultrasonic dispersion to obtain a mixture I;
adding NaBH to mixture one 4 Mixing, adding sodium citrate, and mixing;
after the reaction is finished, separating and washing a solid product, and then redispersing the solid product to obtain a resuspension solution;
centrifuging the heavy suspension at 11000-12500rpm for 10-30min, and collecting the non-precipitated components.
4. A use according to claim 3, characterized in that: the method also comprises the step of preparing reduced graphene oxide by adopting hydrazine hydrate steam to reduce graphene oxide, and specifically comprises the following steps: and respectively placing the suspension of graphene oxide and hydrazine hydrate in two containers, placing the two containers in the same closed space, and stirring for reaction, wherein the stirring reaction time is 5.5-6.5h.
5. A use according to claim 3, characterized in that: in the preparation process of the anode coreactant, HAuCl 4 、rGO、NaBH 4 HAuCl in the mixed reaction system of sodium citrate 4 The concentration of (2) is 18-22mg/mL;
the concentration of rGO is 1.8-2.2mg/mL;
NaBH 4 the concentration of (2) is 0.005-0.015M;
the concentration of sodium citrate is 0.005-0.015M;
in the preparation process of the cathode coreactant, HAuCl 4 、rGO、NaBH 4 HAuCl in mixed reaction system of sodium citrate 4 The concentration of (2) is 18-22mg/mL;
the concentration of rGO is 1.8-2.2mg/mL;
NaBH 4 the concentration of (2) is 0.005-0.015M;
the concentration of sodium citrate is 0.005-0.015M.
6. A use according to claim 3, characterized in that: after the reaction is finished, in the step of separating and washing the solid product, the separation is centrifugal separation, the centrifugal rotation speed is 14500-15500rpm, and the centrifugal time is 30-60min.
7. A use according to claim 3, characterized in that: HAuCl 4 The aqueous solution and the rGO suspension are mixed in proportion, and then the steps of ultrasonic treatment and stirring are included, wherein the ultrasonic treatment time is 5-15min, and the stirring time is 1.5-2.5h.
8. A use according to claim 3, characterized in that: for HAuCl 4 Aqueous solution and rGO suspensionThe process of ultrasonic treatment and stirring of the mixed solution of (a) is repeated 2 to 4 times.
9. A use according to claim 3, characterized in that: to HAuCl 4 Adding NaBH into the mixed solution of the aqueous solution and the rGO suspension 4 Then, after preliminary stirring, carrying out ultrasonic treatment; the time of preliminary stirring is 10-20min, and the time of ultrasonic treatment is 5-15min.
10. A use according to claim 3, characterized in that: adding sodium citrate into the mixed solution, primarily stirring, and performing ultrasonic treatment; the time of preliminary stirring is 20-40min, and the time of ultrasonic treatment is 5-15min.
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