CN111560627B - Star-structure gold nanocrystal and preparation method and application thereof - Google Patents

Star-structure gold nanocrystal and preparation method and application thereof Download PDF

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CN111560627B
CN111560627B CN202010423636.2A CN202010423636A CN111560627B CN 111560627 B CN111560627 B CN 111560627B CN 202010423636 A CN202010423636 A CN 202010423636A CN 111560627 B CN111560627 B CN 111560627B
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CN111560627A (en
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韦露
姜雨晨
毛宇杰
刘枫
魏永生
赵新生
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Jiangsu Normal University
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    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/12—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by electrolysis

Abstract

The invention discloses a star-structure gold nanocrystal and a preparation method and application thereof, wherein the preparation method of the star-structure gold nanocrystal comprises the steps of preparing a eutectic solvent, preparing a gold plating solution, pretreating a glassy carbon electrode and preparing the nanocrystal; the crystal structure of the star-structure gold nanocrystal is that a triangular pyramid is epitaxially grown on each surface of an icosahedron, and the surface miller index of the star-structure gold nanocrystal consists of {331} and an adjacent { hhl } high-index crystal plane; the application of the star-structure gold nanocrystal refers to the application of the star-structure gold nanocrystal as an electrochemical nitrogen fixation catalyst in the field of ammonia synthesis. The preparation method is controllable, simple and feasible, and can accurately regulate and control the morphology of the gold nanocrystals; the prepared gold nanocrystal with the icosahedral structure has high-efficiency performance of synthesizing ammonia by electrocatalytic nitrogen reduction, and has great application value.

Description

Star-structure gold nanocrystal and preparation method and application thereof
Technical Field
The invention relates to a star-shaped structure gold nanocrystal, a preparation method and application thereof, in particular to an icosahedral star-shaped structure gold nanocrystal, a preparation method and application in the field of electrochemical nitrogen fixation.
Background
Ammonia (NH)3) Is one of the most important inorganic compounds in the world, and is a raw material or an intermediate for manufacturing important chemicals such as fertilizers, dyes, medicines and the like. In addition, the content of hydrogen in ammonia molecules is 17.6wt percent (higher than the content of hydrogen in methanol molecules: 12.5wt percent), which is a potential hydrogen storage carrier and is expected to become a new strategy for storing hydrogen in the future. At present, the traditional Haber-Bosch method is mainly used for industrially synthesizing ammonia, but the process needs to be carried out under the conditions of high temperature (400-2Greenhouse gases. In recent years, with the increasing energy and environmental problems, it is urgent to develop a low-energy-consumption and clean ammonia synthesis method which can replace the conventional Haber-Bosch method at normal temperature and pressure. The electrocatalytic Nitrogen Reduction Reaction (NRR) utilizes renewable energy sources (such as solar energy, wind energy and the like) as driving forces to react nitrogen and water at normal temperature and normal pressure to produce ammonia, and is a green, environment-friendly and sustainable nitrogen fixation method. However, the electrocatalytic nitrogen reduction synthesis of ammonia still faces two serious problems, (1) the reaction kinetics are slow: is very stable due to the N.ident.N triple bond (bond energy: 945kJ mol)-1) N-N bond cleavage is very difficult, resulting in extremely slow kinetics of the nitrogen reduction reaction. (2) Hydrogen Evolution Reaction (HER) competition limitation: when NRR is carried out in aqueous solution, the nitrogen reduction reaction potential is very close to the hydrogen evolution reaction potential of water, and the nitrogen reduction reaction potential and the hydrogen evolution reaction potential are in a competitive relationship, so that the nitrogen reduction performance and the Faraday efficiency are obviously reduced. Therefore, development of a catalyst capable of activating N efficiently2Molecularly and effectively inhibiting hydrogen evolution reactionsThe catalyst becomes the key of synthesizing ammonia by electrocatalysis nitrogen reduction.
Gold (Au) is a potential electro-catalytic ammonia synthesis catalyst through nitrogen reduction, and the NRR performance is remarkably improved due to the excellent electro-catalytic performance and the inhibition effect on hydrogen evolution reaction. For example, when the surface of the gold nano-catalyst is a high-index crystal face, the electrocatalytic NRR performance can be obviously improved. This is primarily due to the high index crystal planes having a high density of step or kink atoms, which have a lower coordination number to act as active sites in the electrocatalytic nitrogen reduction reaction, thereby promoting NRR performance. Therefore, the preparation of the nanocrystalline catalyst with the surface of the high-index crystal face structure is an effective way for remarkably improving the reduction performance of the electrocatalytic nitrogen. However, since the high index crystal planes have very high surface energy, they are limited by the thermodynamically lowest total surface energy during crystal growth, resulting in their tendency to disappear during growth, eventually obtaining only nanocrystals surrounded by low index crystal planes of low surface energy ({111} or {100}), such as octahedrons and cubes, etc.
Recent research shows that a green and novel ionic liquid analogue, namely a Eutectic solvent (DES), shows great potential in the aspect of electrochemical shape control synthesis of high-index crystal face structure metal nanocrystals due to a wide electrochemical window and rich characteristic adsorption substances. The eutectic solvent is a eutectic mixture, is usually formed by mixing quaternary ammonium salt and hydrogen bond donors (such as urea, carboxylic acid, polyhydric alcohol and the like) according to a certain proportion, has attracted extensive attention of researchers in various countries around the world due to excellent physical and chemical properties, and has potential application prospects in the fields of separation technology, organic synthesis, metal organic and functional material preparation and the like.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a preparation method of star-structure gold nanocrystals, which can controllably prepare the twenty-face star-structure gold nanocrystals; the second purpose of the invention is to provide the star-structure gold nanocrystals prepared based on the preparation method; the third purpose of the invention is to provide the application of the star-structure gold nanocrystal.
The technical scheme is as follows: the technical scheme adopted by the invention is as follows:
a preparation method of star-structure gold nanocrystals comprises the following steps:
(1) preparing a eutectic solvent: mixing choline chloride and urea in a beaker, sealing, and stirring at 60-80 ℃ to obtain a colorless liquid to prepare a choline chloride-ureido eutectic solvent;
(2) preparing a gold plating solution: dissolving chloroauric acid in the eutectic solvent prepared in the step (1), preparing a gold plating solution at the temperature of 60-80 ℃, and aging to be colorless at the temperature of 25-30 ℃;
(3) pretreating a glassy carbon electrode: the glassy carbon electrode is used as a working electrode, and the glassy carbon electrode is polished by using alumina grinding powder and is prepared for standby after ultrasonic cleaning, and the purpose is to remove alumina on the surface of the electrode;
(4) preparing star-structured gold nanocrystals: placing the working electrode in the step (3) in a three-electrode electrolytic cell filled with the gold plating solution in the step (2), taking a reference electrode as a platinum wire electrode and a counter electrode as a platinum sheet electrode, and adjusting the nucleation potential (E) by using a double-potential step methodN) Nucleation time (t)N) Growth potential (E)G) And growth time (t)G) And depositing at the temperature of 60-80 ℃ to obtain the star-structure gold nanocrystal.
Wherein in the step (1), the mol ratio of choline chloride to urea is 2: 3-1: 3.
Wherein, in the step (2), the concentration of the chloroauric acid in the plating solution is 10-30 mM.
Wherein, in the step (2), the aging time is more than 3 months, preferably 4 months to 5 months.
Wherein, in the step (3), the grain diameter of the aluminum oxide grinding powder is 0.3-5.0 μm, the grinding time is 3-5 min, and the ultrasonic cleaning frequency is 4-6 times.
Wherein, in the step (4), the nucleation potential (E)N) Is-0.95 to-0.1V, and has nucleation time (t)N) 0.2 to 0.3s, growth potential (E)G) Is-0.53 to-0.57V, and the growth time (t)G) Is 300-900 s.
The preparation method of the invention takes the non-aqueous eutectic solvent as the medium without addingUnder the condition of adding any surfactant, the double-potential step method is used for preparing the gold nanocrystals with the icosahedral structure. Wherein, the aging time plays a certain role in the growth of the gold nanocrystals and can promote the formation of the icosahedral structure. Nucleation potential (E)N) The growth potential (E) of gold precursor in the gold plating solution is selected to be near the reduction peak potential on the glassy carbon electrodeG) The gold precursor in the gold plating solution is selected to be near the initial reduction potential of the glassy carbon electrode.
The surface atom arrangement of the twenty-star-shaped gold nanocrystal prepared by the preparation method is characterized by a Scanning Electron Microscope (SEM) for the product obtained by deposition in the step (4), so that the morphology and the dispersion degree of the nanoparticles on the surface of the working electrode are obtained; and (5) characterizing the product obtained by deposition in the step (4) by using a Transmission Electron Microscope (TEM) to obtain the surface atomic arrangement characteristic, namely the Miller index of the crystal surface. According to the characterization results of the scanning electron microscope and the high-resolution transmission electron microscope, a crystal model is established through professional modeling software such as Shape and Materials Studio, the exposed atomic arrangement rule of the surface of the prepared gold nano-crystal is further verified and determined theoretically, the crystal structure is that a triangular cone grows on each surface of an icosahedron in an epitaxial mode, and the surface miller index of the triangular cone is composed of {331} and an adjacent { hhl } high-index crystal surface.
Wherein the grain diameter of the gold nanocrystal with the icosahedral star-shaped structure is 300-500 nm.
The application of the gold nanocrystals with the twenty-star structure as the electrochemical nitrogen fixation catalyst in the field of ammonia synthesis is also within the protection range of the invention, the catalytic performance of the electrochemical nitrogen fixation reaction is researched at normal temperature and normal pressure, the product with the electro-catalytic nitrogen reduction performance is detected by using an ultraviolet-visible spectrum method, and the ammonia production rate and the Faraday efficiency are calculated.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
1. the invention provides a green novel preparation method for preparing a gold nanocrystal with an icosahedral star-shaped structure by using a non-aqueous system eutectic solvent as a medium and applying a double potential step method under the condition of not adding any surfactant;
2. the preparation method is controllable, simple and feasible, and can accurately regulate and control the morphology of the gold nanocrystals;
3. the surface of the twenty-face star-shaped structure gold nanocrystal is a { hhl } high-index crystal face, has high-density step atoms, and provides an active site for electrocatalytic nitrogen reduction reaction;
4. the gold nanocrystal with the icosahedral structure has high-efficiency performance of synthesizing ammonia by electrocatalytic nitrogen reduction, and the ammonia production rate is as high as 49.3 mu g h-1cm-2The Faraday efficiency is as high as 28%, and the method has great application value.
Drawings
Fig. 1 is an SEM image of twenty-star structured gold nanocrystals prepared in example 1 of the present invention, wherein the top left inset is a high-magnification SEM image;
FIG. 2 is a TEM image of an icosahedral-structured gold nanocrystal prepared by the present invention, wherein (a) is a TEM image of example 1, (b) is a local high magnification TEM image of (a), (c) is a TEM image of example 2, and (d) is a TEM image of example 3;
FIG. 3 is an i-t curve of nitrogen reduction reaction at different reaction potentials according to example 4 of the present invention;
FIG. 4 is an ultraviolet absorption spectrum of the nitrogen reduction reaction product of the icosahedral structure gold nanocrystals prepared in example 1 of the present invention at different potentials;
FIG. 5 shows the ammonia production rate and Faraday efficiency of the nitrogen reduction reaction of the icosahedral-structure gold nanocrystals prepared in example 1 of the present invention at different potentials;
FIG. 6 is an SEM image of a spherical commercial gold powder of a comparative example of the present invention;
FIG. 7 is an ultraviolet absorption spectrum of a nitrogen reduction reaction product at a potential of-0.4V of the icosahedral-structured gold nanocrystal prepared in example 1 of the present invention and the spherical commercial gold powder of the comparative example;
fig. 8 is a graph showing ammonia production rate and faraday efficiency of nitrogen reduction reaction at-0.4V potential of the icosahedral-structured gold nanocrystals prepared in example 1 of the present invention and the spherical commercial gold powder of the comparative example.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples.
Example 1
The twenty-star-structured gold nanocrystals of the present example were prepared by the following steps:
(1) preparation of choline chloride-ureido eutectic solvent: adding choline chloride and urea into a round-bottom flask according to the molar ratio of 2:3, sealing, placing in a glycerol bath at 60 ℃, magnetically stirring to obtain a colorless liquid, and drying in a vacuum drying oven at 60 ℃ for 12 hours for later use;
(2) preparing a gold plating solution: weighing 1.24g of chloroauric acid, dissolving in 100mL of the eutectic solvent prepared in the step (1) to prepare a choline chloride-ureido eutectic solvent solution containing 30mM chloroauric acid, and aging in a thermostat at 28 ℃ for 4 months until the solution is colorless for later use;
(3) pretreating a glassy carbon electrode: polishing a glassy carbon electrode (phi is 6mm) serving as a working electrode by using alumina grinding powder with the particle sizes of 1.0 mu m and 0.3 mu m respectively before each electrodeposition for 3 min; then ultrasonically cleaning in an ultra-pure water bath for 5 times, and removing aluminum oxide grinding powder on the surface of the electrode to obtain the surface of a fresh glassy carbon working electrode for later use;
(4) preparing star-structured gold nanocrystals: placing the working electrode treated in the step (3) into a three-electrode electrolytic cell containing 10mL of the plating solution prepared in the step (2), wherein the reference electrode and the counter electrode are respectively a platinum wire electrode and a platinum sheet electrode, and regulating the nucleation potential (E) by using a double-potential step methodN) A nucleation time (t) of-0.97VN) 0.25s, growth potential (E)G) is-0.55V and growth time (t)G) The deposition temperature is 60 ℃ for 500s, and the twenty-star-shaped structure gold nanocrystal is obtained.
The SEM image of the icosahedral-structured gold nanocrystal prepared in this example is shown in fig. 1, the TEM image is shown in fig. 2(a) and 2(b), and the exposed atomic arrangement rule of the icosahedral-structured gold nanocrystal surface prepared by SEM image and TEM image and crystal model establishment analysis can theoretically verify and confirm that the crystal structure is formed by epitaxially growing a triangular pyramid on each surface of an icosahedron, and the surface miller index of the triangular pyramid is composed of {331} and the adjacent { hhl } high index crystal plane.
Example 2
The twenty-star-structured gold nanocrystals of the present example were prepared by the following steps:
(1) preparation of choline chloride-ureido eutectic solvent: adding choline chloride and urea into a round-bottom flask according to the molar ratio of 1:2, sealing, placing in a glycerol bath at 80 ℃, magnetically stirring to obtain a colorless liquid, and drying in a vacuum drying oven at 60 ℃ for 12 hours for later use;
(2) preparing a gold plating solution: weighing 1.24g of chloroauric acid, dissolving in 100mL of the eutectic solvent prepared in the step (1) to prepare a choline chloride-ureido eutectic solvent solution containing 30mM chloroauric acid, and aging in a thermostat at 25 ℃ for 5 months until the solution is colorless for later use;
(3) pretreating a glassy carbon electrode: polishing a glassy carbon electrode (phi is 6mm) serving as a working electrode by using alumina grinding powder with the particle sizes of 1.0 mu m and 0.3 mu m respectively before each electrodeposition for 5 min; then ultrasonically cleaning in an ultra-pure water bath for 4 times, and removing aluminum oxide grinding powder on the surface of the electrode to obtain the surface of a fresh glassy carbon working electrode for later use;
(4) preparing star-structured gold nanocrystals: placing the working electrode treated in the step (3) into a three-electrode electrolytic cell containing 10mL of the plating solution prepared in the step (2), wherein the reference electrode and the counter electrode are respectively a platinum wire electrode and a platinum sheet electrode, and regulating the nucleation potential (E) by using a double-potential step methodN) A nucleation time (t) of-0.95VN) 0.2s, growth potential (E)G) is-0.53V and growth time (t)G) The deposition temperature is 80 ℃ for 300s, and the twenty-star-shaped structure gold nanocrystal is obtained.
A TEM image of the icosahedral-structured gold nanocrystals prepared in this example is shown in fig. 2 (c).
Example 3
(1) Preparation of choline chloride-ureido eutectic solvent: adding choline chloride and urea into a round-bottom flask according to the molar ratio of 1:3, sealing, placing in a glycerol bath at 70 ℃, magnetically stirring to obtain a colorless liquid, and drying in a vacuum drying oven at 60 ℃ for 12 hours for later use;
(2) preparing a gold plating solution: weighing 0.82g of chloroauric acid, dissolving in 200mL of the eutectic solvent prepared in the step (1) to prepare a choline chloride-ureido eutectic solvent solution containing 10mM chloroauric acid, and aging in a thermostat at 30 ℃ for 4 months until the solution is colorless for later use;
(3) pretreating a glassy carbon electrode: polishing a glassy carbon electrode (phi is 6mm) serving as a working electrode by using alumina grinding powder with the particle sizes of 1.0 mu m and 0.3 mu m respectively before each electrodeposition for 4 min; then ultrasonically cleaning in an ultra-pure water bath for 6 times, and removing aluminum oxide grinding powder on the surface of the electrode to obtain the surface of a fresh glassy carbon working electrode for later use;
(4) preparing star-structured gold nanocrystals: placing the working electrode treated in the step (3) into a three-electrode electrolytic cell containing 10mL of the plating solution prepared in the step (2), wherein the reference electrode and the counter electrode are respectively a platinum wire electrode and a platinum sheet electrode, and regulating the nucleation potential (E) by using a double-potential step methodN) A nucleation time (t) of-0.1VN) 0.3s, growth potential (E)G) is-0.57V and growth time (t)G) The deposition temperature is 70 ℃ for 900s, and the twenty-star-shaped structure gold nanocrystal is obtained.
A TEM image of the icosahedral-structured gold nanocrystals prepared in this example is shown in fig. 2 (d).
Example 4
The twenty-star structured gold nanocrystal catalyst electrode prepared in example 1 was placed in an H-type electrolytic cell containing 50mL of nitrogen-saturated 0.1mM HCl supporting electrolyte, the cathode and anode were separated using 211-type Nafion membrane, and the reference electrode and the counter electrode were a saturated hydrogen electrode and a graphite sheet electrode, respectively. Before each electrocatalytic nitrogen reduction reaction, 99.999 percent nitrogen is led into the supporting electrolyte solution in the cathode tank for 1 hour in advance, and the nitrogen flow rate is 50cm3 min-1And the flow rate was continued to be maintained through the cathode cell during the electrocatalytic nitrogen reduction reaction to obtain a nitrogen-saturated 0.1mM HCl supporting electrolyte solution.
The nitrogen reduction reaction was carried out at-0.3V, -0.4V, -0.5V, -0.6V and-0.7V, respectively, at 25 deg.C and 1atm for 2h, and the i-t curves at the respective potentials for the nitrogen reduction reaction were recorded, as shown in FIG. 3.
An indophenol blue colorimetric method is used, and an ultraviolet-visible spectrum method is used for testing nitrogen reduction reaction products under various potentials, and the specific method is as follows: taking 2mL of reaction solution after the nitrogen reduction reaction for 2h, adding 2mL of 1M sodium hydroxide solution containing 5 wt% of salicylic acid and 5 wt% of sodium citrate, adding 1mL of 0.05M sodium hypochlorite, adding 0.2mL of 1 wt% of sodium nitroprusside, mixing uniformly, standing for 1h, and testing by using an ultraviolet spectrophotometer, wherein the test result is shown in FIG. 4 and FIG. 5. By comparison, the icosahedral-structure gold nanocrystals prepared in example 1 of the present invention showed a high ammonia production rate of 49.3 μ g h at-0.4V-1cm-2The Faraday efficiency is as high as 28 percent.
Comparative example
Spherical commercial gold powder (CAS:7440-57-5, 0.5-0.8 μm) was selected as the catalyst, and the SEM image is shown in FIG. 6. The preparation method of the catalyst electrode comprises the following steps: (1) weighing 3.5mg spherical commercial gold powder catalyst and 50 μ L5 wt% Nafion solution, adding into a reagent bottle containing 600 μ L anhydrous ethanol, and ultrasonic dispersing in 25 deg.C constant temperature water bath for 20min to obtain a solution containing 5.83 μ L-1Spherical commercial gold powder catalyst/absolute ethanol slurry of (a); (2) and (2) measuring 15 mu L of spherical commercial gold powder catalyst/absolute ethyl alcohol slurry prepared in the step (1) to be suspended and dropped on the surface of the pretreated glassy carbon electrode (phi is 6mm), and naturally airing for later use.
The performance of the icosahedral-structure gold nanocrystals prepared in example 1 of the present invention was compared with that of the spherical commercial gold powder catalyst of the comparative example in ammonia synthesis by electrocatalytic nitrogen reduction at-0.4V. The test procedure was the same as in example 4, and the test results are shown in fig. 7 and 8. It can be seen that the gold nanocrystals with the icosahedral structure prepared by the invention have the performance of synthesizing ammonia by electrocatalytic nitrogen reduction at-0.4V (the ammonia production rate is 49.3 mu g h)-1cm-2Faraday efficiency: 28 percent) is much higher than the electrocatalytic nitrogen reduction ammonia synthesis performance of the spherical commercial gold powder catalyst (ammonia production rate: 14.2μg h-1cm-2Faraday efficiency: 7.8%).

Claims (7)

1. A preparation method of star-structure gold nanocrystals is characterized by comprising the following steps:
(1) preparing a eutectic solvent: mixing choline chloride and urea in a beaker, sealing, and stirring at 60-80 ℃ to obtain a colorless liquid to prepare a choline chloride-ureido eutectic solvent;
(2) preparing a gold plating solution: dissolving chloroauric acid in the eutectic solvent prepared in the step (1), preparing a gold plating solution at the temperature of 60-80 ℃, and aging at the temperature of 25-30 ℃ until the gold plating solution is colorless, wherein the aging time is more than 3 months;
(3) pretreating a glassy carbon electrode: polishing the glassy carbon electrode by using the glassy carbon electrode as a working electrode and using aluminum oxide grinding powder, and ultrasonically cleaning for later use;
(4) preparing star-structured gold nanocrystals: and (3) placing the working electrode in the step (3) in a three-electrode electrolytic cell filled with the gold plating solution in the step (2), taking a reference electrode as a platinum wire electrode and taking a counter electrode as a platinum sheet electrode, and regulating the nucleation potential, the nucleation time, the growth potential and the growth time by using a double-potential step method, wherein the deposition temperature is 60-80 ℃ to prepare the star-shaped structure gold nanocrystal, wherein the nucleation potential is-0.95-0.1V, the nucleation time is 0.2-0.3 s, the growth potential is-0.53-0.57V, and the growth time is 300-900 s.
2. The method for preparing star-structured gold nanocrystals according to claim 1, wherein: in the step (1), the mol ratio of choline chloride to urea is 2: 3-1: 3.
3. The method for preparing star-structured gold nanocrystals according to claim 1, wherein: in the step (2), the concentration of the chloroauric acid in the plating solution is 10-30 mM.
4. The method for preparing star-structured gold nanocrystals according to claim 1, wherein: in the step (3), the grain diameter of the aluminum oxide grinding powder is 0.3-5.0 μm, the grinding time is 3-5 min, and the ultrasonic cleaning times are 4-6.
5. The star-structured gold nanocrystal prepared according to claim 1, characterized in that: the crystal structure is that a triangular cone is epitaxially grown on each face of an icosahedron, and the surface Miller index of the triangular cone is composed of {331} and an adjacent { hhl } high-index crystal face.
6. The star-structured gold nanocrystal of claim 5, wherein: the grain size of the gold nanocrystal is 300-500 nm.
7. The application of the star-structure gold nanocrystal prepared in claim 1 as an electrochemical nitrogen fixation catalyst in the field of ammonia synthesis, wherein the ammonia production rate of the star-structure gold nanocrystal catalyst reaches 49.3 mu gh under the nitrogen reduction reaction potential of-0.4V-1cm-2The Faraday efficiency reaches 28 percent.
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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Lu Wei.Seeds and Potentials Mediated Synthesis of High-Index Faceted GoldNanocrystals with Enhanced Electrocatalytic Activities.《Langmuir》.2017,第33卷 *
Seeds and Potentials Mediated Synthesis of High-Index Faceted GoldNanocrystals with Enhanced Electrocatalytic Activities;Lu Wei;《Langmuir》;20170628;第33卷;实验部分 *
Synthesis of ammonia via electrochemicalnitrogen reduction on high-index faceted Aunanoparticles with a high faradaic efficiency;Lianqiao Tan;《Chem. Commun》;20191231;摘要 *

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