CN115652358A - Copper-based nanorod electrocatalyst, preparation method and application in electrochemical urea decomposition hydrogen production - Google Patents
Copper-based nanorod electrocatalyst, preparation method and application in electrochemical urea decomposition hydrogen production Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 28
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention discloses a porous foamy copper loaded copper oxide nanowire catalyst, a preparation method and application thereof. The copper oxide nanowire is prepared by simple chemical corrosion and calcination, and the application of the copper oxide nanowire in the field of hydrogen production assisted by electrochemical urea decomposition is explored. Firstly, growing copper hydroxide on the surface of copper oxide in situ through chemical corrosion, and calcining in inert atmosphere to obtain the self-supporting copper oxide nanowire array. The obtained self-supporting material can be directly used as a working electrode, and the defects of the traditional glassy carbon electrode testing method are avoided. The nanowire array has a relatively large specific surface area, and is beneficial to the diffusion of reactants and products in the reaction process. Compared with the traditional nickel-based catalyst, the copper-based catalyst has the characteristics of large reserves and low price, but the research on the field of urea electrochemical decomposition is still lacked. The material prepared by the invention has proper valence and morphology, can be used as an effective urea oxidation electrocatalyst, and shows better activity and selectivity.
Description
Technical Field
The invention relates to the field of electrochemical small organic molecule decomposition and hydrogen production, in particular to a copper oxide nanorod array prepared based on a chemical corrosion effect and application thereof in the field of electrochemical urea decomposition-assisted hydrogen production.
Background
The use of fossil energy which is propelled by industrial revolution brings great convenience to our lives, and the problems of energy shortage and environmental pollution which are caused by the excessive use of fossil fuel also severely restrict the development of society [1] . Hydrogen gas as a new clean green energy source with high calorific value and pollution-free products is gaining more and more research attention in recent years. The traditional hydrogen production by reforming fossil energy has small yield and high pollution; the hydrogen production by the novel renewable energy source is limited by the indirect characteristic of the novel renewable energy source. The hydrogen production by the water electrolysis can efficiently convert the hydrogen into chemical energy and electric energy at any time according to the requirement. Electrolyzed water (H) 2 O→O 2 +H 2 E = 1.23V) consists of two half-reactions, respectively an oxygen evolution reaction occurring at the anode and a hydrogen evolution reaction occurring at the cathode. The oxygen evolution reaction is the speed control step of the whole water electrolysis hydrogen production because of the high reaction energy barrier accompanied by the complicated four-step electron coupling proton process [2][3] . In the past decades, a huge number of electrocatalysts have been developed in response to the slow kinetics of the anodic reaction of electrolyzed water. Representative of these are layered double hydroxides, oxides, sulfides, phosphides, carbon materials, monoatomic compounds, and the like. However, regardless of the development of material science, an overpotential of about 200-500mV always limits the overall efficiency of hydrogen production from water electrolysis [4] 。
Aiming at the problem of larger energy consumption of hydrogen production by water electrolysis, except for developing high-efficiency electrocatalyst, a certain strategy is adopted to reduce the heat of the whole reactionThe mechanical equilibrium potential has also proved to be a valid strategy [5] . Considering that the potential of some small molecules during oxidation is far lower than the oxygen precipitation potential of the anode of the electrolyzed water, the substitution of the small molecule oxidation for the oxygen precipitation reaction provides a new research direction for reducing the energy consumption and improving the efficiency of the electrolyzed water. Common organic substances which can be used for the reaction of oxidizing the anode micromolecules comprise urea, methanol, hydrazine, benzyl alcohol and the like. The urea is an organic substance rich in industrial and agricultural wastewater, and has relatively low equilibrium potential (0.37V vs. 1.23V) [6] . Past studies have shown that metallic nickel rich catalysts generally exhibit better performance for Urea Oxidation (UOR), but are limited by the higher price and conductivity of nickel, resulting in the use of such catalysts in UOR remaining limited.
Reference documents:
[1]S.Chu,A.Majumdar.Opportunities and challenges for a sustainable energy future.Nature,2012,488(7411):294.
[2]G.Gahleitner.Hydrogen from renewable electricity:An international review of power-to-gas pilot plants for stationary applications.International J.Hydrogen Energy,2013,38(5):2039-2061
[3]Lagadec MF,Grimaud A.Water electrolysers with closed and open electrochemical systems.Nat Mater.2020；19:1140–1150.
[4]Song HJ,Yoon H,Ju B,Kim D-W.Highly efficient perovskite-based electrocatalysts for water oxidation in acidic environments:a mini review.Adv Energy Mater.2021；11,2002428.
[5]Zahran,Z.N,Mohamed,E.A,Tsubonouchi,Y,Ishizaki,M,Togashi,T,Kurihara,M,Saito,K,Yui,T,Yagi,M.Electrocatalytic water splitting with unprecedentedly low overpotentials by nickel sulfide nanowires stuffed into carbon nitride scabbards.EnergyEnviron.Sci.2021,14,5358-5365.
[6]Sun W,Li J,Gao W,Kang L,Lei F,Xie J.Recent advances in the pre-oxidation process in electrocatalytic urea oxidation reactions.Chem Commun.2022；58:2430–2442.
disclosure of Invention
The invention aims to solve the problems of high energy consumption, high catalyst price, poor stability and the like of the existing hydrogen production by water electrolysis, and provides a scheme for solving the problem that the efficiency of water electrolysis is limited by higher thermodynamic equilibrium potential. The invention provides a preparation method of a non-noble metal copper-based nano-wire electrocatalyst based on simple chemical corrosion and application thereof in the aspect of electrochemical urea oxidation-assisted hydrogen production.
A copper-based nano-wire electro-catalyst comprises a carrier and CuO or Cu (OH) loaded on the surface of the carrier 2 And CuO or Cu (OH) 2 The shape of a nanorod is presented; the carrier is porous metal.
The carrier is foam copper.
The diameter of the nano rod is 50-500nm, preferably 100-300nm.
The preparation method of the copper-based nanowire electrocatalyst comprises the following steps of:
And 3, heating the catalyst in the step 2 in an inert atmosphere to generate CuO on the surface of the carrier.
Before step 1, the porous metal is cleaned by acetone and/or hydrochloric acid and/or ethanol.
In said step 2, (NH) 4 ) 2 S 2 O 8 And the concentration of 2.5M NaOH in the aqueous solution is 0.05-0.5M and 1-10M respectively, and the treatment time is 10-100min.
In the step 3, the inert atmosphere is selected from argon, helium or nitrogen, and the conditions of the temperature raising treatment are as follows: heating at 150-220 deg.C for 10-200min and 1-5 deg.C for min -1 。
The copper-based nano-wire electro-catalyst is applied to the field of urea electrolysis-assisted hydrogen production.
In the application, a three-electrode system is adopted, a copper-based nano-wire electrocatalyst is used as a working electrode, a mercury-mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode.
In the application, the electrolyte adopts an aqueous solution containing 0.5-3M of potassium hydroxide and 0.1-1M of urea.
Advantageous effects
For the same metal in urea catalytic reactions, different valence states have a significant effect on catalytic performance, and the presence of the metal in the form of the catalyst also affects catalytic activity.
The porous self-supporting copper oxide nanowire CuONWs/CF provided by the invention has excellent performance on urea-assisted hydrogen production by water electrolysis, and the performance is superior to that of most precious metal and non-precious metal-based catalysts reported in literatures. The method has certain significance for developing a novel non-noble metal nickel-based urea electrocatalyst, eliminating the pollution of waste water urea by adopting a more effective method and producing green hydrogen by adopting a more effective method. In addition, the designed material can be used as a suitable substrate and a component to synthesize more complex and effective compounds and the like. The preparation method of the self-supporting copper oxide nanowire CuONWs/CF is simple, has excellent performance, has the potential of being used in a large scale, and has strong research and application significance.
Drawings
Fig. 1 is a schematic view of a crystal structure of a CuO catalyst described in the present invention.
FIG. 2 is a graph showing the comparison between the prices of Cu metal contained in the present invention and Co and Ni metal which are commonly used.
FIG. 3 shows CF, cu (OH) contained in the present invention 2 X-ray diffraction patterns (XRD) of NWs/CF and CuO NWs/CF.
FIG. 4 is a Scanning Electron Microscope (SEM) image at different magnifications of CF included in the present invention.
FIG. 5 is a Scanning Electron Microscope (SEM) image at different magnifications of Cu (OH) 2NWs/CF included in the present invention.
FIG. 6 is a Scanning Electron Microscope (SEM) image at different magnifications of CuO NWs/CF included in the present invention.
FIG. 7 is a transmission electron microscope (SEM) image at different magnifications of CuO NWs/CF described in the present invention.
FIG. 8 is a CuO NWs/CF X-ray photoelectron spectroscopy full spectrum (XPS) as described in the present invention.
FIG. 9 is a Cu 2p X ray photoelectron fine spectrum (XPS) of CuO NWs/CF described in the present invention.
FIG. 10 shows CF, cu (OH) 2 OER and UOR polarization plots for NWs/CF and CuO NWs/CF measured in a three electrode system.
FIG. 11 shows CF, cu (OH) according to the present invention 2 NWs/CF and CuO NWs/CF
FIG. 12 is a Tafel kinetics plot of CuO NWs/CF described in the present invention in catalyzing OER and UOR.
FIG. 13 is the effective current efficiency of CuO NWs/CF described in the present invention at different voltages during catalysis of UOR.
FIG. 14 is a graph of the stability of CuO NWs/CF described in this invention as measured by potentiostatic methods during catalysis of UOR.
FIG. 15 is a graph of the fully hydrolyzed polarization of a two-electrode system consisting of a CuO NWs/CF electrode as the anode and a platinum carbon electrode as the cathode, as described in the present invention.
FIG. 16 is a transmission electron microscopy (SEM) comparison of CuO NWs/CF as described in the present invention before and after catalyzing the UOR reaction.
FIG. 17 is a comparison of the X-ray photoelectron spectra (XPS) of CuO NWs/CF as described in the present invention before and after catalyzing a UOR reaction.
Detailed Description
The large-scale use of the existing water electrolysis hydrogen production technology is mainly limited by higher energy consumption, and the energy requirement of water electrolysis can be effectively reduced by using small-molecule oxidation at the anode instead of the traditional oxygen precipitation reaction. So far, some small molecules capable of being oxidized in the anode have been proposed, and the urea molecules commonly found in industrial and agricultural wastewater are concerned due to the very competitive electrochemical equilibrium potential. However, the performance of the Ni-based catalyst, which is more applied, is still to be improved and the price is relatively expensive. The metal copper is a kind of metal copper with large reserves and reasonable electronic structure and has great potential for being used in the field of catalysis, however, the application of the metal copper-based material is still limited in the field of urea-assisted hydrogen production. Compared with precursors CF and Cu (OH) 2NWs/CF, the copper oxide nanowire array supported by the foam copper and grown in the original mode has excellent urea catalytic performance, faster charge transfer dynamics and more excellent mass transfer capacity. The catalytic material provided by the invention can also be used as a substrate or a precursor to prepare a more effective and more excellent novel catalyst.
EXAMPLE 1 in-situ growth of Cu (OH) with nanowire morphology on surface of copper foam 2 。
First, commercially available 1mm thick copper foam mesh was cut into 1 × 1.5cm 2 And (5) small blocks. And then respectively putting the cut foamy copper into a 3M hydrochloric acid solution, an acetone solution, an ethanol solution and an aqueous solution, cleaning for a plurality of times under an ultrasonic environment, and putting the cleaned material into a 120 ℃ drying oven for drying for 12 hours.
The washed and dried metallic copper foam was placed in a beaker, 100mL of deionized water was added, and 4g of sodium hydroxide and 2.85g of ammonium peroxodisulfate were added so that their molar concentrations were 1 and 0.125mol L, respectively -1 Standing for half an hour, and then obtaining the blue copper hydroxide loaded Cu (OH) 2 Washing the material with deionized water for several times, and drying in an oven at 120 deg.C for 12 hr to obtain Cu (OH) 2 NWs/CF.
Example 2 CuO with a self-supporting nanowire morphology was grown in situ on the surface of copper foam.
Cu (OH) in example 1 2 Placing the NWs/CF precursor in an alumina crucible, and treating at 180 ℃ for 1h in an argon atmosphere, wherein the heating rate in the treatment process is 2 ℃ for min -1 Argon flow rate of 40mL min -1 Before the heat treatment, argon gas was previously introduced into the tube for 30min so that the tube was in an inert atmosphere. The processed material will be changed from blue color of copper hydroxide to black color of copper oxide, and the processed electrode CuO NWs/CF can be used as the tool for subsequent testingUsed as an electrode.
For the catalyst CF, cu (OH) in example 1 2 The NWs/CF and the CuO NWs/CF are respectively subjected to a performance characterization experiment, electrocatalytic urea decomposition and urea-assisted electrolysis water hydrogen evolution performance evaluation, and specific experimental data are as follows:
(I) Performance characterization experiments
1. Firstly, a schematic diagram of the crystal structure of the CuO material is given in FIG. 1, and the understanding of the structure of the material can better guide and develop a novel high-efficiency catalyst. In order to highlight the strong competitiveness of the copper metal adopted by the invention in terms of price, the prices of three common transition metals used as catalytic materials are shown in figure 2, and it can be seen that the price of the copper metal has a very competitive advantage, indicating that the copper metal has a greater potential in terms of practical application.
2. As can be seen from the powder XRD diffractogram of the catalyst in FIG. 3, the copper foam exhibits diffraction peaks at CF, cu (OH) 2 Both NWs/CF and CuO NWs/CF occur, while Cu (OH) 2 The remaining diffraction peaks in both NWs/CF and CuO NWs/CF matched well with the peak positions on the standard cards, which initially demonstrated that Cu (OH) could be grown in situ on the surface of metallic copper foam by our mentioned experimental procedure 2 And CuO species.
3. As shown in fig. 4, the copper foam was characterized by Scanning Electron Microscopy (SEM) and was found to have a smooth surface with no apparent morphology. And Cu (OH) formed after the treatment 2 And CuO species present the shape of the nano-rod, which shows that the material after treatment has a larger specific surface area, and is beneficial to the diffusion of reactants and products in the reaction process, as shown in 5,6.
4. Further observation of the better catalytic CuO NWs/CF by a projection electron microscope (SEM) revealed that the diameter of the CuO nanowires grown on the copper foam was about 200nm, and further high resolution transmission electron microscope tests also showed that the nanorods comprised a material with well-matched lattice stripe size with that of copper oxide, further confirming that the sample surface after treatment was CuO species, as shown in FIG. 7.
5. As shown in FIG. 8, it is found from X-ray photoelectron (XPS) scanning of CuO NWs/CF that both Cu and O elements contained in the material can be observed. Further, by comparison with Cu (OH) 2 High resolution mapping of Cu 2p for NWs/CF and CuO NWs/CF found, cu (OH) 2 Diffraction peak position of NWs/CF compared to Cu (OH) 2 The NWs/CF has obvious leftward shift, and Cu (OH) can be obtained because the XPS technology is sensitive to the information of surface elements of the material 2 Oxidation state ratio of Cu on NWs/CF surface Cu (OH) 2 NWs/CF low, which also helps to demonstrate Cu (OH) at the surface 2 The species is converted to CuO by high temperature inert atmosphere treatment as shown in fig. 9.
(II) electrocatalysis energy measurement test:
1. evaluation of oxygen evolution and Urea Oxidation reaction Performance of catalyst
Because the electrode prepared by the invention is a self-supporting electrode, the prepared material is directly used as a working electrode when evaluating the electrochemical oxidation of urea. In the test process, a three-electrode system is adopted to evaluate the catalytic performance of the material, wherein the material related to the invention is directly used as a working electrode, a mercury-mercury oxide electrode is used as a reference electrode, and a carbon rod with the diameter of 0.5cm is used as a counter electrode. In the course of electrochemical evaluation, 1mol L of an electrolyte solution was used for the oxygen evolution reaction -1 The electrolyte solution adopted in the urea oxidation contains 0.33mol L of potassium hydroxide solution -1 A potassium hydroxide solution of urea.
FIG. 10 shows CF, cu (OH) 2 Linear sweep voltammetry curves (LSV) for OER and UOR for NWs/CF and CuO NWs/CF, it is evident that the catalytic performance of CuO NWs/CF is superior to that of CF, cu (OH) 2 NWs/CF electrocatalysts, particularly CuO NWs/CF, exhibit greater current densities at the same voltage, and the histogram of FIG. 11 more visually compares the three materials OER and UOR at 100mA cm -2 The required voltage at current density, it can be seen that CuO NWs/CF has the best catalytic activity, both for OER and for UOR.
2. Catalyst kinetic behavior and charge transport capability testing:
in order to evaluate the dynamic behavior and charge transport capability of the catalyst in the catalysis process, tafel of CuO NWs/CF in the OER and UOR catalysis processes is further drawn. As can be seen in FIG. 12, tafel slope values (63 mVdec) for CuO NWs/CF in catalyzing UOR -1 ) Much less than the Tafel slope value (131 mVdec) in the catalytic OER process -1 ) This demonstrates that STP has good reaction kinetics in the catalyzed process. The analysis of the current efficiency of CuO NWs/CF in the process of catalyzing UOR shows that the CuO NWs/C has higher and higher catalytic efficiency of catalyzing UOR with the increase of voltage, which indicates that the CuO NWs/C not only has better reaction activity to UOR, but also has good reaction selectivity.
3. And (3) testing the stability of the catalyst:
the stability of CuO NWs/CF in the catalysis of UOR is obtained by chronopotentiometry (CP, test current density fixed at 100mAcm -2 ) It can be seen from figure 14 that the catalyst only initially decayed slightly during the approximately 40 hour measurement, and maintained good stability during the subsequent test period.
4. Evaluation of hydrogen production by water electrolysis assisted by full water electrolysis and urea:
to better evaluate the potential of CuO NWs/CF in urea-assisted hydrogen production applications, we used CuO NWs/CF as the anode. Commercial platinum carbon as the cathode constitutes a two-electrode system. By comparing CuO NWs/CF with the advanced sweep voltammogram of fully-hydrolyzed water and urea-assisted water electrolysis hydrogen production, we find that at 100mA cm -2 The voltage of the UOR// HER system is reduced by about 0.1V compared with OER// HER at the current density of (1), and the superiority of the urea-assisted hydrogen production by water electrolysis in energy conservation and environmental protection is proved, and the figure 15 shows.
5. Evaluation of the Properties of the Material after the reaction
In order to better understand the changes of the material morphology and the electronic structure before and after the reaction, scanning Electron Microscope (SEM) and X-ray photoelectron (XPS) tests were respectively carried out on CuO NWs/CF before and after the catalytic urea oxidation reaction, and the results show that the CuO NWs/CF can be obtained by the method. It can be seen (fig. 16, 17) that there was no significant change in the morphology of the material before and after the reaction, except for a slightly aggregated state after the reaction. The valence state of Cu in CuO NWs/CF does not obviously shift before and after the reaction, which shows that the CuO NWs/CF has better stability before and after the catalysis. In conclusion, the CuONWs/CF synthesized by the method has good catalytic activity and stability in the field of electrochemical hydrogen production assisted by flower forcing urea, and has good application potential.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.
Claims (10)
1. The copper-based nanowire electrocatalyst is characterized by comprising a carrier and CuO or Cu (OH) loaded on the surface of the carrier 2 And CuO or Cu (OH) 2 The shape of the nano-rod is presented; the carrier is porous metal.
2. Copper-based nanowire electrocatalyst according to claim 1, characterized in that the support is copper foam.
3. Copper-based nanowire electrocatalyst according to claim 1, characterized in that the diameter of said nanorods is 50-500nm, preferably 100-300nm.
4. The method for preparing the copper-based nanowire electrocatalyst according to claim 1, comprising the steps of:
step 1, placing porous metal in (NH) -containing solution 4 ) 2 S 2 O 8 And 2.5M NaOH aqueous solution, carrying out reaction;
step 2, cleaning and drying the catalyst in the step 1 to generate Cu (OH) on the surface of the carrier 2 。
5. The method according to claim 4, further comprising a step 3 of subjecting the catalyst in the step 2 to a temperature-raising treatment in an inert atmosphere to form CuO on the surface of the support.
6. The method according to claim 4, wherein the porous metal is further cleaned with acetone and/or hydrochloric acid and/or ethanol before step 1.
7. The method according to claim 4, wherein in the step 2, (NH) 4 ) 2 S 2 O 8 And 2.5M NaOH in the aqueous solution at concentrations of 0.05-0.5M and 1-10M, respectively, for a treatment time of 10-100min.
8. The method according to claim 5, wherein in step 3, the inert atmosphere is selected from argon, helium or nitrogen, and the temperature raising treatment is performed under the following conditions: heating at 150-220 deg.C for 10-200min and at 1-5 deg.C for min -1 。
9. The application of the copper-based nanowire electrocatalyst according to claim 1 in the field of urea electrolysis-assisted hydrogen production.
10. The application of claim 9, wherein a three-electrode system is adopted, the copper-based nanowire electrocatalyst is used as a working electrode, the mercury-mercury oxide electrode is used as a reference electrode, and the carbon rod is used as a counter electrode;
the electrolyte is an aqueous solution containing 0.5-3M potassium hydroxide and 0.1-1M urea.
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