CN111360279A - A kind of preparation method and application of single-atom copper material - Google Patents
A kind of preparation method and application of single-atom copper material Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 113
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 33
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 10
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 7
- LXZIFLXVFHVUKK-UHFFFAOYSA-N pyrene-1,4,5,10-tetracarboxylic acid Chemical compound OC(=O)C1=C2C(C(=O)O)=CC=C(C(C(O)=O)=C3C(O)=O)C2=C2C3=CC=CC2=C1 LXZIFLXVFHVUKK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000002829 reductive effect Effects 0.000 claims description 12
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 11
- -1 hydronium ions Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000011946 reduction process Methods 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- JEVOQXUAWFYIBD-UHFFFAOYSA-N pyrene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C2C(C(=O)O)=CC3=CC=CC4=CC=C1C2=C34 JEVOQXUAWFYIBD-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 238000000151 deposition Methods 0.000 abstract description 5
- 239000010411 electrocatalyst Substances 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003780 insertion Methods 0.000 abstract description 2
- 230000037431 insertion Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 75
- 238000006722 reduction reaction Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 9
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 8
- 239000002953 phosphate buffered saline Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000009620 Haber process Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002253 near-edge X-ray absorption fine structure spectrum Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000003839 X-ray absorption fine structure (XAFS) spectra Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract
Description
技术领域technical field
本发明涉及一种单原子铜材料领域具体地为单原子催化剂,更具体涉及一种应用于选择性合成氨领域的单原子铜材料的电催化剂的制备以及应用。The invention relates to the field of single-atom copper materials, in particular to single-atom catalysts, and more particularly to the preparation and application of an electrocatalyst of single-atom copper materials used in the field of selective ammonia synthesis.
背景技术Background technique
由氮气和氢气分子合成氨(Haber-Bosch工艺)是20世纪最伟大的发明之一。如今,这个具有100多年历史的生产方法是世界上大部分人工合成氨的主要来源,占年产量的90%。氨及其衍生物(包括尿素)是肥料的重要组成部分。据估计,如果不使用Haber-Bosch工艺中的人工肥料,全球粮食生产只能支撑当今世界人口的一小部分。然而,由于化石燃料(主要是天然气)是H2前体的主要来源,若在未来继续使用该方法,将越来越多地造成严重的环境问题。此外,N2和H2之间反应的缓慢动力学进一步加剧这一问题。要确保工艺的持续高效运转,则必须升高反应温度(500℃)和压力(>200atm)。因此,这个能量要求极高的工艺过程每年需消耗大约2%的世界总能源供给,并每年释放4亿吨二氧化碳,以便将氨生产维持在满足当前需求所需的水平。因此,开发一种可在大气压和室温下进行并实现清洁、安全和可持续地生产NH3的催化方法是极具工业价值意义的。The synthesis of ammonia from nitrogen and hydrogen molecules (the Haber-Bosch process) is one of the greatest inventions of the 20th century. Today, this 100-year-old production method is the main source of most of the world's synthetic ammonia, accounting for 90% of annual production. Ammonia and its derivatives (including urea) are important components of fertilizers. It is estimated that without the use of artificial fertilizers in the Haber-Bosch process, global food production could support only a fraction of the world's population today. However, since fossil fuels (mainly natural gas) are the main source of H2 precursors, continued use of this method in the future will increasingly cause serious environmental problems. Furthermore, the slow kinetics of the reaction between N and H further exacerbates the problem. To ensure continued efficient operation of the process, the reaction temperature (500°C) and pressure (>200 atm) must be increased. As a result, this energy-demanding process consumes approximately 2% of the world's total energy supply annually and releases 400 million tons of carbon dioxide annually in order to maintain ammonia production at the levels needed to meet current demand. Therefore, it is of great industrial value to develop a catalytic method that can perform clean, safe and sustainable NH3 production at atmospheric pressure and room temperature.
近年来,电化学方法提供了将可再生电力直接转化为化学品和化学能载体的希望。然而电化学N2还原合成氨已被证明在实践中实现极具挑战性,主要是因为N2是一种高度稳定(键能为941kJ mol-1).且不可极化的分子。目前报道的NRR合成氨产率比Haber-Bosch工艺低了两三个数量级。使用除N2以外的替代氮源是一种可能的提升合成氨产率和选择性的方案。硝酸根阴离子(NO3-)是一种潜在的氮源,因为N=O键具有相对较低的解离能(204kJmol-1),并且大量存在于肥料细菌分解产生的农业废物中。因此,如果在环境条件下能将NO3-选择性还原NH3,则可以通过消除水体污染和废物资源的再循环利用过程实现NH3的绿色生产。目前报道的电催化系统大多数都通过五电子过程将NO3-主要还原为N2,并且几乎不产生NH3。这是因为形成N2的电化学电位(1.25V vs.NHE,pH=0)比NH3形成的电位(1.20V)更为正。因此,NO3-还原为N2在热力学上比还原为NH3更有利。另外,由于动力学的限制,NO3-还原的合成氨的电位也大多发生析氢反应电位区域。在反应过程中,催化剂表面也会存在析氢竞争反应问题,产生更大量的H2。这意味着这些体系也消耗过量的电子供体用于生产NH3,导致较低的法拉第效率。因此,设计选择性地产生NH3而不产生H2的电催化剂也是十分必要的。In recent years, electrochemical methods have offered hope for the direct conversion of renewable electricity into chemicals and chemical energy carriers. However, electrochemical N2 reduction to ammonia synthesis has proven to be extremely challenging to achieve in practice, mainly because N2 is a highly stable (bond energy of 941 kJ mol −1 ) and non-polarizable molecule. The currently reported NRR yields for ammonia synthesis are two or three orders of magnitude lower than the Haber-Bosch process. The use of alternative nitrogen sources other than N2 is a possible solution to improve ammonia yield and selectivity. Nitrate anion (NO 3− ) is a potential nitrogen source because the N=O bond has a relatively low dissociation energy (204 kJmol −1 ) and is abundantly present in agricultural waste resulting from the decomposition of fertilizer bacteria. Therefore, if NO 3- can selectively reduce NH 3 under ambient conditions, the green production of NH 3 can be realized through the process of eliminating water pollution and recycling of waste resources. Most of the electrocatalytic systems reported so far mainly reduce NO 3- to N 2 through a five-electron process, and produce almost no NH 3 . This is because the electrochemical potential for N2 formation (1.25 V vs. NHE, pH=0) is more positive than that for NH3 formation (1.20 V). Therefore, the reduction of NO3- to N2 is thermodynamically more favorable than the reduction to NH3 . In addition, due to the limitation of kinetics, the potential of NO3 - reduced synthetic ammonia also mostly occurs in the hydrogen evolution reaction potential region. During the reaction process, the catalyst surface also has the problem of hydrogen evolution competition, which produces a larger amount of H 2 . This means that these systems also consume excess electron donors for the production of NH3 , resulting in lower Faradaic efficiencies. Therefore, it is also necessary to design electrocatalysts that selectively generate NH3 without H2 .
目前,虽然具有不同尺寸、形貌的多相催化剂已被广泛地报道,但是这些催化剂材料并不能被精确的调控活性位点,从而导致它们的合成氨选择性不能得到有效地提升。单原子催化剂由于具备高分散、可精准调控的活性位点而被广泛地关注。其制备方法主要有质量分离技术(mass-selected soft-landing techniques)和湿化学方法(Lei,Y.,Mehmood,F.,Lee,S.,et al.Increased silver activity for direct propyleneepoxidation via subnanometer size effects.Science 2010,328:224-228.Hackett,S.F.,Brydson,R.M.,Gass,M.H.,et al.High-activity,single-site mesoporous Pd/Al2O3 catalysts for selective aerobic oxidation of allylicalcohols.Angew.Chem.,Int.Ed.2007,46,8593-8596.)。然而这两种方式存在制备工艺复杂、低产量、高耗费等缺点,使其实际应用推广受到限制。At present, although heterogeneous catalysts with different sizes and morphologies have been widely reported, these catalyst materials cannot precisely control the active sites, resulting in their inability to effectively improve their selectivity for ammonia synthesis. Single-atom catalysts have attracted extensive attention due to their highly dispersed and precisely tunable active sites. Its preparation methods mainly include mass-selected soft-landing techniques and wet chemical methods (Lei, Y., Mehmood, F., Lee, S., et al.Increased silver activity for direct propyleneepoxidation via subnanometer size effects .Science 2010,328:224-228.Hackett,SF,Brydson,RM,Gass,MH,et al.High-activity,single-site mesoporous Pd/Al 2 O 3 catalysts for selective aerobic oxidation of allylicalcohols.Angew.Chem ., Int. Ed. 2007, 46, 8593-8596.). However, these two methods have disadvantages such as complex preparation process, low yield and high consumption, which limit their practical application and promotion.
然而目前为止,尚未有工艺简单、可以大批量制备以及低成本制备的高效的具有良好的合成氨选择性的单原子铜材料电催化剂的现有技术;本申请旨在解决上述问题。However, so far, there is no prior art for an efficient single-atom copper material electrocatalyst with good ammonia synthesis selectivity, which is simple in process, can be prepared in large quantities and can be prepared at low cost; the present application aims to solve the above problems.
发明内容SUMMARY OF THE INVENTION
本发明旨在克服现有技术的不足,提出一种单原子铜材料的制备方法,以及一种单原子铜材料,以及其单原子铜材料的应用。The invention aims to overcome the deficiencies of the prior art, and provides a preparation method of a single-atom copper material, a single-atom copper material, and an application of the single-atom copper material.
为实现上述目的,本申请提出将单原子铜嵌入至3,4,9,10-芘四羧酸二酐分子晶格结构中(3,4,9,10-perylenetetracarboxylic dianhydride,PTCDA,以下均简称为PTCDA),进一步地得到含有单原子的铜材料,进一步地将其用作NO3-还原合成氨电催化剂。In order to achieve the above purpose, the present application proposes to embed single-atom copper into the molecular lattice structure of 3,4,9,10-pyrenetetracarboxylic dianhydride (3,4,9,10-perylenetetracarboxylic dianhydride, PTCDA, hereinafter referred to as As PTCDA), a single-atom-containing copper material was further obtained, which was further used as an electrocatalyst for NO3 - reduction synthesis of ammonia.
具体地,为实现上述目的,本发明采用如下制备方法得到单原子铜材料。Specifically, in order to achieve the above object, the present invention adopts the following preparation method to obtain a single-atom copper material.
所述制备方法包括如下步骤:The preparation method comprises the following steps:
步骤一,将PTCDA还原,并使PTCDA中掺入水合氢离子;Step 1, reducing PTCDA and incorporating hydronium ions into PTCDA;
步骤二,将步骤一所得到的还原态的PTCDA置于低浓度Cu2+离子溶液中,优选地,Cu2+离子浓度为0.0001-0.01M,优选地Cu2+离子浓度为0.001-0.01M;In
步骤三,将PTCDA电极表面自发生电极原位自还原沉淀反应,Cu2+置换水合氢离子,并发生还原过程,得到单原子铜耦合PTCDA催化剂。In the third step, the electrode in-situ self-reduction precipitation reaction occurs on the surface of the PTCDA electrode, Cu 2+ replaces the hydronium ion, and a reduction process occurs to obtain a single-atom copper-coupled PTCDA catalyst.
优选地,步骤一中,还原过程中采用三电极电解池进行活化,对PTCDA电极采用任选地一次或者多次阴极扫描,所述三电极电解池采用1.0Mol/L的HCL中进行。Preferably, in step 1, a three-electrode electrolytic cell is used for activation during the reduction process, and one or more cathode scans are optionally used for the PTCDA electrode, and the three-electrode electrolytic cell is carried out in 1.0 Mol/L HCL.
优选地,步骤二中,所述Cu2+离子优选为,可溶性的铜盐,优选地为氯化铜、硝酸铜、硫酸铜等,所述铜离子浓度优选为0.001mol/L-0.5mol/L,所述电极原位自还原沉积的时间优选为50-5000s,优选为100-2000s,更优选500-1000s,Preferably, in
本申请还提出一种单原子铜材料,该单原子铜材料由单原子铜嵌入至3,4,9,10-芘四羧酸二酐分子晶格结构中;其采用如下方式嵌入:步骤一,将PTCDA还原,并使PTCDA中掺入水合氢离子;The present application also proposes a single-atom copper material, the single-atom copper material is embedded into the molecular lattice structure of 3,4,9,10-pyrenetetracarboxylic dianhydride by single-atom copper; the single-atom copper material is embedded in the following manner: Step 1 , reducing PTCDA and incorporating hydronium ions into PTCDA;
步骤二,将步骤一所得到的还原态的PTCDA置于低浓度Cu2+离子溶液中,优选地,Cu2+离子浓度为0.0001-0.01M,优选地Cu2+离子浓度为0.001-0.01M;In
步骤三,将PTCDA电极表面自发生电极原位自还原沉淀反应,Cu2+置换水合氢离子,并发生还原过程,得到单原子铜耦合PTCDA催化剂。In the third step, the electrode in-situ self-reduction precipitation reaction occurs on the surface of the PTCDA electrode, Cu 2+ replaces the hydronium ion, and a reduction process occurs to obtain a single-atom copper-coupled PTCDA catalyst.
优选地,Cu2+掺杂时间为0-3600s,掺杂量为0.096-1.0mg,优选地为0.096、0.197、0.309mg,PTCDA在电极的涂覆量为13mg cm-2;Preferably, the Cu 2+ doping time is 0-3600s, the doping amount is 0.096-1.0 mg, preferably 0.096, 0.197, 0.309 mg, and the coating amount of PTCDA on the electrode is 13 mg cm -2 ;
本申请还提出一种单原子铜材料的应用,一种单原子铜材料,单原子铜嵌入至3,4,9,10-芘四羧酸二酐分子晶格结构中,形成的单原子铜材料用于合成氨反应,优选地合成氨反应为采用硝酸根阴离子作为氮源进行的合成氨反应。The present application also proposes an application of a single-atom copper material, a single-atom copper material, where the single-atom copper is embedded in the molecular lattice structure of 3,4,9,10-pyrenetetracarboxylic dianhydride, and the formed single-atom copper The material is used for ammonia synthesis reaction, preferably ammonia synthesis reaction is ammonia synthesis reaction using nitrate anion as nitrogen source.
优选地,所述单原子铜嵌入至3,4,9,10-芘四羧酸二酐分子晶格结构中,采用如下方法实现:步骤一,将PTCDA还原,并使PTCDA中掺入水合氢离子;Preferably, the single-atom copper is embedded in the molecular lattice structure of 3,4,9,10-pyrene tetracarboxylic dianhydride, which is achieved by the following method: step 1, reducing PTCDA and incorporating hydrated hydrogen into PTCDA ion;
步骤二,将步骤一所得到的还原态的PTCDA置于低浓度Cu2+离子溶液中,优选地,Cu2+离子浓度为0.0001-0.01M,优选地Cu2+离子浓度为0.001-0.01M;In
步骤三,将PTCDA电极表面自发生电极原位自还原沉淀反应,Cu2+置换水合氢离子,并发生还原过程,得到单原子铜耦合PTCDA催化剂。In the third step, the electrode in-situ self-reduction precipitation reaction occurs on the surface of the PTCDA electrode, Cu 2+ replaces the hydronium ion, and a reduction process occurs to obtain a single-atom copper-coupled PTCDA catalyst.
优选地,合成氨反应中,氮源为硝酸根或者亚硝酸根,阴极电位为-0.1-到-1.0V,优选地,阴极电位为-0.2到-0.8V,优选地,阴极电位为-0.3到-0.6,更优选为-0.4V左右,其NH3产率为305.7±29.8μg h-1cm-2,NH3生成的法拉第产率为80.0±5.9%,总法拉第效率为96.0±1.6%。Preferably, in the ammonia synthesis reaction, the nitrogen source is nitrate or nitrite, the cathode potential is -0.1- to -1.0V, preferably, the cathode potential is -0.2 to -0.8V, preferably, the cathode potential is -0.3 to -1.0V -0.6, more preferably around -0.4V, the NH3 yield is 305.7±29.8 μg h -1 cm -2 , the faradaic yield of NH3 is 80.0±5.9%, and the overall Faradaic efficiency is 96.0±1.6%.
本发明的有益效果:Beneficial effects of the present invention:
1)本发明利用简单的电极原位自还原沉积方法得到单原子铜催化剂(PTCDA/Cu),克服了传统单原子催化制备需要复杂的制备工艺、低产量、高成本等缺陷;1) The present invention utilizes a simple electrode in-situ self-reduction deposition method to obtain a single-atom copper catalyst (PTCDA/Cu), which overcomes the defects of traditional single-atom catalytic preparation requiring complex preparation technology, low yield, and high cost;
2)并且通过独特的结构具有抑制析氢反应的属性,从而获得了较好的电化学NO3-还原合成氨性能;2) And through the unique structure, it has the property of inhibiting the hydrogen evolution reaction, so as to obtain better electrochemical NO3-reduction synthesis ammonia performance;
3)合成氨反应条件温和,并且具有较高的时氨产率/法拉第效率和总法拉第效率。3) The reaction conditions for ammonia synthesis are mild, and the ammonia yield/Faraday efficiency and total Faradaic efficiency are relatively high.
附图说明Description of drawings
图1是本发明a)PTCDA在1.0M HCl体系的CV图;Fig. 1 is the CV diagram of the present invention a) PTCDA in 1.0M HCl system;
b)还原的PTCDA在0.001M CuSO4溶液中的开路电位与时间关系曲线;b) Open circuit potential versus time curve of reduced PTCDA in 0.001M CuSO4 solution ;
图2是PTCDA、还原的PTCDA、PTCDA/Low Cu、PTCDA/Cu和PTCDA/High Cu的XRD图谱;Figure 2 is the XRD patterns of PTCDA, reduced PTCDA, PTCDA/Low Cu, PTCDA/Cu and PTCDA/High Cu;
图3是PTCDA/Cu的a)元素分布图、b)Cu LMM Auger峰的XPS光谱、c)X射线吸收近边结构光谱、d)延伸X射线吸收精细结构光谱;Figure 3 is a) element distribution diagram of PTCDA/Cu, b) XPS spectrum of Cu LMM Auger peak, c) X-ray absorption near-edge structure spectrum, d) extended X-ray absorption fine structure spectrum;
图4是PTCDA/Cu在0.1M PBS、含有NO2 -的0.1M PBS和含有NO3 -的0.1M PBS中测试得到的LSV曲线;Figure 4 is the LSV curve obtained by testing PTCDA/Cu in 0.1M PBS, 0.1M PBS containing NO 2 - and 0.1M PBS containing NO 3 - ;
图5是5a)不同电位下的NH3产率和法拉第效率;b)不同电位下NH3和NO2 -两者总的法拉第效率;Figure 5 is 5a) NH3 yield and Faradaic efficiency at different potentials; b) total Faradaic efficiency of both NH3 and NO2- at different potentials;
图6是PTCDA/High Cu、PTCDA/Low Cu、Cu foam(泡沫铜上负载等量的PTCDA)和Electrodeposition of Cu(根据LSV扫描相同的电位范围沉积等量的铜)的总法拉第效率对比图。Figure 6 is a graph comparing the total Faradaic efficiencies of PTCDA/High Cu, PTCDA/Low Cu, Cu foam (equivalent PTCDA loaded on copper foam) and Electrodeposition of Cu (equivalent copper deposited from the same potential range from LSV sweep).
具体实施方式Detailed ways
为了使本申请的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本申请进行进一步详细说明。应当理解,此处描述的具体实施例仅仅用以解释本申请,并不用于限定本申请。In order to make the purpose, technical solutions and advantages of the present application more clearly understood, the present application will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, but not to limit the present application.
1)单原子铜材料的制备。1) Preparation of single-atom copper materials.
发明人研究了:首先将PTCDA还原,并使其掺入水合氢离子(H3O+)。我们记录了三电极电解池中PTCDA电极在1.0M HCl的循环伏安曲线(CV)。在第一个循环中,阴极扫描显示一个在-0.62V附近的还原峰(图1a),对应于PTCDA的还原反应和H3O+的掺入过程。在随后的阳极扫描期间,观察到在+0.26V处的一个氧化峰。因此,电极表现出可逆的行为,但是存在约0.88V的极化。这主要归因于有机小分子材料较差的导电性。在经过初始的活化之后,继续对PTCDA进行阴极扫描,使其最终处于还原态。然后将其置于低浓度Cu2+离子溶液(0.001MCuSO4)中。在该体系中,PTCDA电极表面自发生了Cu2+置换水合氢离子,并发生还原过程。The inventors studied: First, PTCDA was reduced and incorporated into hydronium ions (H 3 O + ). We recorded cyclic voltammetry (CV) curves of PTCDA electrodes in 1.0 M HCl in a three-electrode electrolysis cell. In the first cycle, the cathodic scan showed a reduction peak around −0.62 V (Fig. 1a), corresponding to the reduction reaction of PTCDA and the incorporation of H3O + . During the subsequent anodic scan, an oxidation peak at +0.26V was observed. Therefore, the electrode exhibits reversible behavior, but there is a polarization of about 0.88V. This is mainly attributed to the poor electrical conductivity of organic small-molecule materials. After the initial activation, the cathodic scanning of PTCDA was continued to make it finally in the reduced state. It was then placed in a low concentration Cu 2+ ion solution (0.001 MCuSO 4 ). In this system, Cu 2+ replaced the hydronium ions on the surface of the PTCDA electrode, and a reduction process occurred.
由图2的XRD图谱可知,经过阴极扫描后,PTCDA的XRD晶面发生明显右移。这主要归因于水合氢离子的插入引起PTCDA的晶格间距减小。It can be seen from the XRD pattern in Fig. 2 that after the cathode scanning, the XRD crystal plane of PTCDA is obviously shifted to the right. This is mainly attributed to the reduction of the lattice spacing of PTCDA caused by the insertion of hydronium ions.
图3a是PTCDA/Cu的元素分布图,从中可以观察到Cu元素均匀的分布在PTCDA中,证实了Cu分散掺杂在PTCDA分子中。Figure 3a is the element distribution diagram of PTCDA/Cu, from which it can be observed that Cu elements are uniformly distributed in PTCDA, confirming that Cu is dispersed and doped in PTCDA molecules.
图3b-d的Cu LMM Auger峰的XPS光谱、X射线吸收近边结构光谱和延伸X射线吸收精细结构光谱证实Cu-O-C键的存在,表明通过电极原位自还原沉积方法可成功合成单原子铜耦合PTCDA催化剂。本工作根据开路电位随着时间的不同变化,分别得到了三个不同铜掺杂量的PTCDA/Cu电极(PTCDA/Low Cu:600s、PTCDA/Cu:1200s、PTCDA/High Cu:3600s,图1b),Cu的掺杂量分别为0.096、0.197、0.309mg。The XPS spectra, X-ray absorption near-edge structure spectra and extended X-ray absorption fine structure spectra of Cu LMM Auger peaks in Fig. 3b–d confirm the existence of Cu-O-C bonds, indicating that single atoms can be successfully synthesized by the electrode in-situ self-reductive deposition method. Copper-coupled PTCDA catalyst. In this work, three PTCDA/Cu electrodes with different amounts of copper doping (PTCDA/Low Cu: 600 s, PTCDA/Cu: 1200 s, PTCDA/High Cu: 3600 s, PTCDA/High Cu: 3600 s, respectively, are obtained according to the different changes of open circuit potential, Fig. 1b ), and the doping amounts of Cu were 0.096, 0.197, and 0.309 mg, respectively.
2)合成氨反应2) Ammonia synthesis reaction
发明人还研究了:The inventors also studied:
首先在含硝酸盐/亚硝酸盐和不含硝酸盐/亚硝酸盐的电解液中进行了线性扫描伏安(LSV)测试,确定在该体系中相关反应的还原起始电位。图4显示了0.1M PBS(磷酸缓冲盐溶液)、含有500ppm NO2 -的0.1M PBS和含有500ppm NO3 -的0.1M PBS中PTCDA/Cu的LSV图。在空白的LSV图中,我们观察到纯PTCDA的两个特征还原电流峰。当施加更多的负电位时,PTCDA/Cu表面没有看到明显的析氢电流,表明在较宽的负电位范围内PTCDA/Cu对HER具有较差的活性,这个性质将有利于提升后续的电催化合成氨反应的选择性。First, linear sweep voltammetry (LSV) tests were carried out in electrolytes containing nitrate/nitrite and without nitrate/nitrite to determine the reduction onset potentials of the relevant reactions in this system. Figure 4 shows LSV plots of PTCDA/Cu in 0.1 M PBS (phosphate buffered saline ) , 0.1 M PBS with 500 ppm NO2- and 0.1 M PBS with 500 ppm NO3- . In the blank LSV plot, we observed two characteristic reduction current peaks of pure PTCDA. When more negative potential was applied, no obvious hydrogen evolution current was seen on the surface of PTCDA/Cu, indicating that PTCDA/Cu has poor activity for HER in a wide negative potential range, and this property will be beneficial to improve the subsequent electrolysis. Selectivity of the catalytic ammonia synthesis reaction.
发明人还研究了不同施加电位对PTCDA/Cu(0.1M PBS(pH=7))电催化还原产物(铵和亚硝酸盐)的影响(-0.1和-0.6V vs.RHE之间)。在这里,亚硝酸盐是中间产物,铵是电催化还原硝酸盐的最终产物。The inventors also investigated the effect of different applied potentials (between -0.1 and -0.6 V vs. RHE) on the electrocatalytic reduction products (ammonium and nitrite) of PTCDA/Cu (0.1 M PBS (pH=7)). Here, nitrite is an intermediate product and ammonium is the final product of electrocatalytic reduction of nitrate.
从图5a可知,随着阴极电位的增大,NH3产率逐渐增大,并在-0.5V vs.RHE达到最大值(405.0±31.9μg h-1cm-2)。对于NH3生成的法拉第产率,在施加电位为-0.4V~-0.5Vvs.RHE时可达到80~81%的最大值。此外,根据图5b可知,PTCDA/Cu可在宽电位范围(-0.1V~-0.5V vs.RHE)内保持86%以上的总法拉第效率(total faradaric efficiency),并且在-0.3V vs.RHE时达到96.8±2.3%的最大值。结合氨产率结果来看,-0.4V vs.RHE是该体系最佳的反应施加电位,其NH3产率为305.7±29.8μg h-1cm-2,NH3生成的法拉第产率为80.0±5.9%,总法拉第效率为96.0±1.6%。此外,在-0.6V vs.RHE时氨产率/法拉第效率和总法拉第效率都呈现下降的趋势,这主要归因于析氢竞争反应在高电位下逐渐占据优势。It can be seen from Fig. 5a that with the increase of cathode potential, the NH 3 yield gradually increased and reached the maximum value (405.0±31.9 μg h −1 cm −2 ) at −0.5 V vs. RHE. For the Faradaic yield of NH3 generation, the maximum value of 80-81% can be reached when the applied potential is -0.4V to -0.5V vs. RHE. In addition, according to Figure 5b, PTCDA/Cu can maintain more than 86% total faradaric efficiency in a wide potential range (-0.1V ~ -0.5V vs. RHE), and at -0.3V vs. RHE reached a maximum value of 96.8±2.3%. Combined with the results of ammonia yield, -0.4V vs. RHE is the best reaction potential for this system, the NH 3 yield is 305.7±29.8μg h -1 cm -2 , and the Faradaic yield of NH 3 is 80.0 ±5.9% with an overall Faradaic efficiency of 96.0±1.6%. In addition, both the ammonia yield/Faraday efficiency and the total Faradaic efficiency showed a decreasing trend at −0.6 V vs. RHE, which was mainly attributed to the gradual dominance of the competing hydrogen evolution reaction at high potentials.
3)Cu掺杂量对性能影响为证实适量Cu掺杂量的PTCDA/Cu在提升硝酸盐还原合成氨效率方面的优势,发明人还研究了:3) Effect of Cu doping amount on performance In order to confirm the advantages of PTCDA/Cu with an appropriate amount of Cu doping in improving the efficiency of nitrate reduction for ammonia synthesis, the inventors also studied:
首先,将一块商业碳(C cloth)布(3cm×2cm)用浓HNO3预处理24小时,在表面上形成羰基。将所处理好的碳布在稀盐酸溶液中浸泡2~3天。之后,用去离子水冲洗数次,并在60℃的烘箱中干燥过夜。将PTCDA粉末与炭黑(Super P)以9:1的质量比混合,并研磨约10分钟。然后将该混合物分散在四氢呋喃(THF)于nafion(5%)体积比为9:1的溶剂中,密闭超声1小时。然后将其均匀浇铸到碳布集电器上,并在~60℃下真空干燥干燥12小时。每个电极的PTCDA负载质量为~13.0mg cm-2。First, a piece of commercial carbon (C cloth) cloth ( 3 cm × 2 cm) was pretreated with concentrated HNO for 24 h to form carbonyl groups on the surface. Soak the treated carbon cloth in dilute hydrochloric acid solution for 2 to 3 days. After that, it was rinsed several times with deionized water and dried in an oven at 60 °C overnight. The PTCDA powder was mixed with carbon black (Super P) in a mass ratio of 9:1 and milled for about 10 minutes. The mixture was then dispersed in a solvent of tetrahydrofuran (THF) in nafion (5%) in a volume ratio of 9:1 and sonicated for 1 hour in a closed state. It was then uniformly cast onto carbon cloth current collectors and dried under vacuum at ~60°C for 12 hours. The PTCDA loading mass per electrode was -13.0 mg cm -2 .
不同Cu掺杂量的PTCDA/Cu电极可通过简单的电极原位自还原沉积方法得到。首先通过循环伏安法将PTCDA电极在1.0M盐酸体系进行还原,在这个过程中水合离子会插入到PTCDA结构中(Reduced PTCDA)。随后,将电极转移到0.001M CuSO4溶液中。在该环境下,由于PTCDA的氧化电位大于Cu2+/Cu0的还原电势,PTCDA将逐渐被氧化,而Cu2+将替代水合离子嵌入至PTCDA中,并被还原为单质Cu0。根据开路电位随着时间的不同变化,分别得到了三个不同Cu掺杂量的PTCDA/Cu电极(PTCDA/Low Cu:600s、PTCDA/Cu:1200s、PTCDA/High Cu:3600s),Cu的掺杂量分别为0.096、0.197、0.309mg。PTCDA/Cu electrodes with different Cu doping amounts can be obtained by a simple electrode in-situ self-reductive deposition method. First, the PTCDA electrode was reduced in a 1.0 M hydrochloric acid system by cyclic voltammetry, during which hydrated ions were inserted into the PTCDA structure (Reduced PTCDA). Subsequently, the electrodes were transferred into 0.001 M CuSO4 solution. In this environment, since the oxidation potential of PTCDA is greater than the reduction potential of Cu 2+ /Cu 0 , PTCDA will be gradually oxidized, while Cu 2+ will intercalate into PTCDA instead of hydrated ions and be reduced to elemental Cu 0 . According to the different changes of open circuit potential with time, three PTCDA/Cu electrodes with different Cu doping amounts (PTCDA/Low Cu: 600s, PTCDA/Cu: 1200s, PTCDA/High Cu: 3600s) were obtained respectively. The impurities were 0.096, 0.197, 0.309 mg, respectively.
发明人进一步研究它们的性能,测试了PTCDA/High Cu、PTCDA/Low Cu、Cu foam(泡沫铜上负载等量的PTCDA)和Electrodeposition of Cu(根据LSV扫描相同的电位范围沉积等量的铜)电极的硝酸盐还原合成氨性能。综合分析来看,所有的Cu基电极都具有电还原硝酸盐合成氨的性能,体现了Cu基催化剂可选择性地合成氨产物。然而,它们之间的法拉第效率存在明显区别。图6是它们的总法拉第效率对比图,PTCDA/Cu展现了最高的总法拉第效率值(96.0±1.6%),而PTCDA/High Cu、PTCDA/Low Cu、Cu foam和Electrodepositionof Cu的总法拉第效率分别为69.4±9.6%、78.4±12.7%、55.2±9.4%和74.1±12.6%。这个结果表明了适量Cu掺杂的PTCDA电极可获得更高的电催化硝酸盐还原合成氨的反应选择性。The inventors further investigated their properties, testing PTCDA/High Cu, PTCDA/Low Cu, Cu foam (equivalent PTCDA loaded on foamed copper) and Electrodeposition of Cu (equivalent copper deposited from the same potential range according to LSV sweep) Nitrate reduction performance of electrodes for ammonia synthesis. From the comprehensive analysis, all Cu-based electrodes have the performance of electroreduction of nitrate to synthesize ammonia, which reflects that Cu-based catalysts can selectively synthesize ammonia products. However, there is a clear difference in Faradaic efficiency between them. Figure 6 is a comparison chart of their total Faradaic efficiencies, PTCDA/Cu exhibits the highest total Faradaic efficiency value (96.0±1.6%), while the total Faradaic efficiencies of PTCDA/High Cu, PTCDA/Low Cu, Cu foam and Electrodeposition of Cu, respectively were 69.4±9.6%, 78.4±12.7%, 55.2±9.4% and 74.1±12.6%. This result indicates that a moderate amount of Cu-doped PTCDA electrode can achieve higher electrocatalytic nitrate reduction reaction selectivity for ammonia synthesis.
上述实施例仅为本申请的优选示例性的实施例,并非对本发明的保护范围作出具体的限制,但凡采用本发明的发明构思,以及在此基础上基于非创造性劳动作出的任何变化,均应属于本发明的保护范围之内。The above-mentioned embodiments are only the preferred exemplary embodiments of the present application, and do not specifically limit the protection scope of the present invention. Any changes made based on the inventive concept of the present invention and based on non-creative work should be It belongs to the protection scope of the present invention.
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CN113068714A (en) * | 2021-04-01 | 2021-07-06 | 联科华技术有限公司 | Monoatomic copper preparation capable of replacing traditional agricultural copper preparation and preparation method thereof |
CN113403633A (en) * | 2021-05-10 | 2021-09-17 | 杭州师范大学 | Preparation method of Cu-C-N metal organic frame electrocatalyst for reducing nitrate into ammonia |
CN113463131A (en) * | 2021-07-27 | 2021-10-01 | 广东电网有限责任公司 | Copper monatomic catalyst and preparation method and application thereof |
CN113862701A (en) * | 2021-10-18 | 2021-12-31 | 苏州大学 | Preparation method of copper monatomic catalytic material and electrode and application of copper monatomic catalytic material and electrode in production of ammonia by reduction of nitrate |
CN114538575A (en) * | 2022-02-18 | 2022-05-27 | 苏州科技大学 | Electrochemical reduction device and method for high nitrate nitrogen wastewater |
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CN112206797A (en) * | 2020-10-28 | 2021-01-12 | 苏州大学 | Cu(I)@Ti3C2TxMXene catalytic material, electrode and application in nitrate radical reduction |
CN113068714A (en) * | 2021-04-01 | 2021-07-06 | 联科华技术有限公司 | Monoatomic copper preparation capable of replacing traditional agricultural copper preparation and preparation method thereof |
CN113403633A (en) * | 2021-05-10 | 2021-09-17 | 杭州师范大学 | Preparation method of Cu-C-N metal organic frame electrocatalyst for reducing nitrate into ammonia |
CN113403633B (en) * | 2021-05-10 | 2022-05-10 | 杭州师范大学 | Preparation method of Cu-C-N metal organic framework electrocatalyst for reducing nitrate into ammonia |
CN113463131B (en) * | 2021-07-27 | 2022-10-04 | 广东电网有限责任公司 | Copper monatomic catalyst and preparation method and application thereof |
CN113463131A (en) * | 2021-07-27 | 2021-10-01 | 广东电网有限责任公司 | Copper monatomic catalyst and preparation method and application thereof |
CN113862701B (en) * | 2021-10-18 | 2023-06-13 | 苏州大学 | Preparation method of copper monoatomic catalytic material and electrode and application of copper monoatomic catalytic material and electrode in reduction of nitrate to ammonia production |
CN113862701A (en) * | 2021-10-18 | 2021-12-31 | 苏州大学 | Preparation method of copper monatomic catalytic material and electrode and application of copper monatomic catalytic material and electrode in production of ammonia by reduction of nitrate |
CN114538575A (en) * | 2022-02-18 | 2022-05-27 | 苏州科技大学 | Electrochemical reduction device and method for high nitrate nitrogen wastewater |
CN114538575B (en) * | 2022-02-18 | 2023-08-29 | 苏州科技大学 | Electrochemical reduction device and method for high-nitrate nitrogen wastewater |
CN116219473A (en) * | 2023-02-11 | 2023-06-06 | 浙江大学 | Preparation and application methods of in-situ self-optimizing atomic-level copper catalyst |
CN116219473B (en) * | 2023-02-11 | 2024-01-30 | 浙江大学 | Preparation and application methods of in-situ self-optimizing atomic-level copper catalyst |
CN118253305A (en) * | 2024-04-03 | 2024-06-28 | 兰州大学 | Hollow carbon fiber composite material capable of catalyzing nitrate to reduce ammonia and preparation method and application thereof |
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