CN111841575B - Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof - Google Patents
Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111841575B CN111841575B CN202010656528.XA CN202010656528A CN111841575B CN 111841575 B CN111841575 B CN 111841575B CN 202010656528 A CN202010656528 A CN 202010656528A CN 111841575 B CN111841575 B CN 111841575B
- Authority
- CN
- China
- Prior art keywords
- porous copper
- sulfur
- composite catalyst
- based composite
- ammonia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010949 copper Substances 0.000 title claims abstract description 138
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 64
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 239000011593 sulfur Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 36
- 229920001021 polysulfide Polymers 0.000 claims abstract description 24
- 239000005077 polysulfide Substances 0.000 claims abstract description 24
- 150000008117 polysulfides Polymers 0.000 claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 125000004434 sulfur atom Chemical group 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000005987 sulfurization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000001678 irradiating effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000004913 activation Effects 0.000 description 4
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000009620 Haber process Methods 0.000 description 1
- 108010020943 Nitrogenase Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000002784 hot electron Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域technical field
本发明属于光催化合成氨技术领域，涉及一种表面硫修饰的多孔铜基复合催化剂及其制备方法和在光催化合成氨方面的应用。The invention belongs to the technical field of photocatalytic ammonia synthesis, and relates to a surface sulfur-modified porous copper-based composite catalyst, a preparation method thereof and an application in photocatalytic ammonia synthesis.
背景技术Background technique
氨(NH3)是一种重要的化学物质，全球每年的氨产量超过1.5亿吨，促进着人口增长和现代社会的发展。工业上生产氨通过Haber-Bosch工艺将N2和H2在高温高压下转化为NH3，该过程消耗了大量能源并排放出数百万吨CO2到大气中，对地球环境造成严重的污染。因此N2在温和条件下转化为NH3的反应因其可满足当前能源和环境的需求而引起了巨大的关注。与温和条件下的生物固氮酶类似，光催化N2还原为NH3的反应为更清洁、更可持续的NH3生产提供了一种可供替代的无碳策略。N2分子的键长为107.8pm，非极性氮氮三键(N≡N)键能为945KJ/mol，因此N2分子具有极高的稳定性，它的活化被看作是N2还原过程中的瓶颈，因此开发新的能有效激活N2分子的方法具有重要意义。通过人们的各种努力，从理论和实验两方面证明了N2分子激活过程中电子向反键轨道的转变是一个关键步骤。这个过程可以通过光催化来实现，在光催化过程中，热电子参与催化反应。虽然在N2分子的活化转化方面已经取得了一定的进展，但仍迫切需要新的有效活化N2分子的策略。Ammonia (NH 3 ) is an important chemical substance, and the global annual ammonia production exceeds 150 million tons, which promotes population growth and the development of modern society. The industrial production of ammonia converts N 2 and H 2 into NH 3 under high temperature and pressure through the Haber-Bosch process. This process consumes a lot of energy and emits millions of tons of CO 2 into the atmosphere, causing serious pollution to the earth's environment. Therefore, the conversion of N2 to NH3 under mild conditions has attracted great attention because it can meet the current energy and environmental demands. Similar to biological nitrogenase under mild conditions, the photocatalytic reduction of N2 to NH3 offers an alternative carbon-free strategy for cleaner and more sustainable NH3 production. The bond length of the N2 molecule is 107.8pm, and the bond energy of the non-polar nitrogen-nitrogen triple bond (N≡N) is 945KJ/mol, so the N2 molecule has extremely high stability, and its activation is regarded as N2 reduction The bottleneck in the process, so it is of great significance to develop new methods that can effectively activate N2 molecules. Through people's various efforts, it has been proved from both theoretical and experimental aspects that the transition of electrons to antibonding orbitals is a key step in the activation of N2 molecules. This process can be achieved by photocatalysis, in which hot electrons participate in catalytic reactions. Although some progress has been made in the activated transformation of N2 molecules, new strategies to effectively activate N2 molecules are still urgently needed.
近年来，局域表面等离激元共振(LSPR)效应由于能够提供足够的光生电子、促进N2的活化而受到广泛关注。局域表面等离激元共振(LSPR)为共振光子诱导的价电子的集体振荡。当光入射到金属纳米颗粒表面时，若入射光子的频率与表面电子的固有频率一致时，光子会被集体震动的电子捕获，金属纳米颗粒表面的自由电子与被捕获的光电子耦合形成一种特殊的电磁模式，产生自由电子局域共振现象。局域表面等离基元共振效应的特征在于共振频率下的光学消光系数升高以及纳米颗粒表面处电场的增强。光学消光系数的增强在漫反射紫外-可见光吸收谱中表现为局域表面等离子体共振峰。有关研究已经证明，可利用等离子体金属颗粒(Ag、Au和Cu)的局域表面等离基元共振效应引起直接的光化学反应。In recent years, the localized surface plasmon resonance (LSPR) effect has attracted extensive attention due to its ability to provide sufficient photogenerated electrons and promote the activation of N2 . Localized surface plasmon resonance (LSPR) is the collective oscillation of valence electrons induced by resonant photons. When light is incident on the surface of metal nanoparticles, if the frequency of the incident photons is consistent with the natural frequency of surface electrons, the photons will be captured by collectively vibrating electrons, and the free electrons on the surface of metal nanoparticles are coupled with the captured photoelectrons to form a special Electromagnetic mode, resulting in free electron localized resonance phenomenon. The LSPR effect is characterized by a rise in the optical extinction coefficient at the resonance frequency and an enhancement of the electric field at the nanoparticle surface. The enhancement of the optical extinction coefficient manifests as a localized surface plasmon resonance peak in the diffuse reflectance UV-Vis absorption spectrum. Related studies have demonstrated that the localized surface plasmon resonance effect of plasmonic metal particles (Ag, Au, and Cu) can be used to induce direct photochemical reactions.
多孔金属是一种兼具功能和结构双重属性的新型工程材料。这种轻质功能材料不仅具有良好的导电性、优异的延展性等金属特性，而且具备稳定性高、体积密度低、比表面积大等特点，用于光催化中可为反应提供大量的活性位点。因此，开发具有等离激元共振效应的多孔铜基的催化剂在N2光固定领域中具有良好的前景。Porous metal is a new type of engineering material with dual properties of function and structure. This lightweight functional material not only has metal properties such as good electrical conductivity and excellent ductility, but also has the characteristics of high stability, low bulk density, and large specific surface area. It can provide a large number of active sites for reactions in photocatalysis. point. Therefore, the development of porous Cu-based catalysts with plasmon resonance effect holds great promise in the field of N2 photofixation.
发明内容Contents of the invention
为了解决现有多孔金属催化剂催化活性低的技术问题，本发明的目的在于提供一种表面硫修饰的多孔铜基复合催化剂及其制备方法和应用，通过多硫化物溶液来控制多孔铜的硫化程度，硫吸附于多孔铜的表面对其进行修饰，表面的硫原子不仅可以通过调节电子性质来增强N2吸附，而且能够通过接受和贡献H原子直接参与催化过程，进而显著提升其催化性能。本发明的制备过程简便，该催化剂用于光催化合成氨时，催化剂活性高，性质稳定，能多次重复利用。In order to solve the technical problem of low catalytic activity of existing porous metal catalysts, the object of the present invention is to provide a surface sulfur-modified porous copper-based composite catalyst and its preparation method and application, and to control the sulfide degree of porous copper through polysulfide solution , sulfur is adsorbed on the surface of porous copper to modify it, and the sulfur atoms on the surface can not only enhance N2 adsorption by adjusting the electronic properties, but also directly participate in the catalytic process by accepting and donating H atoms, thereby significantly improving its catalytic performance. The preparation process of the invention is simple and convenient. When the catalyst is used for photocatalytic synthesis of ammonia, the catalyst has high catalyst activity, stable properties and can be reused many times.
为了实现上述技术目的，本发明采用如下技术方案：In order to realize above-mentioned technical purpose, the present invention adopts following technical scheme:
一种表面硫修饰的多孔铜基复合催化剂，由多硫化物溶液和多孔铜粉末混合反应制得；所述硫吸附于多孔铜的表面，S和Cu的摩尔比为3：100。A surface sulfur-modified porous copper-based composite catalyst is prepared by the mixed reaction of polysulfide solution and porous copper powder; the sulfur is adsorbed on the surface of porous copper, and the molar ratio of S and Cu is 3:100.
本发明还提供了上述表面硫修饰的多孔铜基复合催化剂的制备方法，将多硫化物溶液和多孔铜粉末混合反应即得复合催化剂。The invention also provides a preparation method of the above-mentioned surface sulfur-modified porous copper-based composite catalyst. The composite catalyst is obtained by mixing and reacting polysulfide solution and porous copper powder.
优选的，所述多硫化物溶液中硫的浓度为135.5mmol/L，多硫化物溶液和多孔铜的液固比为7mL/g。Preferably, the concentration of sulfur in the polysulfide solution is 135.5mmol/L, and the liquid-solid ratio of the polysulfide solution to the porous copper is 7mL/g.
优选的，所述多硫化物溶液的配制过程为：Preferably, the preparation process of the polysulfide solution is:
(1)先配置浓度为50mmol/L的Na2S溶液，再取11.7mLNa2S溶液和32mg硫粉混合得悬浊液；(1) First prepare Na 2 S solution with a concentration of 50mmol/L, then take 11.7mL of Na 2 S solution and 32mg of sulfur powder and mix to obtain a suspension;
(2)将悬浊液于80℃下保温12h，即得到硫的浓度为135.5mmol/L的多硫化物溶液。(2) Keep the suspension at 80° C. for 12 hours to obtain a polysulfide solution with a sulfur concentration of 135.5 mmol/L.
优选的，所述多孔铜是以Cu40Zn60粉末为原料，通过酸完全刻蚀掉Cu40Zn60粉末中的Zn而获得。Preferably, the porous copper is obtained by using Cu 40 Zn 60 powder as a raw material, and completely etching away Zn in the Cu 40 Zn 60 powder by acid.
本发明还提供了上述表面硫修饰的多孔铜基复合催化剂的应用，将其用于光催化合成氨。The present invention also provides the application of the above-mentioned surface sulfur-modified porous copper-based composite catalyst, which is used for photocatalytic synthesis of ammonia.
本发明通过严格控制S和Cu的摩尔比，以多硫化物溶液来控制多孔铜的硫化程度，将多硫化物溶液和多孔铜粉末混合反应得到表面硫修饰的多孔铜基复合催化剂。如表1所示，为不同样品的EXAFS Cu K边的拟合参数。多孔铜、0.2-S/Cu、1％-S/Cu、3％-S/Cu、7％-Cu2S/Cu和20％-Cu2S/Cu的Cu-Cu配位数分别为6.4、5.7、5.1、4.7、4.1和3.5。发明人发现，当S和Cu的摩尔比偏小时(0.2-S/Cu和1％-S/Cu)，由于硫化度极低，制得的样品中均未有Cu-S配位；当S和Cu的摩尔比为3时，制得的样品中出现了Cu-S配位，但其配位数仅为0.2；而当S和Cu的摩尔比偏大时(7％-Cu2S/Cu和20％-Cu2S/Cu)，制得的样品中Cu-S配位增加至0.5和1.2，结合不同样品的XRD可以得出，在0.2％-S/Cu、1％-S/Cu和3％-S/Cu中S原子主要对Cu表面进行修饰，而在7％-Cu2S/Cu和20％-Cu2S/Cu中则明显形成了Cu2S纳米晶。The invention strictly controls the molar ratio of S and Cu, controls the vulcanization degree of porous copper with a polysulfide solution, and mixes and reacts the polysulfide solution and porous copper powder to obtain a surface sulfur-modified porous copper-based composite catalyst. As shown in Table 1, it is the fitting parameters of EXAFS Cu K-edge of different samples. The Cu-Cu coordination numbers of porous copper, 0.2-S/Cu, 1%-S/Cu, 3%-S/Cu, 7%-Cu 2 S/Cu and 20%-Cu 2 S/Cu are 6.4 , 5.7, 5.1, 4.7, 4.1 and 3.5. The inventors have found that when the molar ratio of S and Cu is small (0.2-S/Cu and 1%-S/Cu), due to the extremely low degree of sulfidation, there is no Cu-S coordination in the prepared sample; when S When the molar ratio of S and Cu is 3, Cu-S coordination appears in the prepared sample, but its coordination number is only 0.2; while when the molar ratio of S and Cu is too large (7%-Cu 2 S/ Cu and 20%-Cu 2 S/Cu), the Cu-S coordination in the prepared samples increased to 0.5 and 1.2, combined with the XRD of different samples, it can be concluded that at 0.2%-S/Cu, 1%-S/ S atoms in Cu and 3%-S/Cu mainly modified the surface of Cu, while in 7%-Cu 2 S/Cu and 20%-Cu 2 S/Cu, Cu 2 S nanocrystals were obviously formed.
表1不同样品的EXAFS Cu K边的拟合参数。Table 1 Fitting parameters of EXAFS Cu K-edges for different samples.
其中，aN：配位数；bR：键长；cσ2：德拜-沃勒因子；dΔE0：内电位校正；R factor：拟合优度；S0 2设置为0.829。Among them, a N: coordination number; b R: bond length; c σ 2 : Debye-Waller factor; d ΔE 0 : internal potential correction; R factor: goodness of fit; S 0 2 is set to 0.829.
该复合催化剂中，硫吸附于多孔铜的表面对其进行修饰，表面的S原子不仅可以通过调节电子性质来增强N2吸附，而且能够通过接受和贡献H原子直接参与催化过程。当复合催化剂在光照和水存在的条件下会形成S-H键，通过氢键的相互作用显著增强了N2分子的吸附和活化，进而显著提升其催化性能。In this composite catalyst, sulfur is adsorbed on the surface of porous copper to modify it, and the surface S atoms can not only enhance N2 adsorption by adjusting the electronic properties, but also directly participate in the catalytic process by accepting and donating H atoms. When the composite catalyst forms SH bonds in the presence of light and water, the adsorption and activation of N2 molecules are significantly enhanced through the interaction of hydrogen bonds, thereby significantly improving its catalytic performance.
本发明的优势在于：The advantages of the present invention are:
(1)本发明通过严格控制S和Cu的摩尔比，以多硫化物溶液来控制多孔铜的硫化程度即可得到表面硫修饰的多孔铜基复合催化剂，其制备方法简便、重复性好。(1) In the present invention, by strictly controlling the molar ratio of S and Cu, a polysulfide solution is used to control the degree of sulfidation of porous copper to obtain a surface sulfur-modified porous copper-based composite catalyst. The preparation method is simple and repeatable.
(2)本发明的复合催化剂中，硫吸附于多孔铜的表面对其进行修饰，表面的S原子不仅可以通过调节电子性质来增强N2吸附，而且能够通过接受和贡献H原子直接参与催化过程，进而显著提升其催化性能。(2) In the composite catalyst of the present invention, sulfur is adsorbed on the surface of porous copper to modify it, and the S atoms on the surface can not only enhance N2 adsorption by adjusting electronic properties, but also directly participate in the catalytic process by accepting and donating H atoms , thereby significantly improving its catalytic performance.
(3)本发明的3％-S/Cu复合催化剂用于光催化合成氨时，催化剂活性高，性质稳定，能多次重复利用。(3) When the 3%-S/Cu composite catalyst of the present invention is used for photocatalytic synthesis of ammonia, it has high catalyst activity, stable properties and can be reused many times.
附图说明Description of drawings
图1为本发明实施例1中3％-S/Cu的SEM表面形貌图。FIG. 1 is a SEM surface topography diagram of 3%-S/Cu in Example 1 of the present invention.
如图1所示，3％-S/Cu复合催化剂为平均孔径约0.7μm的多孔结构。As shown in Figure 1, the 3%-S/Cu composite catalyst has a porous structure with an average pore diameter of about 0.7 μm.
图2为本发明实施例1中3％-S/Cu、对比例1中多孔铜粉末、对比例2中0.2％-S/Cu、对比例3中1％-S/Cu、对比例4中7％-Cu2S/Cu和对比例5中20％-Cu2S/Cu的X射线衍射图。Fig. 2 is 3%-S/Cu in Example 1 of the present invention, porous copper powder in Comparative Example 1, 0.2%-S/Cu in Comparative Example 2, 1%-S/Cu in Comparative Example 3, and in Comparative Example 4 X-ray diffraction patterns of 7%-Cu 2 S/Cu and 20%-Cu 2 S/Cu in Comparative Example 5.
如图2所示，随着硫化程度的增加，7％-Cu2S/Cu中出现微弱的Cu2S特征峰，该特征峰在20％-Cu2S/Cu中更加明显。As shown in Figure 2, with the increase of the degree of sulfidation, a weak characteristic peak of Cu 2 S appears in 7%-Cu 2 S/Cu, and the characteristic peak is more obvious in 20%-Cu 2 S/Cu.
图3为本发明实施例2中3％-S/Cu和对比例1中多孔铜粉末的漫反射紫外可见(UV-Vis)光谱。3 is the diffuse reflectance ultraviolet-visible (UV-Vis) spectrum of 3%-S/Cu in Example 2 of the present invention and the porous copper powder in Comparative Example 1. FIG.
如图3所示，3％-S/Cu和多孔铜在波长为540nm左右处出现一个吸收峰，对应于Cu骨架的等离激元共振效应，且3％-S/Cu的吸收峰延伸到近红外区，显示了增强的光捕获能力。As shown in Figure 3, 3%-S/Cu and porous copper have an absorption peak at a wavelength of about 540nm, which corresponds to the plasmon resonance effect of the Cu skeleton, and the absorption peak of 3%-S/Cu extends to near-infrared region, showing enhanced light-harvesting ability.
图4为本发明实施例1中3％-S/Cu、对比例1中多孔铜粉末、对比例2中0.2％-S/Cu、对比例3中1％-S/Cu、对比例4中7％-Cu2S/Cu和对比例5中20％-Cu2S/Cu的N2-程序升温脱附曲线。Fig. 4 is 3%-S/Cu in Example 1 of the present invention, porous copper powder in Comparative Example 1, 0.2%-S/Cu in Comparative Example 2, 1%-S/Cu in Comparative Example 3, and in Comparative Example 4 N 2 -Temperature-programmed desorption curves of 7%-Cu 2 S/Cu and 20%-Cu 2 S/Cu in Comparative Example 5.
如图4所示，200-500℃的峰属于对N2的化学吸附，3％-S/Cu对N2的化学吸附峰最强，显示了最强的对N2的吸附能力。相比之下0.2％-S/Cu、1％-S/Cu、7％-Cu2S/Cu、20％-Cu2S/Cu对N2的化学吸附峰较弱，而多孔铜则没有明显的化学吸附峰。As shown in Figure 4, the peak at 200-500 °C belongs to the chemisorption of N2 , and the chemisorption peak of 3%-S/Cu for N2 is the strongest, showing the strongest adsorption capacity for N2 . In contrast, 0.2%-S/Cu, 1%-S/Cu, 7% -Cu2S /Cu, 20% -Cu2S /Cu have weaker chemisorption peaks for N2 , while porous copper has no Obvious chemisorption peaks.
图5为本发明实施例1中3％-S/Cu的循环使用稳定性图。Fig. 5 is a cycle stability graph of 3%-S/Cu in Example 1 of the present invention.
具体实施方式Detailed ways
下面结合具体实施例，进一步阐述本发明。值得说明，这些实施例仅用于说明本发明，而不用于限定本发明的保护范围。在实际应用中技术人员根据本发明做出的改进和调整，仍属于本发明的保护范围。Below in conjunction with specific embodiment, further illustrate the present invention. It is worth noting that these examples are only used to illustrate the present invention, and are not intended to limit the protection scope of the present invention. Improvements and adjustments made by skilled personnel according to the present invention in practical applications still belong to the protection scope of the present invention.
多硫化物水溶液的配制：Preparation of polysulfide aqueous solution:
(1)先配置浓度为50mmol/L的Na2S溶液，取11.7mL该溶液和32mg硫粉加入20mL的小玻璃瓶中；(1) Prepare a Na 2 S solution with a concentration of 50mmol/L first, take 11.7mL of the solution and 32mg of sulfur powder and add it to a 20mL small glass bottle;
(2)将所得悬浊液置于80℃的烘箱中保温12h，溶液的颜色变成亮黄色即得到硫的浓度为135.5mmol/L的多硫化物水溶液。(2) Place the obtained suspension in an oven at 80° C. for 12 hours, and the color of the solution turns bright yellow to obtain a polysulfide aqueous solution with a sulfur concentration of 135.5 mmol/L.
多孔铜的制备：Preparation of porous copper:
(1)先配置浓度为0.5mol/L的硫酸溶液，取200mL该溶液加入500mL的烧杯中，一边搅拌一边加入5.0g Cu40Zn60粉末，在室温下搅拌2h；(1) Prepare a sulfuric acid solution with a concentration of 0.5mol/L first, take 200mL of the solution and add it to a 500mL beaker, add 5.0g of Cu 40 Zn 60 powder while stirring, and stir at room temperature for 2 hours;
(2)将所得产物用去离子水洗至上清液呈中性后，在5000rpm的转速下离心10min收集固体，于60℃下真空干燥1h得到多孔铜粉末。(2) The obtained product was washed with deionized water until the supernatant was neutral, and the solid was collected by centrifugation at 5000 rpm for 10 min, and vacuum-dried at 60° C. for 1 h to obtain porous copper powder.
实施例1Example 1
3％-S/Cu催化剂的制备：Preparation of 3%-S/Cu catalyst:
(1)取0.7mL配置好的多硫化物溶液和100mg多孔铜粉末混合于20mL水溶液中，在室温下搅拌1h；(1) Take 0.7mL of prepared polysulfide solution and 100mg of porous copper powder, mix them in 20mL of aqueous solution, and stir at room temperature for 1h;
(2)将所得产物用去离子水洗3次后，在5000rpm的转速下离心10min收集固体，于60℃下真空干燥1h即得，记为3％-S/Cu。(2) The obtained product was washed 3 times with deionized water, centrifuged at 5000rpm for 10min to collect the solid, and vacuum-dried at 60°C for 1h to obtain the obtained product, which was recorded as 3%-S/Cu.
光催化合成氨：Photocatalytic synthesis of ammonia:
(1)在100-mL的光反应器中加入10mg 3％-S/Cu催化剂和20mL去离子水；(1) Add 10 mg of 3%-S/Cu catalyst and 20 mL of deionized water into a 100-mL photoreactor;
(2)在室温下，向悬浊液中以约30mL·min-1的流速鼓氮气30min，然后剧烈搅拌该悬浊液，同时以光源照射；(2) At room temperature, blow nitrogen into the suspension at a flow rate of about 30mL min-1 for 30 minutes, then vigorously stir the suspension while irradiating it with a light source;
(3)反应后测得合成氨的产率，其不同光源下的氨产率见表2：(3) record the productive rate of synthetic ammonia after the reaction, the ammonia productive rate under its different light sources is shown in Table 2:
表2 3％-S/Cu催化剂在不同光源下的氨产率Table 2 Ammonia yields of 3%-S/Cu catalysts under different light sources
重复利用实验：Reuse experiments:
(1)将3％-S/Cu催化剂光催化反应后的悬浊液以8000rpm的转速离心10min后，对所得上清液进行氨检测，并将滤得的沉淀物用去离子水冲洗数次后作为下一次光催化合成氨实验的催化剂；(1) After centrifuging the suspension after the photocatalytic reaction of the 3%-S/Cu catalyst at a speed of 8000rpm for 10min, the resulting supernatant was subjected to ammonia detection, and the filtered precipitate was washed several times with deionized water Afterwards, it will be used as the catalyst for the next photocatalytic ammonia synthesis experiment;
(2)在20mL去离子水中加入洗涤后的3％-S/Cu催化剂，室温下以约30mL·min-1速率向悬浊液中鼓入氮气30min。随后在光照强度为250mW·cm-2的氙灯下边照射边剧烈搅拌30min；(2) Add the washed 3%-S/Cu catalyst into 20 mL of deionized water, and bubble nitrogen into the suspension at a rate of about 30 mL·min −1 for 30 min at room temperature. Then under the xenon lamp whose light intensity is 250mW·cm -2 , stir vigorously for 30min while irradiating;
(3)重复上述实验步骤，循环实验共10次，其结果如图4所示，循环反应10次后，95％的原始反应活性被保留，显示了3％-S/Cu优异的催化稳定性。(3) Repeat the above experimental steps, and the cycle experiment is 10 times in total. The results are shown in Figure 4. After 10 cycles of reaction, 95% of the original reaction activity is retained, showing the excellent catalytic stability of 3%-S/Cu .
对比例1Comparative example 1
直接采用未硫化的多孔铜粉末进行光催化合成氨：Direct use of unsulfurized porous copper powder for photocatalytic synthesis of ammonia:
(1)在100-mL的光反应器中加入10mg多孔铜粉末和20mL去离子水；(1) Add 10 mg of porous copper powder and 20 mL of deionized water to a 100-mL photoreactor;
(2)在室温下，向悬浊液中以约30mL·min-1的流速鼓氮气30min，然后剧烈搅拌该悬浊液，同时以光源照射；(2) At room temperature, blow nitrogen into the suspension at a flow rate of about 30mL min-1 for 30 minutes, then vigorously stir the suspension while irradiating it with a light source;
(3)反应后测得合成氨的产率，其不同光源下的氨产率见表3：(3) record the productive rate of synthetic ammonia after the reaction, the ammonia productive rate under its different light sources is shown in Table 3:
表3多孔铜催化剂在不同光源下的氨产率Table 3 Ammonia yields of porous copper catalysts under different light sources
对比例2Comparative example 2
0.2％-S/Cu催化剂的制备：Preparation of 0.2%-S/Cu catalyst:
(1)取0.047mL配置好的多硫化物溶液和100mg多孔铜粉末混合于20mL水溶液中，在室温下搅拌1h；(1) Take 0.047mL prepared polysulfide solution and 100mg porous copper powder and mix them in 20mL aqueous solution, stir at room temperature for 1h;
(2)将所得产物用去离子水洗3次后，在5000rpm的转速下离心10min收集固体，于60℃下真空干燥1h即得，记为0.2％-S/Cu。(2) The obtained product was washed three times with deionized water, centrifuged at 5000 rpm for 10 min to collect the solid, and dried in vacuum at 60° C. for 1 h to obtain the obtained product, which was recorded as 0.2%-S/Cu.
光催化合成氨：Photocatalytic synthesis of ammonia:
(1)在100-mL的光反应器中加入10mg 0.2％-S/Cu催化剂和20mL去离子水；(1) Add 10 mg of 0.2%-S/Cu catalyst and 20 mL of deionized water into a 100-mL photoreactor;
(2)在室温下，向悬浊液中以约30mL·min-1的流速鼓氮气30min，然后剧烈搅拌该悬浊液，同时以光源照射；(2) At room temperature, blow nitrogen into the suspension at a flow rate of about 30mL min-1 for 30 minutes, then vigorously stir the suspension while irradiating it with a light source;
(3)反应后测得合成氨的产率，其不同光源下的氨产率见表4：(3) record the productive rate of synthetic ammonia after the reaction, the ammonia productive rate under its different light sources is shown in Table 4:
表4 0.2％-S/Cu催化剂在不同光源下的氨产率Table 4 Ammonia yields of 0.2%-S/Cu catalysts under different light sources
对比例3Comparative example 3
1％-S/Cu催化剂的制备：Preparation of 1%-S/Cu catalyst:
(1)取0.23mL配置好的多硫化物溶液和100mg多孔铜粉末混合于20mL水溶液中，在室温下搅拌1h；(1) Mix 0.23mL of prepared polysulfide solution and 100mg of porous copper powder in 20mL of aqueous solution, and stir at room temperature for 1 hour;
(2)将所得产物用去离子水洗3次后，在5000rpm的转速下离心10min收集固体，于60℃下真空干燥1h即得，记为1％-S/Cu。(2) The obtained product was washed 3 times with deionized water, centrifuged at 5000rpm for 10min to collect the solid, and vacuum-dried at 60°C for 1h to obtain the obtained product, which was recorded as 1%-S/Cu.
光催化合成氨：Photocatalytic synthesis of ammonia:
(1)在100-mL的光反应器中加入10mg 1％-S/Cu催化剂和20mL去离子水；(1) Add 10 mg of 1%-S/Cu catalyst and 20 mL of deionized water into a 100-mL photoreactor;
(2)在室温下，向悬浊液中以约30mL·min-1的流速鼓氮气30min，然后剧烈搅拌该悬浊液，同时以光源照射；(2) At room temperature, blow nitrogen into the suspension at a flow rate of about 30mL min-1 for 30 minutes, then vigorously stir the suspension while irradiating it with a light source;
(3)反应后测得合成氨的产率，其不同光源下的氨产率见表5：(3) record the productive rate of synthetic ammonia after the reaction, the ammonia productive rate under its different light sources is shown in Table 5:
表5 1％-S/Cu催化剂在不同光源下的氨产率Table 5 Ammonia yields of 1%-S/Cu catalysts under different light sources
对比例4Comparative example 4
7％-Cu2S/Cu催化剂的制备：Preparation of 7%-Cu 2 S/Cu catalyst:
(1)取1.63mL配置好的多硫化物溶液和100mg多孔铜粉末混合于20mL水溶液中，在室温下搅拌1h；(1) Mix 1.63mL of prepared polysulfide solution and 100mg of porous copper powder in 20mL of aqueous solution, and stir at room temperature for 1h;
(2)将所得产物用去离子水洗3次后，在5000rpm的转速下离心10min收集固体，于60℃下真空干燥1h即得，记为7％-Cu2S/Cu。(2) The obtained product was washed 3 times with deionized water, centrifuged at 5000rpm for 10min to collect the solid, and vacuum-dried at 60°C for 1h to obtain the obtained product, which was recorded as 7%-Cu 2 S/Cu.
光催化合成氨：Photocatalytic synthesis of ammonia:
(1)在100-mL的光反应器中加入10mg 7％-Cu2S/Cu催化剂和20mL去离子水；(1) Add
(2)在室温下，向悬浊液中以约30mL·min-1的流速鼓氮气30min，然后剧烈搅拌该悬浊液，同时以光源照射；(2) At room temperature, blow nitrogen into the suspension at a flow rate of about 30mL min-1 for 30 minutes, then vigorously stir the suspension while irradiating it with a light source;
(3)反应后测得合成氨的产率，其不同光源下的氨产率见表6：(3) record the productive rate of synthetic ammonia after the reaction, the ammonia productive rate under its different light sources is shown in Table 6:
表6 7％-Cu2S/Cu催化剂在不同光源下的氨产率Table 6 Ammonia yields of 7%-Cu 2 S/Cu catalysts under different light sources
对比例5Comparative example 5
20％-Cu2S/Cu催化剂的制备：Preparation of 20%-Cu 2 S/Cu catalyst:
(1)取4.67mL配置好的多硫化物溶液和100mg多孔铜粉末混合于20mL水溶液中，在室温下搅拌1h；(1) Mix 4.67mL of prepared polysulfide solution and 100mg of porous copper powder in 20mL of aqueous solution, and stir at room temperature for 1 hour;
(2)将所得产物用去离子水洗3次后，在5000rpm的转速下离心10min收集固体，于60℃下真空干燥1h即得，记为20％-Cu2S/Cu。(2) The obtained product was washed 3 times with deionized water, centrifuged at 5000rpm for 10min to collect the solid, and vacuum-dried at 60°C for 1h to obtain the obtained product, which was recorded as 20%-Cu 2 S/Cu.
光催化合成氨：Photocatalytic synthesis of ammonia:
(1)在100-mL的光反应器中加入10mg 20％-Cu2S/Cu催化剂和20mL去离子水；(1) Add 10 mg of 20%-Cu 2 S/Cu catalyst and 20 mL of deionized water into a 100-mL photoreactor;
(2)在室温下，向悬浊液中以约30mL·min-1的流速鼓氮气30min，然后剧烈搅拌该悬浊液，同时以光源照射；(2) At room temperature, blow nitrogen into the suspension at a flow rate of about 30mL min-1 for 30 minutes, then vigorously stir the suspension while irradiating it with a light source;
(3)反应后测得合成氨的产率，其不同光源下的氨产率见表7：(3) record the productive rate of synthetic ammonia after the reaction, the ammonia productive rate under its different light sources is shown in Table 7:
表7 20％-Cu2S/Cu催化剂在不同光源下的氨产率Table 7 Ammonia yields of 20%-Cu 2 S/Cu catalysts under different light sources
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010656528.XA CN111841575B (en) | 2020-07-09 | 2020-07-09 | Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010656528.XA CN111841575B (en) | 2020-07-09 | 2020-07-09 | Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111841575A CN111841575A (en) | 2020-10-30 |
| CN111841575B true CN111841575B (en) | 2022-11-22 |
Family
ID=73153561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010656528.XA Active CN111841575B (en) | 2020-07-09 | 2020-07-09 | Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111841575B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113499788A (en) * | 2021-07-16 | 2021-10-15 | 中南大学 | Diatomite-surface cobalt-doped nano pyrite composite material and preparation and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB574641A (en) * | 1940-08-23 | 1946-01-15 | Du Pont | Improvements in and relating to catalysts |
| FR1272087A (en) * | 1960-08-08 | 1961-09-22 | Aquitaine Petrole | Process for preparing mercaptans |
| CN105655131A (en) * | 2016-01-08 | 2016-06-08 | 吉林大学 | A solar cell Cu2S/FTO counter electrode and preparation method thereof by electrochemical deposition |
| CN107497455A (en) * | 2017-09-28 | 2017-12-22 | 福州大学 | A kind of preparation method and applications of the ultra-thin Bismuth tungstate nano-sheet photochemical catalyst of Determination of Trace Sulfur surface modification |
| CN107768629A (en) * | 2017-09-30 | 2018-03-06 | 哈尔滨工业大学 | A kind of preparation method and applications of sea urchin shape cupric oxide, carbon and sulphur composite |
| CN110743551A (en) * | 2019-09-30 | 2020-02-04 | 中南大学 | Ammonia porous copper-iron bimetallic catalyst synthesized by photocatalysis and application thereof |
-
2020
- 2020-07-09 CN CN202010656528.XA patent/CN111841575B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB574641A (en) * | 1940-08-23 | 1946-01-15 | Du Pont | Improvements in and relating to catalysts |
| FR1272087A (en) * | 1960-08-08 | 1961-09-22 | Aquitaine Petrole | Process for preparing mercaptans |
| CN105655131A (en) * | 2016-01-08 | 2016-06-08 | 吉林大学 | A solar cell Cu2S/FTO counter electrode and preparation method thereof by electrochemical deposition |
| CN107497455A (en) * | 2017-09-28 | 2017-12-22 | 福州大学 | A kind of preparation method and applications of the ultra-thin Bismuth tungstate nano-sheet photochemical catalyst of Determination of Trace Sulfur surface modification |
| CN107768629A (en) * | 2017-09-30 | 2018-03-06 | 哈尔滨工业大学 | A kind of preparation method and applications of sea urchin shape cupric oxide, carbon and sulphur composite |
| CN110743551A (en) * | 2019-09-30 | 2020-02-04 | 中南大学 | Ammonia porous copper-iron bimetallic catalyst synthesized by photocatalysis and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Chemical Immobilization and Conversion of Active Polysulfides Directly by Copper Current Collector: A New Approach to Enabling Stable Room-Temperature Li-S and Na-S Batteries;Li, PR et.al;《ADVANCED ENERGY MATERIALS》;20180516;第8卷(第22期);第2页左栏第2-4段，图2 * |
| Li, PR et.al.Chemical Immobilization and Conversion of Active Polysulfides Directly by Copper Current Collector: A New Approach to Enabling Stable Room-Temperature Li-S and Na-S Batteries.《ADVANCED ENERGY MATERIALS》.2018,第8卷(第22期), * |
| 多硫化钠法表征纯铜带表面清洁度;彭展南等;《中南大学学报(自然科学版)》;20170730;第48卷(第7期);第1720页1.1节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111841575A (en) | 2020-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lin et al. | Functional carbon nitride materials in photo‐Fenton‐like catalysis for environmental remediation | |
| Patnaik et al. | An overview of the structural, textural and morphological modulations of gC 3 N 4 towards photocatalytic hydrogen production | |
| You et al. | State-of-the-art recent progress in MXene-based photocatalysts: a comprehensive review | |
| Lei et al. | ZIF-8 derived hollow CuO/ZnO material for study of enhanced photocatalytic performance | |
| Diarmand-Khalilabad et al. | g-C3N4 nanosheets decorated with carbon dots and CdS nanoparticles: novel nanocomposites with excellent nitrogen photofixation ability under simulated solar irradiation | |
| Wang et al. | Optimized design of BiVO4/NH2-MIL-53 (Fe) heterostructure for enhanced photocatalytic degradation of methylene blue and ciprofloxacin under visible light | |
| CN112588283B (en) | Carbon quantum dot/mesoporous Kong Cengzhuang titanium dioxide and preparation method and application thereof | |
| Cherrak et al. | Preparation of nano-TiO 2/diatomite composites by non-hydrolytic sol–gel process and its application in photocatalytic degradation of crystal violet | |
| CN105722592A (en) | Tethered transition metals promoted photocatalytic system for efficient hydrogen evolutions | |
| Wei et al. | Synthesis of Fe2O3/g-C3N4 composite with efficient photocatalytic degradation for methyl orange | |
| Azam et al. | In-situ synthesis of TiO2/La2O2CO3/rGO composite under acidic/basic treatment with La3+/Ti3+ as mediators for boosting photocatalytic H2 evolution | |
| Jin et al. | Z-scheme mpg-C3N4/Ag6Si2O7 heterojunction for highly efficient photocatalytic degradation of organic pollutants under visible light | |
| CN113856702B (en) | Cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst and preparation method and application thereof | |
| Zhang et al. | Multicomponent hydroxides supported Cu/Cu2O nanoparticles for high efficient photocatalytic ammonia synthesis | |
| CN115805072B (en) | A supported AgPt alloy photocatalyst and its preparation method and application | |
| Liu et al. | Photocatalytic activity study of ZnO modified with nitrogen–sulfur co-doped carbon quantum dots under visible light | |
| Zhang et al. | Core@ Shell structured coal fly ash Magnetospheres@ C/g-C3N4 for degradation of Rh B via photo-Fenton catalysis | |
| Wang et al. | Ultra-deep desulfurization of model diesel fuel over Pr/Ce–N–TiO2 assisted by visible light | |
| Zhou et al. | Highly efficient and selective photocatalytic CO 2 reduction using MIL-125 (Ti) and based on LiFePO 4 and CuO QDs surface–interface regulation | |
| CN111841575B (en) | Surface sulfur modified porous copper-based composite catalyst and preparation method and application thereof | |
| CN106423223A (en) | A kind of cake-shaped porous structure MoSe2@TiO2 photocatalyst and its preparation method | |
| Meena et al. | Synthesis of g-C3N4/ZnO nanostructures via mechano-thermal method for photocatalytic degradation of methylene blue dye | |
| Quan et al. | Superior performance in visible-light-driven hydrogen evolution reaction of three-dimensionally ordered macroporous SrTiO 3 decorated with Zn x Cd 1− x S | |
| CN108940348B (en) | Silver chromate/sulfur-doped nitrogen carbon Z-type photocatalyst and preparation method thereof | |
| Xiao et al. | Preparation of ternary BiVO4/g-C3N4/diatomite composites for enhanced photodegradation of rhodamine B and formaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |