CN111333079A - Boron phosphide material and preparation method thereof - Google Patents
Boron phosphide material and preparation method thereof Download PDFInfo
- Publication number
- CN111333079A CN111333079A CN202010157474.2A CN202010157474A CN111333079A CN 111333079 A CN111333079 A CN 111333079A CN 202010157474 A CN202010157474 A CN 202010157474A CN 111333079 A CN111333079 A CN 111333079A
- Authority
- CN
- China
- Prior art keywords
- boron
- powder
- preparation
- phosphide
- source material
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 84
- FFBGYFUYJVKRNV-UHFFFAOYSA-N boranylidynephosphane Chemical compound P#B FFBGYFUYJVKRNV-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 71
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052796 boron Inorganic materials 0.000 claims abstract description 44
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 42
- 239000011574 phosphorus Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000004907 flux Effects 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 14
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 239000006011 Zinc phosphide Substances 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- YMEKEHSRPZAOGO-UHFFFAOYSA-N boron triiodide Chemical compound IB(I)I YMEKEHSRPZAOGO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 4
- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229940048462 zinc phosphide Drugs 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000010411 electrocatalyst Substances 0.000 abstract description 3
- 239000010453 quartz Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 239000008204 material by function Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003517 fume Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical group [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/14—Compounds containing boron and nitrogen, phosphorus, sulfur, selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Description
技术领域technical field
本发明属于功能材料领域，具体涉及一种磷化硼材料及其制备方法。The invention belongs to the field of functional materials, in particular to a boron phosphide material and a preparation method thereof.
背景技术Background technique
功能材料是指通过光、电、磁、热、化学、生化等作用后具有特定功能的材料，在国外，常将这类材料称为功能材料（Functional Materials）、特种材料（SpecialityMaterials）或精细材料（Fine Materials）。功能材料的涉及面广，一般来说具体包括光、电功能、磁功能、分离功能、形状记忆功能等，这类材料相对于通常的结构材料而言，一般除了具有机械特性外，还具有其他的功能特性，因此，被统称为功能材料。 Functional materials refer to materials that have specific functions after the action of light, electricity, magnetism, heat, chemistry, biochemistry, etc. In foreign countries, such materials are often referred to as functional materials (Functional Materials), special materials (SpecialityMaterials) or fine materials (Fine Materials). Functional materials cover a wide range, generally including optical, electrical functions, magnetic functions, separation functions, shape memory functions, etc. Compared with ordinary structural materials, such materials generally have other mechanical properties in addition to mechanical properties. The functional properties, therefore, are collectively referred to as functional materials.
半导体材料是室温下导电性介于导电材料和绝缘材料之间的一类功能材料，目前应用广泛。其中，磷化硼作为一种III-V半导体材料，由两种重量轻、含量丰富的硼和磷元素组成，其具有强共价键。1957年Popper等人（Popper, P.; Ingles, T., Boron phosphide,a III–V compound of zinc-blende structure. Nature 1957, 179 (4569), 1075-1075.）首次研究磷化硼的晶体结构证明其具有立方闪锌矿结构。磷化硼的化学性质稳定，耐化学腐蚀，不受浓矿物酸或碱水溶液的侵蚀，同时也显示出良好的热稳定性，1000℃以下能完美抵抗空气的氧化和分解，磷化硼具有的独特性能使其成为许多实际应用的潜在竞争者。而磷化硼中硼元素的高丰度、间接宽禁带与高电子迁移率使其有望成为极端环境下高效循环的稳定光电催化剂。Semiconductor materials are a class of functional materials with electrical conductivity at room temperature between conductive materials and insulating materials, and are currently widely used. Among them, boron phosphide, as a III-V semiconductor material, is composed of two light-weight and abundant boron and phosphorus elements, which have strong covalent bonds. In 1957, Popper et al. (Popper, P.; Ingles, T., Boron phosphide, a III–V compound of zinc-blende structure. Nature 1957, 179 (4569), 1075-1075.) first studied the crystal of boron phosphide The structure proves that it has a cubic sphalerite structure. The chemical properties of boron phosphide are stable, resistant to chemical corrosion, not corroded by concentrated mineral acids or alkaline aqueous solutions, and also show good thermal stability, and can perfectly resist the oxidation and decomposition of air below 1000 °C. Unique properties make it a potential contender for many practical applications. The high abundance of boron, indirect wide band gap and high electron mobility in boron phosphide make it promising as a stable photocatalyst for efficient cycling in extreme environments.
此外，近年来，磷化硼作为无金属催化剂，不仅光催化水制氢被广泛研究，电催化进行固氮反应产生氨气的研究也备受关注。而研究表明，材料粒径与结构形貌是影响磷化硼材料催化性能的主要因素，因此当前很多研究人员致力于控制磷化硼材料的粒径与结构形貌。这些研究中，三维分级结构是催化材料研究领域的热点，同时具有分级结构和其他特殊形貌（空心、团簇与球链）结构的微纳米材料将具有高的表面积和规则排列的不易发生团聚的孔结构，因而被认为是非常有前景的催化材料。但由于合成的挑战，形成均相的磷化硼晶体已经不容易。同时硼的高度惰性需要至少1200 K的温度来反应才能熔化，在这样的高温下，磷的高蒸气压及易导致反应混合物中磷的耗尽，形成不均匀的多相样品。这些元素反应性的巨大差异使磷化硼晶体本身的合成就具有十足的挑战性。目前，不同结构形貌的磷化硼晶体制备也仅仅实现了晶粒大小的调控与纤维状形貌的可控合成，制成具有微纳米组装分级结构的磷化硼材料尚未实现。In addition, in recent years, boron phosphide, as a metal-free catalyst, has not only been widely studied in photocatalytic water for hydrogen production, but also in electrocatalytic nitrogen fixation reaction to produce ammonia gas. Studies have shown that material particle size and structure morphology are the main factors affecting the catalytic performance of boron phosphide materials. Therefore, many researchers are currently focusing on controlling the particle size and structure morphology of boron phosphide materials. In these studies, the three-dimensional hierarchical structure is the hot spot in the field of catalytic materials research, and the micro-nano materials with hierarchical structure and other special morphological (hollow, cluster and ball chain) structures will have high surface area and regular arrangement, which is not easy to agglomerate. Therefore, it is considered to be a very promising catalytic material. But the formation of homogeneous boron phosphide crystals has not been easy due to synthetic challenges. At the same time, the high inertness of boron requires a temperature of at least 1200 K for the reaction to melt. At such a high temperature, the high vapor pressure of phosphorus and the depletion of phosphorus in the reaction mixture easily lead to the formation of heterogeneous heterogeneous samples. The large differences in the reactivity of these elements make the synthesis of boron phosphide crystals inherently challenging. At present, the preparation of boron phosphide crystals with different structures and morphologies only realizes the control of grain size and the controllable synthesis of fibrous morphology, and the preparation of boron phosphide materials with micro-nano assembly hierarchical structure has not yet been realized.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明有必要提供一种磷化硼材料及其制备方法，本发明中以金属作为助熔剂，将硼源和磷源经高温溶液生长后，得到具有分级结构的磷化硼材料，该方法工艺简单，生产成本较低，且生产安全性高，得到的磷化硼材料具有不同的结构形貌以及间接宽带隙与高电子迁移率，解决了现有技术中尚无有效方法制备出分级结构的磷化硼材料的技术问题。In view of this, it is necessary in the present invention to provide a boron phosphide material and a preparation method thereof. In the present invention, a metal is used as a flux, and a boron source and a phosphorus source are grown in a high temperature solution to obtain a boron phosphide material with a hierarchical structure. The method is simple in process, low in production cost, and high in production safety, and the obtained boron phosphide materials have different structures and morphologies, as well as indirect wide band gaps and high electron mobility, which solves the problem that there is no effective preparation method in the prior art. Technical problems of boron phosphide materials with hierarchical structure.
为了实现上述目的，本发明采用以下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种磷化硼材料的制备方法，包括以下步骤：A preparation method of boron phosphide material, comprising the following steps:
取硼源材料和磷源材料混合后，制成均匀的第一粉末；After the boron source material and the phosphorus source material are mixed, a uniform first powder is prepared;
向所述第一粉末中加入金属助熔剂并混合均匀，制得第二粉末；adding a metal flux to the first powder and mixing uniformly to prepare a second powder;
将所述第二粉末于真空条件下进行高温反应后，依次经酸洗、水洗、干燥，制得所述磷化硼材料。After the second powder is subjected to a high temperature reaction under vacuum conditions, the boron phosphide material is prepared by successively undergoing acid washing, water washing and drying.
进一步的，所述硼源材料选自无定形硼粉、单晶硼颗粒或碘化硼。Further, the boron source material is selected from amorphous boron powder, single crystal boron particles or boron iodide.
进一步的，所述磷源材料选自无定形红磷粉、结晶度95%以上的单质磷、磷化锌、磷化镍或磷化铜。Further, the phosphorus source material is selected from amorphous red phosphorus powder, elemental phosphorus with a crystallinity of more than 95%, zinc phosphide, nickel phosphide or copper phosphide.
进一步的，所述金属助熔剂包括镍、锡、铜、镁、银、铟或锑。Further, the metal flux includes nickel, tin, copper, magnesium, silver, indium or antimony.
进一步的，所述第一粉末中，所述硼源材料和所述磷源材料按照硼元素与磷元素的摩尔比为1：（1-5）进行混合；Further, in the first powder, the boron source material and the phosphorus source material are mixed according to a molar ratio of boron element to phosphorus element of 1:(1-5);
所述第二粉末中，硼元素与所述金属助熔剂中金属元素的摩尔比为1：（1-4）。In the second powder, the molar ratio of the boron element to the metal element in the metal flux is 1:(1-4).
进一步的，所述真空条件为真空度介于1.0×10-3~9.0×10-3Pa。Further, the vacuum condition is that the vacuum degree is between 1.0×10 -3 to 9.0×10 -3 Pa.
进一步的，所述高温反应的具体步骤为：首先以2~10℃/min的速率升温至500~900℃，再以0.08~10℃/min的速率升温到1000~1200℃，保温0.5~6天后，以1~10℃/h的降温速率降至500~900℃，最后自然降温。Further, the specific steps of the high temperature reaction are: firstly, the temperature is raised to 500 to 900°C at a rate of 2 to 10°C/min, then to 1000 to 1200°C at a rate of 0.08 to 10°C/min, and the temperature is maintained for 0.5 to 6°C. After a few days, the temperature is lowered to 500-900°C at a cooling rate of 1-10°C/h, and finally the temperature is naturally lowered.
进一步的，所述酸洗采用的洗液为王水，所述酸洗的具体步骤为将高温反应后的样品置于王水中浸泡处理。Further, the lotion used in the pickling is aqua regia, and the specific step of the pickling is to soak the sample after the high temperature reaction in the aqua regia.
本发明的另一个目的在于提供一种磷化硼材料，其采用前述任一方案中所述的制备方法制得。Another object of the present invention is to provide a boron phosphide material, which is prepared by the preparation method described in any one of the preceding schemes.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明中将硼源材料和磷源材料，在金属助熔剂的作用下，经高温溶液生长、酸洗处理，使得制得磷化硼材料具有分级结构，且该制备方法工艺简单，其由于避免了使用磷化氢、溴化硼等危险气体，极大的提高了生产的安全性，降低了对环境的污染；使用的助熔剂为廉价的金属助熔剂，生产成本较低。In the present invention, the boron source material and the phosphorus source material are grown and pickled in a high-temperature solution under the action of a metal flux, so that the prepared boron phosphide material has a hierarchical structure, and the preparation method has a simple process. The use of phosphine, boron bromide and other dangerous gases greatly improves the safety of production and reduces environmental pollution; the flux used is cheap metal flux, and the production cost is low.
通过本发明中的制备方法通过调控硼源、磷源材料与金属助熔剂的配比，以及高温反应控制程序可制得不同结构形貌的磷化硼材料，且这些磷化硼材料具有间接宽带隙与高电子迁移率，作为光、电催化剂具有良好的应用前景。Through the preparation method of the present invention, by adjusting the ratio of the boron source, the phosphorus source material and the metal flux, and the high temperature reaction control program, boron phosphide materials with different structures and morphologies can be prepared, and these boron phosphide materials have indirect broadband. Gap and high electron mobility, it has good application prospects as photocatalysts and electrocatalysts.
附图说明Description of drawings
图1本发明实施例中制得的微纳组装分级结构磷化硼材料的XRD图谱；Fig. 1 is the XRD pattern of the micro-nano assembly hierarchical structure boron phosphide material prepared in the embodiment of the present invention;
图2为本发明实施例中制得的微纳组装分级结构磷化硼材料的SEM图谱；Fig. 2 is the SEM spectrum of the micro-nano assembly hierarchical structure boron phosphide material prepared in the embodiment of the present invention;
图3为实施例1中纳米颗粒组成的空心分级结构磷化硼材料的XPS图谱；Fig. 3 is the XPS spectrum of the hollow hierarchical structure boron phosphide material composed of nanoparticles in Example 1;
图4为实施例1中纳米颗粒组成的空心分级结构磷化硼材料的N2吸-脱附图。FIG. 4 is the N 2 adsorption-desorption diagram of the hollow hierarchical structure boron phosphide material composed of nanoparticles in Example 1. FIG.
具体实施方式Detailed ways
为了便于理解本发明，下面将结合具体的实施例对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施方式。相反地，提供这些实施方式的目的是使对本发明的公开内容理解的更加透彻全面。In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to specific embodiments. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that a thorough and complete understanding of the present disclosure is provided.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本发明。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention.
本发明的第一个方面公开了一种磷化硼材料的制备方法，包括以下步骤：A first aspect of the present invention discloses a preparation method of boron phosphide material, comprising the following steps:
取硼源材料和磷源材料混合后，制成均匀的第一粉末；After the boron source material and the phosphorus source material are mixed, a uniform first powder is prepared;
向所述第一粉末中加入金属助熔剂并混合均匀，制得第二粉末；adding a metal flux to the first powder and mixing uniformly to prepare a second powder;
将所述第二粉末于真空条件下进行高温反应后，依次经酸洗、水洗、干燥，制得所述磷化硼材料。After the second powder is subjected to a high temperature reaction under vacuum conditions, the boron phosphide material is prepared by successively undergoing acid washing, water washing and drying.
本发明中以金属作为助熔剂，与硼源材料、磷源材料进行混合后高温反应，再依次经过酸洗、水洗、干燥制得具有分级结构的磷化硼材料，其中，金属助熔剂的作用在于降低反应物熔点，其有利于降低磷化硼晶体的结晶温度。此外，将硼源材料与磷源材料制成均匀粉末以无可见块状为准，且这里的制粉方式不做具体的限定，只要能制成混合均匀的粉末即可，在本发明的一些具体的实施方式中，优选的采用研磨的方式。In the present invention, metal is used as a flux, mixed with boron source material and phosphorus source material, and then reacted at a high temperature, and then pickled, washed with water, and dried to obtain boron phosphide material with a hierarchical structure. Among them, the role of the metal flux is The purpose is to lower the melting point of the reactants, which is beneficial to lower the crystallization temperature of boron phosphide crystals. In addition, the boron source material and the phosphorus source material are made into uniform powders as long as there are no visible lumps, and the pulverizing method here is not specifically limited, as long as a uniformly mixed powder can be made. In some aspects of the present invention In a specific embodiment, the grinding method is preferably used.
进一步的，本发明中采用的硼源材料和磷源材料可以为本领域中的常规选择，但考虑到杂质、副产物等影响，本发明的一些具体的实施方式中，优选的， 所述硼源材料选自无定形硼粉、单晶硼颗粒或碘化硼；所述磷源材料选自无定形红磷粉、结晶度95%以上的单质磷、磷化锌、磷化镍或磷化铜，从而极大的避免了生成难除去的杂质。更进一步的，选用高质量的磷源材料或自带助熔剂的磷源材料（如磷化锌、磷化铜或磷化镍）可以避免生成磷化硼晶体的次级产物B2P12。Further, the boron source material and phosphorus source material used in the present invention may be conventional choices in the field, but considering the influence of impurities, by-products, etc., in some specific embodiments of the present invention, preferably, the boron The source material is selected from amorphous boron powder, single crystal boron particles or boron iodide; the phosphorus source material is selected from amorphous red phosphorus powder, elemental phosphorus with a crystallinity of more than 95%, zinc phosphide, nickel phosphide or phosphide copper, thus greatly avoiding the formation of difficult-to-remove impurities. Further, the selection of high-quality phosphorus source materials or phosphorus source materials with flux (such as zinc phosphide, copper phosphide or nickel phosphide) can avoid the formation of the secondary product B2P12 of boron phosphide crystals.
进一步的，本发明中所述金属助熔剂可以为本领域中常规的金属助熔剂如镍或铜，此外，本发明中还优选了部分低熔点金属作为金属助熔剂，其有利于降低反应温度，可提及的实例包括但不限于锡、镁、银、铟或锑。Further, the metal fluxing agent in the present invention can be a conventional metal fluxing agent in the field such as nickel or copper. In addition, in the present invention, some low melting point metals are also preferred as the metal fluxing agent, which is beneficial to reduce the reaction temperature, Examples that may be mentioned include, but are not limited to, tin, magnesium, silver, indium or antimony.
本发明中硼源材料与磷源材料、金属助熔剂的添加量可以不做具体的限定，按照任意比例混合其均可以制得本发明中所述的磷化硼材料，区别仅在于硼源材料与磷源材料、金属助熔剂的配比不同，得到的磷化硼材料的分级结构也会不同，优选的，在本发明的一些具体的实施方式中，所述第一粉末中，所述硼源材料和所述磷源材料按照硼元素与磷元素的摩尔比为1：（1-5）进行混合；所述第二粉末中，硼元素与所述金属助熔剂中金属元素的摩尔比为1：（1-4）。In the present invention, the addition amount of the boron source material, the phosphorus source material and the metal flux may not be specifically limited, and the boron phosphide material described in the present invention can be obtained by mixing them in any proportion, and the difference is only in the boron source material. Different from the ratio of phosphorus source material and metal flux, the hierarchical structure of the obtained boron phosphide material will also be different. Preferably, in some specific embodiments of the present invention, in the first powder, the boron phosphide material is The source material and the phosphorus source material are mixed according to a molar ratio of boron element to phosphorus element of 1: (1-5); in the second powder, the molar ratio of boron element to the metal element in the metal flux is 1: (1-4).
进一步的，一般单晶生长均是在真空条件下进行，本发明的高温反应优选在高真空条件下进行，一方面避免反应过程中与氧气生成氧化物，另一方面也是为了给磷释放蒸汽压提供空间，优选的，所述真空条件的真空度介于1.0×10-3~9.0×10-3Pa。更进一步的，在本发明的一些具体的实施方式中，高温反应优选在卧式管式炉中进行，具体操作为：将第二粉末置入石英管中，在高真空条件下火焰密封，将密封后的石英管放在刚玉磁舟内，一并置于卧式管式炉中进行高温反应。可以理解的是，前述高温反应的具体步骤仅用于举例，并不局限于前述步骤，只要在真空条件下进行的高温反应均可用于本发明中。Further, generally single crystal growth is carried out under vacuum conditions, and the high-temperature reaction of the present invention is preferably carried out under high vacuum conditions, on the one hand to avoid the formation of oxides with oxygen during the reaction process, and on the other hand to release the vapor pressure for phosphorus. Provide space, preferably, the vacuum degree of the vacuum condition is between 1.0×10 -3 to 9.0×10 -3 Pa. Further, in some specific embodiments of the present invention, the high-temperature reaction is preferably carried out in a horizontal tube furnace, and the specific operations are: placing the second powder in a quartz tube, flame sealing under high vacuum conditions, and The sealed quartz tube is placed in a corundum magnetic boat and placed in a horizontal tube furnace for high temperature reaction. It can be understood that the specific steps of the aforementioned high-temperature reaction are only for example, and are not limited to the aforementioned steps, as long as the high-temperature reaction performed under vacuum conditions can be used in the present invention.
进一步的，本发明中的高温反应优选的采用不同的升温速率分段进行，具体的，所述高温反应的具体步骤为：首先以2~10℃/min的速率升温至500~900℃，再以0.08~10℃/min的速率升温到1000~1200℃，保温0.5~6天后，以1~10℃/h的降温速率降至500~900℃，最后自然降温。首先采用较高的升温速率（2-10℃/min）是因为在500℃-900℃以内反应物不熔融无法发生反应，因此加快升温速率可以节约时间，900℃左右反应开始发生，此时降低升温速率可以保证反应充分，提高晶体质量，在降温时也是同样的道理。Further, the high-temperature reaction in the present invention is preferably carried out in stages with different heating rates. Specifically, the specific steps of the high-temperature reaction are: firstly, the temperature is raised to 500-900°C at a rate of 2-10°C/min, and then the temperature is increased to 500-900°C. The temperature is raised to 1000~1200°C at a rate of 0.08~10°C/min, and after 0.5~6 days of heat preservation, it is lowered to 500~900°C at a cooling rate of 1~10°C/h, and finally cooled naturally. First, a higher heating rate (2-10°C/min) is used because the reactants are not melted and cannot react within 500°C-900°C. Therefore, increasing the heating rate can save time. The reaction begins to occur at around 900°C, and then decreases The heating rate can ensure sufficient reaction and improve crystal quality, and the same is true when cooling.
进一步的，由于反应后会在样品中会残余未反应完的金属助熔剂以及一些副产物，因此，必须采用酸液洗去金属助熔剂和其他副产物，优选的，所述酸洗采用的洗液为王水，这是由于王水能够充分剔除干净未反应完的金属助熔剂和副产物，具体的，只需将高温反应后的样品置于王水中浸泡处理即可，可以理解的是，这里对处理时间不再具体的限定，可根据具体情况适当延长或缩短酸洗时间。Further, since the unreacted metal flux and some by-products will remain in the sample after the reaction, an acid solution must be used to wash off the metal flux and other by-products. The liquid is aqua regia. This is because aqua regia can fully remove unreacted metal fluxes and by-products. Specifically, it is only necessary to soak the samples after high temperature reaction in aqua regia. It is understandable that, The treatment time is not specifically limited here, and the pickling time can be appropriately extended or shortened according to specific circumstances.
本发明的第二个方面公开了一种磷化硼材料，其采用如本发明第一个方面所述的制备方法制得。The second aspect of the present invention discloses a boron phosphide material, which is prepared by the preparation method described in the first aspect of the present invention.
该磷化硼材料具有微纳组装分级结构，这种结构具有简介宽带隙及高电子迁移率，作为光、电催化剂具有良好的应用前景。The boron phosphide material has a micro-nano assembly hierarchical structure, the structure has a brief wide band gap and high electron mobility, and has a good application prospect as a photocatalyst and an electrocatalyst.
下面结合具体的实施例对本发明的技术方案进行更加清楚、完整的说明。The technical solutions of the present invention will be more clearly and completely described below with reference to specific embodiments.
实施例1Example 1
按照硼元素与磷元素的摩尔比为1：1，称取无定形硼粉与无定形磷粉作为原材料，混合研磨成均匀的第一粉末；According to the molar ratio of boron element and phosphorus element being 1:1, take amorphous boron powder and amorphous phosphorus powder as raw materials, mix and grind to form a uniform first powder;
向所述第一粉末中加入金属助熔剂高纯锡粉（纯度98%以上），混合均匀制成第二粉末，其中，硼元素与金属助熔剂中锡元素的摩尔比为1：1；Add metal flux high-purity tin powder (purity of more than 98%) to the first powder, and mix uniformly to make a second powder, wherein the molar ratio of boron element to tin element in the metal flux is 1:1;
将第二粉末置入石英管中，在高真空（1.0×10-3 Pa）条件下火焰密封后，将真空密封后的石英管放在刚玉磁舟内，一并置于卧式管式炉中进行高温反应，高温反应具体为以10℃/min的速率升温至500℃，再以3℃/min的速率升温到1000℃，保温0.5天后以3℃/h的降温速率降至900℃，最后自然降温到室温。Put the second powder into a quartz tube, and after flame sealing under high vacuum (1.0×10 -3 Pa) conditions, place the vacuum-sealed quartz tube in a corundum magnetic boat and place it in a horizontal tube furnace together The high-temperature reaction is carried out in the middle, and the high-temperature reaction is specifically heated to 500°C at a rate of 10°C/min, then heated to 1000°C at a rate of 3°C/min, and then lowered to 900°C at a cooling rate of 3°C/h after holding for 0.5 days. Finally cool down to room temperature naturally.
在通风橱中配20mL王水置于烧杯，取出高温反应后的样品放入烧杯中处理2h后，用去离子水离心洗涤至溶液呈中性，将得到的沉淀物放置于干燥箱中80℃干燥，得到具有空心兼具分级结构的磷化硼粉体。Put 20 mL of aqua regia in a fume hood and put it in a beaker, take out the sample after high temperature reaction and put it in the beaker for 2 hours, then wash it with deionized water by centrifugation until the solution is neutral, and place the obtained precipitate in a drying box at 80°C After drying, boron phosphide powder having a hollow and hierarchical structure is obtained.
将本实施例中的磷化硼粉体分别进行XRD、SEM表征，结果如图1（a）和图2（a）中所示，图1（a）磷化硼粉体的XRD特征峰与标准卡片一一对应，而图2（a）中的SEM图证实了本实施例中的磷化硼粉体具有纳米颗粒组成的空心兼具分级结构；进一步的，对本实施例中的磷化硼粉体进行了XPS和N2吸-脱附表征，如图3和图4中所示，可以看出，B 1s区188.2eV峰和P 2s区188.97 eV、P 2p区130.4eV和131.2eV峰分别归属于磷化硼的B和P物种，经N2吸-脱附表征可知磷化硼粉体的比表面积为1.65m2/g，单点平均孔径为150 Å，以上均说明了本实施例中成功制备了具有空心兼具分级结构的磷化硼粉体。The boron phosphide powder in this example was characterized by XRD and SEM respectively. The results are shown in Figure 1(a) and Figure 2(a), and the XRD characteristic peaks of the boron phosphide powder in Figure 1(a) are the same as The standard cards correspond one by one, and the SEM image in Figure 2(a) confirms that the boron phosphide powder in this example has a hollow and hierarchical structure composed of nanoparticles; The powders were characterized by XPS and N adsorption - desorption, as shown in Figure 3 and Figure 4, it can be seen that the peaks of 188.2 eV in the B 1s region and 188.97 eV in the P 2s region, 130.4 eV and 131.2 eV in the P 2p region They belong to the B and P species of boron phosphide, respectively. The N 2 adsorption-desorption characterization shows that the specific surface area of the boron phosphide powder is 1.65 m 2 /g, and the single-point average pore size is 150 Å. The above all illustrate this implementation. In the example, boron phosphide powder with hollow and hierarchical structure was successfully prepared.
实施例2Example 2
按照硼元素与磷元素的摩尔比为1：1，称取碘化硼与块状磷作为原材料，混合研磨成均匀的第一粉末；According to the molar ratio of boron element and phosphorus element being 1:1, weigh boron iodide and bulk phosphorus as raw materials, mix and grind to form a uniform first powder;
向所述第一粉末中加入金属助熔剂铟粉，混合均匀制成第二粉末，其中，硼元素与金属助熔剂中铟元素的摩尔比为1：1；Adding metal flux indium powder to the first powder, and mixing uniformly to prepare a second powder, wherein the molar ratio of boron element to indium element in the metal flux is 1:1;
将第二粉末置于石英管中，在高真空（3.0×10-3 Pa）条件下火焰密封后，将真空密封后的石英管放在刚玉磁舟内，一并置于卧式管式炉中进行高温反应，高温反应具体为以10℃/min的速率升温至500℃，再以0.08℃/min的速率升温到1100℃，保温6天后以1℃/h、3℃/h或10℃/h的降温速率降至900℃，最后自然降温到室温。The second powder was placed in a quartz tube, and after flame sealing under high vacuum (3.0×10 -3 Pa) conditions, the vacuum-sealed quartz tube was placed in a corundum magnetic boat and placed in a horizontal tube furnace. The high temperature reaction is carried out at a rate of 10°C/min to 500°C, and then to 1100°C at a rate of 0.08°C/min. The cooling rate of /h was reduced to 900 °C, and finally the temperature was naturally cooled to room temperature.
在通风橱中配20mL王水置于烧杯，取出高温反应后的样品放入烧杯中处理2h后，用去离子水离心洗涤至溶液呈中性，将得到的沉淀物放置于干燥箱中80℃干燥，均得到具有团簇兼具分级结构的磷化硼粉体。Put 20 mL of aqua regia in a fume hood and put it in a beaker, take out the sample after high temperature reaction and put it in the beaker for 2 hours, then wash it with deionized water by centrifugation until the solution is neutral, and place the obtained precipitate in a drying box at 80°C After drying, boron phosphide powders with clusters and hierarchical structures were obtained.
将本实施例中的磷化硼粉体分别进行XRD、SEM表征，结果如图1（b）和图2（b）中所示的，可以看出图1（b）磷化硼粉体的XRD特征峰与标准卡片完全对应，说明本实施例中成功制备出了磷化硼粉体，而SEM图则证实了该磷化硼粉体具有微米棒状晶体组成的团簇兼具分级的花状结构。The boron phosphide powder in this example was characterized by XRD and SEM respectively. The results are shown in Figure 1(b) and Figure 2(b), it can be seen that the boron phosphide powder in Figure 1(b) has The XRD characteristic peaks completely correspond to the standard card, indicating that boron phosphide powder was successfully prepared in this example, and the SEM image confirms that the boron phosphide powder has clusters composed of micron rod-like crystals and a graded flower-like shape. structure.
实施例3Example 3
按照硼元素与磷元素的摩尔比为1：3，称取硼单晶（纯度93%以上）与磷粉作为原材料，混合研磨成均匀的第一粉末；According to the molar ratio of boron element to phosphorus element is 1:3, weigh boron single crystal (purity above 93%) and phosphorus powder as raw materials, mix and grind to form a uniform first powder;
向所述第一粉末中加入金属助熔剂高纯镍（纯度99%以上），混合均匀制成第二粉末，其中，硼元素与金属助熔剂中镍元素的摩尔比为1：1；Adding metal flux high-purity nickel (above 99% purity) to the first powder, and mixing uniformly to make a second powder, wherein the molar ratio of boron element to nickel element in the metal flux is 1:1;
将第二粉末置入石英管中，在高真空（6.0×10-3 Pa）条件下火焰密封后，将真空密封后的石英管放在刚玉磁舟内，一并置于卧式管式炉中进行高温反应，高温反应具体为以10℃/min的速率升温至500℃，再以0.8或3℃/min的速率升温到1200℃，保温0.5或3天后以3℃/h的降温速率降至900℃，最后自然降温到室温。Put the second powder into a quartz tube, and after flame sealing under high vacuum (6.0×10 -3 Pa) conditions, place the vacuum-sealed quartz tube in a corundum magnetic boat and place it in a horizontal tube furnace. The high-temperature reaction is carried out in the middle, and the high-temperature reaction is specifically heated to 500°C at a rate of 10°C/min, then heated to 1200°C at a rate of 0.8 or 3°C/min, and then kept for 0.5 or 3 days. to 900°C, and finally cooled down to room temperature naturally.
在通风橱中配20mL王水置于烧杯，取出高温反应后的样品放入烧杯中处理2h后，用去离子水离心洗涤至溶液呈中性，将得到的沉淀物放置于干燥箱中80℃干燥，均得到具有串珠式分级结构的磷化硼材料。Put 20 mL of aqua regia in a fume hood and put it in a beaker, take out the sample after high temperature reaction and put it in the beaker for 2 hours, then wash it with deionized water by centrifugation until the solution is neutral, and place the obtained precipitate in a drying box at 80°C After drying, boron phosphide materials with beaded hierarchical structure are obtained.
将本实施例中的磷化硼粉体分别进行XRD、SEM表征，结果如图1（c）和图2（c）中所示的，图1（c）磷化硼粉体的XRD特征峰与标准卡片完全对应，说明本实施例成功制备了磷化硼粉体，而SEM图则证实了该磷化硼粉体具有纤维与颗粒组成的串珠式分级结构。The boron phosphide powder in this example was characterized by XRD and SEM respectively. The results are shown in Figure 1 (c) and Figure 2 (c), Figure 1 (c) XRD characteristic peaks of the boron phosphide powder It completely corresponds to the standard card, indicating that the boron phosphide powder is successfully prepared in this example, and the SEM image confirms that the boron phosphide powder has a beaded hierarchical structure composed of fibers and particles.
实施例4Example 4
按照硼元素与磷元素的摩尔比为1：3，称取无定形硼粉与块状赤磷源作为原材料，混合研磨成均匀的第一粉末；According to the molar ratio of boron element and phosphorus element being 1:3, the amorphous boron powder and the massive red phosphorus source are weighed as raw materials, mixed and ground into a uniform first powder;
向所述第一粉末中加入金属助熔剂镍网，混合均匀制成第二粉末，其中，硼元素与金属助熔剂中镍元素的摩尔比为1：2；Adding a metal flux nickel mesh to the first powder, and mixing uniformly to make a second powder, wherein the molar ratio of boron element to nickel element in the metal flux is 1:2;
将第二粉末置入石英管中，在高真空（6.0×10-3 Pa）条件下火焰密封后，将真空密封后的石英管放在刚玉磁舟内，一并置于卧式管式炉中进行高温反应，高温反应具体为以10℃/min的速率升温至500℃，再以0.08℃/min的速率升温到1100℃，保温3天后以1℃/h的降温速率降至900℃，最后自然降温到室温。Put the second powder into a quartz tube, and after flame sealing under high vacuum (6.0×10 -3 Pa) conditions, place the vacuum-sealed quartz tube in a corundum magnetic boat and place it in a horizontal tube furnace. The high temperature reaction is carried out at a rate of 10°C/min to 500°C, and then to 1100°C at a rate of 0.08°C/min, and the temperature is lowered to 900°C at a cooling rate of 1°C/h after holding for 3 days. Finally cool down to room temperature naturally.
在通风橱中配20mL王水置于烧杯，取出高温反应后的样品放入烧杯中处理2h后，用去离子水离心洗涤至溶液呈中性，将得到的沉淀物放置于干燥箱中80℃干燥，得到具有纤维状结构的磷化硼材料。Put 20 mL of aqua regia in a fume hood and put it in a beaker, take out the sample after high temperature reaction and put it in the beaker for 2 hours, then wash it with deionized water by centrifugation until the solution is neutral, and place the obtained precipitate in a drying box at 80°C After drying, a boron phosphide material with a fibrous structure is obtained.
将本实施例中的磷化硼材料分别进行XRD、SEM表征，结果如图1（d）和图2（d）中所示的，图1（d）磷化硼粉体的XRD特征峰与标准卡片完全对应，说明本实施例成功制备了磷化硼材料，而SEM图则证实了磷化硼粉体具有纤维状结构。The boron phosphide material in this example was characterized by XRD and SEM respectively. The results are shown in Figure 1(d) and Figure 2(d), and the XRD characteristic peaks of the boron phosphide powder in Figure 1(d) are the same as those shown in Figure 1(d). The standard card corresponds exactly, indicating that the boron phosphide material is successfully prepared in this example, and the SEM image confirms that the boron phosphide powder has a fibrous structure.
实施例5Example 5
按照硼元素与磷元素的摩尔比为1：2，称取硼单晶与块状磷作为原材料，混合研磨成均匀的第一粉末；According to the molar ratio of boron element and phosphorus element being 1:2, weigh the boron single crystal and the bulk phosphorus as raw materials, mix and grind them into a uniform first powder;
向所述第一粉末中加入金属助熔剂高纯锑（纯度99%以上），混合均匀制成第二粉末，其中，硼元素与金属助熔剂中锑元素的摩尔比为1：4；Add metal flux high-purity antimony (more than 99% purity) to the first powder, and mix uniformly to prepare a second powder, wherein the molar ratio of boron element to antimony element in the metal flux is 1:4;
将第二粉末置入石英管中，在高真空（9.0×10-3 Pa）条件下火焰密封后，将真空密封后的石英管放在刚玉磁舟内，一并置于卧式管式炉中进行高温反应，高温反应具体为以10℃/min的速率升温至500℃，再以0.08℃/min的速率升温到1100℃，保温3天后以1℃/h的降温速率降至900℃，最后自然降温到室温。Put the second powder into a quartz tube, and after flame sealing under high vacuum (9.0×10 -3 Pa) conditions, place the vacuum-sealed quartz tube in a corundum magnetic boat and place it in a horizontal tube furnace together The high temperature reaction is carried out at a rate of 10°C/min to 500°C, and then to 1100°C at a rate of 0.08°C/min, and the temperature is lowered to 900°C at a cooling rate of 1°C/h after holding for 3 days. Finally cool down to room temperature naturally.
在通风橱中配20mL王水置于烧杯，取出高温反应后的样品放入烧杯中处理2h后，用去离子水离心洗涤至溶液呈中性，将得到的沉淀物放置于干燥箱中80℃干燥，得到具有空心兼具分级结构的磷化硼粉体。Put 20 mL of aqua regia in a fume hood and put it in a beaker, take out the sample after high temperature reaction and put it in the beaker for 2 hours, then wash it with deionized water by centrifugation until the solution is neutral, and place the obtained precipitate in a drying box at 80°C After drying, boron phosphide powder having a hollow and hierarchical structure is obtained.
实施例6Example 6
按照硼元素与磷元素的摩尔比为1：5，称取无定形硼粉与无定形磷粉作为原材料，混合研磨成均匀的第一粉末；According to the molar ratio of boron element and phosphorus element being 1:5, the amorphous boron powder and the amorphous phosphorus powder are weighed as raw materials, mixed and ground into a uniform first powder;
向所述第一粉末中加入金属助熔剂镁粉（纯度98%以上），混合均匀制成第二粉末，其中，硼元素与金属助熔剂中镁元素的摩尔比为1：1；Adding metal flux magnesium powder (purity of more than 98%) to the first powder, and mixing uniformly to make a second powder, wherein the molar ratio of boron element and magnesium element in the metal flux is 1:1;
将第二粉末置入石英管中，在高真空（6.0×10-3 Pa）条件下火焰密封后，将真空密封后的石英管放在刚玉磁舟内，一并置于卧式管式炉中进行高温反应，高温反应具体为以10℃/min的速率升温至500℃，再以3℃/min的速率升温到1100℃，保温14天后以3℃/h的降温速率降至900℃，最后自然降温到室温。Put the second powder into a quartz tube, and after flame sealing under high vacuum (6.0×10 -3 Pa) conditions, place the vacuum-sealed quartz tube in a corundum magnetic boat and place it in a horizontal tube furnace. The high-temperature reaction is carried out in the middle, and the high-temperature reaction is specifically heated to 500°C at a rate of 10°C/min, then heated to 1100°C at a rate of 3°C/min, and then lowered to 900°C at a cooling rate of 3°C/h after holding for 14 days. Finally cool down to room temperature naturally.
在通风橱中配20mL王水置于烧杯，取出高温反应后的样品放入烧杯中处理2h后，用去离子水离心洗涤至溶液呈中性，将得到的沉淀物放置于干燥箱中80℃干燥，得到具有空心兼具分级结构的磷化硼粉体。Put 20 mL of aqua regia in a fume hood and put it in a beaker, take out the sample after high temperature reaction and put it in the beaker for 2 hours, then wash it with deionized water by centrifugation until the solution is neutral, and place the obtained precipitate in a drying box at 80°C After drying, boron phosphide powder having a hollow and hierarchical structure is obtained.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be regarded as the scope described in this specification.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed as a limitation on the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can also be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010157474.2A CN111333079B (en) | 2020-03-09 | 2020-03-09 | Boron phosphide material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010157474.2A CN111333079B (en) | 2020-03-09 | 2020-03-09 | Boron phosphide material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111333079A true CN111333079A (en) | 2020-06-26 |
| CN111333079B CN111333079B (en) | 2022-01-28 |
Family
ID=71176078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010157474.2A Active CN111333079B (en) | 2020-03-09 | 2020-03-09 | Boron phosphide material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111333079B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385210A (en) * | 2021-06-08 | 2021-09-14 | 太原理工大学 | Photocatalytic hydrogen production catalyst and preparation method and application thereof |
| KR20240126329A (en) * | 2023-02-13 | 2024-08-20 | 서울대학교산학협력단 | Method for producing cubic boron phosphide and cubic boron phosphide produced thereby |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106029563A (en) * | 2013-12-23 | 2016-10-12 | 皮埃尔和玛利居里大学(巴黎第六大学) | Preparation of boron phosphide by reduction of boron phosphate with alkali metal |
| CN110284195A (en) * | 2019-07-18 | 2019-09-27 | 南方科技大学 | Boron phosphide single crystal and preparation method and application thereof |
| CN110723740A (en) * | 2019-10-23 | 2020-01-24 | 西安交通大学 | Method for preparing high-thermal-conductivity boron phosphide by molten salt growth method |
-
2020
- 2020-03-09 CN CN202010157474.2A patent/CN111333079B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106029563A (en) * | 2013-12-23 | 2016-10-12 | 皮埃尔和玛利居里大学(巴黎第六大学) | Preparation of boron phosphide by reduction of boron phosphate with alkali metal |
| CN110284195A (en) * | 2019-07-18 | 2019-09-27 | 南方科技大学 | Boron phosphide single crystal and preparation method and application thereof |
| CN110723740A (en) * | 2019-10-23 | 2020-01-24 | 西安交通大学 | Method for preparing high-thermal-conductivity boron phosphide by molten salt growth method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385210A (en) * | 2021-06-08 | 2021-09-14 | 太原理工大学 | Photocatalytic hydrogen production catalyst and preparation method and application thereof |
| KR20240126329A (en) * | 2023-02-13 | 2024-08-20 | 서울대학교산학협력단 | Method for producing cubic boron phosphide and cubic boron phosphide produced thereby |
| KR102789869B1 (en) * | 2023-02-13 | 2025-04-03 | 서울대학교산학협력단 | Method for producing cubic boron phosphide and cubic boron phosphide produced thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111333079B (en) | 2022-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107665984B (en) | Preparation method of lithium-sulfur battery positive electrode material based on phosphorus-doped graphene-loaded nickel phosphide material | |
| Li et al. | Surface doping for photocatalytic purposes: relations betweenparticle size, surface modifications, and photoactivity ofSnO2: Zn2+ nanocrystals | |
| CN102773110B (en) | Preparation method of coin-shaped hollow structure SnS2/SnO2 composite photocatalyst material | |
| CN101219783B (en) | Method for producing electrode material with ferrophosphorus | |
| CN111774083B (en) | Preparation method of hydrogen evolution catalyst of low-temperature phosphorus-doped carbon nitride-loaded high-dispersion palladium, product and application | |
| CN114471639B (en) | Transition metal element doping and cadmium sulfide loaded transition metal phosphide photocatalytic material with sulfur vacancies and preparation method thereof | |
| CN107902690B (en) | Preparation method of micron-sized tin dioxide | |
| CN111333079A (en) | Boron phosphide material and preparation method thereof | |
| CN106554033A (en) | The method that aluminate lanthanum powder is prepared using molten-salt growth method | |
| CN114524466B (en) | A kind of synthetic method of highly active catalyst | |
| CN109772394B (en) | Phosphorus-doped carbon/cuprous oxide composite catalyst, preparation method and application thereof | |
| CN114904550A (en) | A kind of method for efficiently preparing melamine self-assembled supramolecular material | |
| CN115074771A (en) | Ni3ZnC0.7/Ni heterogeneous nanoparticle electrocatalyst covered by nitrogen-doped carbon nanotubes and preparation method thereof | |
| CN108823599A (en) | A kind of preparation method of monodisperse NiO nano material | |
| CN104045117A (en) | A kind of synthesis method of multi-morphology FeS2 pyrite photoelectric material | |
| CN118106011A (en) | Amorphous copper composite material and preparation method and application thereof | |
| KR101606794B1 (en) | ZnS-ZnO COMPOSITE FORMING METHOD USING THERMAL TREATMENT AND ZnS-ZnO COMPOSITE PRODUCED THEREOF | |
| CN113307246B (en) | Carbon-loaded transition metal/transition metal nitride composite material and preparation method thereof | |
| CN105540651B (en) | A method for preparing spherical tin oxide nanomaterials | |
| CN115212882A (en) | A kind of porous copper silicide intermetallic compound material and its preparation and application | |
| CN114751448B (en) | A method for preparing blue titanium oxide nanoparticles | |
| CN107935020A (en) | A kind of Cu2The controllable method for preparing of O nanofibers | |
| AU2021106790A4 (en) | BiVO4/PROTONATED g-C3N4/AgI TERNARY COMPOSITE PHOTOCATALYST AND PREPARATION METHOD THEREOF | |
| CN114261987B (en) | A kind of BiOCl1-xBrx powder and its preparation method and application | |
| CN118079924A (en) | Fe-Ni co-doped perovskite catalyst and preparation method thereof |
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 |