CN109985643A - 一种原位加溴制备小尺寸PdKBr@HSC的方法 - Google Patents
一种原位加溴制备小尺寸PdKBr@HSC的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 31
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims description 23
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims description 23
- 229910052794 bromium Inorganic materials 0.000 title claims description 23
- 238000002360 preparation method Methods 0.000 title description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 142
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 79
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 56
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 56
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 56
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 56
- 239000000047 product Substances 0.000 claims abstract description 54
- 235000019441 ethanol Nutrition 0.000 claims abstract description 42
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000004090 dissolution Methods 0.000 claims abstract description 20
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- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000000460 chlorine Substances 0.000 claims abstract description 10
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
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- 239000002105 nanoparticle Substances 0.000 claims description 11
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- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
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- 239000000693 micelle Substances 0.000 claims description 8
- -1 polyoxyethylene Polymers 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 210000002969 egg yolk Anatomy 0.000 claims description 7
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
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- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 5
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- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 4
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- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 4
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 1
- 230000003628 erosive effect Effects 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 125000001246 bromo group Chemical class Br* 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
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- ASRSBXRMOCLKQC-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)-n-methoxyacetamide Chemical compound CONC(=O)COC1=CC=C(Cl)C=C1C ASRSBXRMOCLKQC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
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- B01J35/393—Metal or metal oxide crystallite size
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/398—Egg yolk like
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Abstract
本发明公开了一种原位加溴制备小尺寸PdKBr@HSC的方法,包括如下步骤:(1)以烷烃和醇类试剂的混合物作为油相,聚乙二醇单十六醚等作为表面活性剂,将其混合溶解,得A品;(2)将KBr加入氯钯酸溶液得B品;(3)加入NaBH4溶液,加入NH3·H2O,加入TEOS,加入乙醇,最后经乙醇离心洗涤,得PdKBr@SiO2催化剂;(4)PdKBr@SiO2分散到去离子水和乙醇混合液中,加入CTAB得C品;(5)向C品中加入间苯二酚、甲醛,得PdKBr@SiO2@RF/CTAB;(6)将PdKBr@SiO2@RF/CTAB碳化、刻蚀、还原后得到最终产物PdKBr@HSC。本发明的PdKBr@HSC催化剂具有活性组分尺寸小、均一且不易脱落的特点。
Description
技术领域
本发明涉及一种过氧化氢催化剂的制备方法,特别是一种原位加溴制备小尺寸PdKBr@HSC的方法。
背景技术
氢氧直接合成过氧化氢法在过氧化氢生产方法中,具有工艺简单、操作费用低、产品清洁、原子经济性强等优点,但H2O2的选择性和产率却很低,远达不到工业生产的要求。催化剂催化活性和其对H2O2的选择性是影响氢氧直接合成过氧化氢法的关键因素。目前,对氢氧直接合成过氧化氢催化剂的研究主要集中于负载型Pd基催化剂,这种催化剂存在选择性低、循环利用率低的问题,主要原因是活性组分Pd在载体上分散不均匀,部分活性组分Pd团聚不能充分利用;同时,一部分Pd尺寸过小,产生较多的不饱和位点,这些不饱和位点使得反应向副反应方向进行,降低催化剂选择性。另外,催化剂在使用过程中,活性组分会从载体上脱落,导致催化剂循环利用率低。因此,设计制备活性组分尺寸小、均一且不易脱落的催化剂具有十分重要的意义。
发明内容
本发明的目的在于,提供一种原位加溴制备小尺寸PdKBr@HSC的方法。本发明的PdKBr@HSC催化剂具有活性组分尺寸小、均一且不易脱落的特点。
本发明的技术方案:一种原位加溴制备小尺寸PdKBr@HSC的方法,包括如下步骤:
(1)以环己烷、正庚烷或异辛烷和正辛醇、乙醇、丙醇、正丁醇、叔丁醇、正戊醇、异戊醇、正己醇或正庚醇的混合物作为油相,聚氧乙烯烷基醚、聚氧乙烯异辛基苯基醚、壬基酚聚氧乙烯醚或十二烷基硫酸钠作为表面活性剂,将其混合溶解,得A品;
(2)将KBr、NaBr或NH3·Br作为功能分子加入氯钯酸溶液中,溶解后加入A品中作为水相,形成反向胶束,得B品;
(3)将B品搅拌均匀后加入NaBH4溶液,反应后继续加入NH3·H2O,待NH3·H2O充分分散在钯纳米粒子周围后逐滴加入TEOS进行反应,然后加入乙醇,最后经乙醇离心洗涤,得PdKBr@SiO2催化剂;
(4)以PdKBr@SiO2催化剂作为模板剂,分散到去离子水和乙醇混合液中,搅拌均匀,加入CTAB并搅拌至CTAB完全分散溶解,得C品;
(5)然后向C品中加入间苯二酚,至间苯二酚完全溶解后加入氨水,搅拌后加入甲醛反应,然后经乙醇离心洗涤得PdKBr@SiO2@RF/CTAB;
(6)将PdKBr@SiO2@RF/CTAB碳化,将碳化的产物PdKBr@SiO2@C分散于H2O中,加入HF溶液刻蚀,除去SiO2得到PdKBr@HCS的蛋黄壳结构纳米球,将PdKBr@HCS于氢气气氛下还原后得到最终产物PdKBr@HSC。
前述的原位加溴制备小尺寸PdKBr@HSC的方法,具体步骤如下:
(1)以35-45ml环己烷、正庚烷或异辛烷和5-15ml正辛醇、乙醇、丙醇、正丁醇、叔丁醇、正戊醇、异戊醇、正己醇或正庚醇的混合物作为油相,6-7g聚氧乙烯烷基醚、聚氧乙烯异辛基苯基醚、壬基酚聚氧乙烯醚或十二烷基硫酸钠作为表面活性剂,将其混合后在30-40℃溶解,得A品;
(2)将0.02-0.04gKBr、NaBr或NH3·Br作为功能分子加入1ml浓度为0.07-0.08M的氯钯酸溶液中,溶解后加入A品中作为水相,形成反向胶束,得B品;
(3)将B品搅拌1-3h后加入250-350μL浓度为10wt%的NaBH4溶液,反应5-15min后继续加入2-4mlNH3·H2O,待NH3·H2O充分分散在钯纳米粒子周围后逐滴加入TEOS进行反应5-7h,然后加入40-60ml乙醇,最后经乙醇离心洗涤,得PdKBr@SiO2催化剂;
(4)以步骤(3)制得的PdKBr@SiO2催化剂作为模板剂,分散到60-80ml去离子水和30-40ml乙醇组成的混合液中,于30-40℃搅拌5-15min,加入2-3gCTAB,并在30-40℃搅拌至CTAB完全分散溶解,得C品;
(5)然后向C品中加入0.3-0.4g间苯二酚,至间苯二酚完全溶解后加入氨水,搅拌0.5-1.5h后加入甲醛反应10-15h,然后经乙醇离心洗涤得PdKBr@SiO2@RF/CTAB;
(6)将步骤(5)制得的PdKBr@SiO2@RF/CTAB碳化,将碳化的产物PdKBr@SiO2@C分散于30-40mlH2O中,加入3-7mlHF溶液,在常温刻蚀10-15h,除去SiO2得到PdKBr@HCS的蛋黄壳结构纳米球,将PdKBr@HCS于氢气气氛下还原2-3h后得到最终产物PdKBr@HSC。
前述的原位加溴制备小尺寸PdKBr@HSC的方法,所述步骤(1)中,是将40ml环己烷、10ml正辛醇和6.521g聚乙二醇单十六醚在35℃混合。
前述的原位加溴制备小尺寸PdKBr@HSC的方法,所述步骤(2)中,是将0.03gKBr作为功能分子加入1ml浓度为0.075M的氯钯酸溶液中。
前述的原位加溴制备小尺寸PdKBr@HSC的方法,所述步骤(3)中,是将B品搅拌2h后加入300μL浓度为10wt%的NaBH4溶液,反应10min后继续加入3mlNH3·H2O,待NH3·H2O充分分散在钯纳米粒子周围后逐滴加入TEOS进行反应6h,然后加入50ml乙醇。
前述的原位加溴制备小尺寸PdKBr@HSC的方法,所述步骤(4)中,PdKBr@SiO2催化剂是经超声分散至混合液中。
前述的原位加溴制备小尺寸PdKBr@HSC的方法,所述步骤(4)中,是将PdKBr@SiO2催化剂分散到70ml去离子水和35ml乙醇组成的混合液中,于35℃搅拌10min,加入2.3gCTAB,并在35℃搅拌至CTAB完全分散溶解。
前述的原位加溴制备小尺寸PdKBr@HSC的方法,所述步骤(5)中,是向C品中加入0.35g间苯二酚,至间苯二酚完全溶解后加入氨水,搅拌1h后加入甲醛反应12h。
前述的原位加溴制备小尺寸PdKBr@HSC的方法,所述步骤(6)中,所述碳化是在氮气气氛下从室温升到140-160℃,并在该温度下保温0.5-1.5h,随后升温到550-650℃,并保温1.5-2.5h。
前述的原位加溴制备小尺寸PdKBr@HSC的方法,所述步骤(6)中,碳化的产物PdKBr@SiO2@C是分散于35mlH2O中,加入5mlHF溶液,在常温刻蚀12h。
本发明的有益效果
本发明通过添加溴化物为功能分子制备出的中空核壳结构催化剂PdKBr@HSC,应用于氢氧直接合成过氧化氢中,与传统氢氧直接合成催化剂相比,具有以下优点:
(1)制备出的催化剂活性组分Pd尺寸小,在活性组分添加量相同的情况下,为反应物提供更多的活性表面积作为反应场所,提高催化剂活性;
(2)原位添加KBr,沉积在活性组分Pd表面,覆盖边角位等不饱和活性位点,均一性更好,可阻止副反应的发生,提高催化剂对H2O2的选择性;
(3)活性组分被包覆于多孔碳壳中,使活性组分Pd在使用过程中不易脱落,提高催化剂重复使用效率。
附图说明
图1为本发明方法的流程图;
图2为本发明PdKBr@HSC的透射电镜图;
图3为本发明PdKBr@HSC活性组分Pd颗粒尺寸统计;
图4为本发明PdKBr@HCS的活性评价图。
由图2可以看出,以PdKBr@SiO2为硬模板,酚醛树脂(RF)为碳源,通过自组装法可成功制备出尺寸较为均一、包覆效果好的中空核壳结构催化剂PdKBr@HCS。
由图3看出,催化剂PdKBr@HSC的活性组分Pd粒子平均尺寸为4.52nm,小于现有中空核壳结构催化剂活性组分尺寸。
由图4可见,催化剂PdKBr@HCS的H2转化率、收率、选择性分别为50%,38%、76%,对氢氧直接合成过氧化氢具有优良活性,产率达到2305mmol(gPd.h)-1。在活性组分量相同的情况下,小尺寸的Pd粒子暴露出的活性表面更多,使得活性组分Pd利用率高,对氢气转化率达到50%,同时Br的加入有效抑制了催化剂对H2O2的分解与氢化活性,使得催化剂对过氧化氢的选择性达到76%。
具体实施方式
下面结合实施例对本发明作进一步的说明,但并不作为对本发明限制的依据。
本发明的实施例
实施例1
(1)制备PdKBr@SiO2:以环己烷(40mL)、正辛醇(10mL)作为油相,聚乙二醇单十六醚(Brij56)(6.521g)作为表面活性剂,于35℃下混合溶解;0.03gKBr作为功能分子加入1mL浓度0.075M的氯钯酸溶液中,溶解后逐滴加入上述油相溶液中作为水相,形成反向胶束。由于水相与油相不相容,两相界面处会形成一个刚性很强的刚性膜,所以水相会形成一个独立纳米级的微型反应器(图1-I)。上述溶液搅拌2h后加入300μL的NaBH4(10wt%)溶液,二价态的钯离子(Pd2+)被NaBH4迅速还原成钯纳米粒子(图1-II)。反应10min后逐滴加入3mlNH3·H2O,提供TEOS水解的碱性环境,之后待氨水充分分散在钯纳米粒子周围后逐滴加入TEOS,在碱性条件下TEOS会水解形成SiO2。在水相微型反应器中,水解形成的SiO2会包覆钯纳米粒子。反应6h后加入50mL乙醇,乙醇会溶解Brij56破除水相与油相之间的刚性膜(破乳),之后经乙醇离心洗涤,最后得到PdKBr@SiO2催化剂。
(2)制备PdKBr@SiO2@RF:由反向胶束法制备得到的PdKBr@SiO2催化剂作为模板剂超声分散到70mL去离子水和30mL乙醇中,于35℃下搅拌10min;加入2.3gCTAB,在35℃条件下持续搅拌30min待CTAB完全分散溶解。在这一过程中由于在水相中,PdKBr@SiO2的SiO2层表面带负电荷,CTAB解离形成的季铵离子(CTMA+)由于静电作用吸附在SiO2表面(图1-IV),从而阻止了它们的团聚。然后加入0.35g间苯二酚,30min后待间苯二酚完全溶解后加入氨水,搅拌1h后加入甲醛;氨水提供间苯二酚和甲醛缩聚形成酚醛树脂(RF)的碱性环境。间苯二酚与甲醛在碱性条件下的缩聚反应比较缓慢,在这一过程中,中间产物羟甲基取代物的形成会扩散到由于与季铵离子的静电相互作用的二氧化硅粒子表面,而这些物种的缩合反应会围绕SiO2粒子的纳米孔形成一个RF聚合层。反应12h后经乙醇离心洗涤3次得到PdKBr@SiO2@RF/CTAB。
(3)制备PdKBr@HSC:PdKBr@SiO2@RF的碳化,在氮气气氛下从室温升到150℃,并在该温度下保温1h,随后升温到600℃,并保温2h,在这一过程中除去CTAB,并且酚醛树脂被炭化。热解的产物PdKBr@SiO2@C分散于35mlH2O,加入5mlHF溶液常温刻蚀12h,除去SiO2得到PdKBr@HCS的蛋黄壳结构纳米球。PdKBr@HCS于氢气气氛下还原2.5h得到最终产物PdKBr@HSC。
实施例2
(1)以35ml正庚烷和5ml丙醇的混合物作为油相,6g壬基酚聚氧乙烯醚作为表面活性剂,将其混合后在30℃溶解,得A品;
(2)将0.02gNH3·Br作为功能分子加入1ml浓度为0.07M的氯钯酸溶液中,溶解后加入A品中作为水相,形成反向胶束,得B品;
(3)将B品搅拌1h后加入250μL浓度为10wt%的NaBH4溶液,反应5min后继续加入2mlNH3·H2O,待NH3·H2O充分分散在钯纳米粒子周围后逐滴加入TEOS进行反应5h,然后加入40ml乙醇,最后经乙醇离心洗涤,得PdKBr@SiO2催化剂;
(4)以步骤(3)制得的PdKBr@SiO2催化剂作为模板剂,分散到60ml去离子水和30ml乙醇组成的混合液中,于30℃搅拌5min,加入2gCTAB,并在30℃搅拌至CTAB完全分散溶解,得C品;
(5)然后向C品中加入0.3g间苯二酚,至间苯二酚完全溶解后加入氨水,搅拌0.5h后加入甲醛反应10h,然后经乙醇离心洗涤得PdKBr@SiO2@RF/CTAB;
(6)将步骤(5)制得的PdKBr@SiO2@RF/CTAB碳化,将碳化的产物PdKBr@SiO2@C分散于30mlH2O中,加入3mlHF溶液,在常温刻蚀10h,除去SiO2得到PdKBr@HCS的蛋黄壳结构纳米球,将PdKBr@HCS于氢气气氛下还原2-3h后得到最终产物PdKBr@HSC。
实施例3
(1)以45ml异辛烷和15ml正庚醇的混合物作为油相,7g十二烷基硫酸钠作为表面活性剂,将其混合后在40℃溶解,得A品;
(2)将0.04gNaBr作为功能分子加入1ml浓度为0.08M的氯钯酸溶液中,溶解后加入A品中作为水相,形成反向胶束,得B品;
(3)将B品搅拌3h后加入350μL浓度为10wt%的NaBH4溶液,反应15min后继续加入4mlNH3·H2O,待NH3·H2O充分分散在钯纳米粒子周围后逐滴加入TEOS进行反应7h,然后加入60ml乙醇,最后经乙醇离心洗涤,得PdKBr@SiO2催化剂;
(4)以步骤(3)制得的PdKBr@SiO2催化剂作为模板剂,分散到80ml去离子水和40ml乙醇组成的混合液中,于40℃搅拌15min,加入3gCTAB,并在40℃搅拌至CTAB完全分散溶解,得C品;
(5)然后向C品中加入0.4g间苯二酚,至间苯二酚完全溶解后加入氨水,搅拌1.5h后加入甲醛反应15h,然后经乙醇离心洗涤得PdKBr@SiO2@RF/CTAB;
(6)将步骤(5)制得的PdKBr@SiO2@RF/CTAB碳化,将碳化的产物PdKBr@SiO2@C分散于40mlH2O中,加入7mlHF溶液,在常温刻蚀15h,除去SiO2得到PdKBr@HCS的蛋黄壳结构纳米球,将PdKBr@HCS于氢气气氛下还原3h后得到最终产物PdKBr@HSC。
Claims (10)
1.一种原位加溴制备小尺寸PdKBr@HSC的方法,其特征在于,包括如下步骤:
(1)以环己烷、正庚烷或异辛烷和正辛醇、乙醇、丙醇、正丁醇、叔丁醇、正戊醇、异戊醇、正己醇或正庚醇的混合物作为油相,聚氧乙烯烷基醚、聚氧乙烯异辛基苯基醚、壬基酚聚氧乙烯醚或十二烷基硫酸钠作为表面活性剂,将其混合溶解,得A品;
(2)将KBr、NaBr或NH3˙Br作为功能分子加入氯钯酸溶液中,溶解后加入A品中作为水相,形成反向胶束,得B品;
(3)将B品搅拌均匀后加入NaBH4溶液,反应后继续加入NH3·H2O,待NH3·H2O充分分散在钯纳米粒子周围后逐滴加入TEOS进行反应,然后加入乙醇,最后经乙醇离心洗涤,得PdKBr@SiO2催化剂;
(4)以PdKBr@SiO2催化剂作为模板剂,分散到去离子水和乙醇混合液中,搅拌均匀,加入CTAB并搅拌至CTAB完全分散溶解,得C品;
(5)然后向C品中加入间苯二酚,至间苯二酚完全溶解后加入氨水,搅拌后加入甲醛反应,然后经乙醇离心洗涤得PdKBr@SiO2@RF/CTAB;
(6)将PdKBr@SiO2@RF/CTAB碳化,将碳化的产物PdKBr@SiO2@C分散于H2O中,加入HF溶液刻蚀,除去SiO2得到PdKBr@HCS的蛋黄壳结构纳米球,将PdKBr@HCS于氢气气氛下还原后得到最终产物PdKBr@HSC。
2.根据权利要求1所述的原位加溴制备小尺寸PdKBr@HSC的方法,其特征在于,具体步骤如下:
(1)以35-45ml环己烷、正庚烷或异辛烷和5-15ml正辛醇、乙醇、丙醇、正丁醇、叔丁醇、正戊醇、异戊醇、正己醇或正庚醇的混合物作为油相,6-7g聚氧乙烯烷基醚、聚氧乙烯异辛基苯基醚、壬基酚聚氧乙烯醚或十二烷基硫酸钠作为表面活性剂,将其混合后在30-40℃溶解,得A品;
(2)将0.02-0.04g KBr、NaBr或NH3˙Br作为功能分子加入1ml浓度为0.07-0.08M的氯钯酸溶液中,溶解后加入A品中作为水相,形成反向胶束,得B品;
(3)将B品搅拌1-3h后加入250-350μL浓度为10wt%的NaBH4溶液,反应5-15min后继续加入2-4ml NH3·H2O,待NH3·H2O充分分散在钯纳米粒子周围后逐滴加入TEOS进行反应5-7h,然后加入40-60ml乙醇,最后经乙醇离心洗涤,得PdKBr@SiO2催化剂;
(4)以步骤(3)制得的PdKBr@SiO2催化剂作为模板剂,分散到60-80ml去离子水和30-40ml乙醇组成的混合液中,于30-40℃搅拌5-15min,加入2-3g CTAB,并在30-40℃搅拌至CTAB完全分散溶解,得C品;
(5)然后向C品中加入0.3-0.4g间苯二酚,至间苯二酚完全溶解后加入氨水,搅拌0.5-1.5h后加入甲醛反应10-15h,然后经乙醇离心洗涤得PdKBr@SiO2@RF/CTAB;
(6)将步骤(5)制得的PdKBr@SiO2@RF/CTAB碳化,将碳化的产物PdKBr@SiO2@C分散于30-40ml H2O中,加入3-7ml HF溶液,在常温刻蚀10-15h,除去SiO2得到PdKBr@HCS的蛋黄壳结构纳米球,将PdKBr@HCS于氢气气氛下还原2-3h后得到最终产物PdKBr@HSC。
3.根据权利要求2所述的原位加溴制备小尺寸PdKBr@HSC的方法,其特征在于:所述步骤(1)中,是将40ml环己烷、10ml正辛醇和6.521g聚乙二醇单十六醚在35℃混合。
4.根据权利要求2所述的原位加溴制备小尺寸PdKBr@HSC的方法,其特征在于:所述步骤(2)中,是将0.03g KBr作为功能分子加入1ml浓度为0.075M的氯钯酸溶液中。
5.根据权利要求2所述的原位加溴制备小尺寸PdKBr@HSC的方法,其特征在于:所述步骤(3)中,是将B品搅拌2h后加入300μL浓度为10wt%的NaBH4溶液,反应10min后继续加入3mlNH3·H2O,待NH3·H2O充分分散在钯纳米粒子周围后逐滴加入TEOS进行反应6h,然后加入50ml乙醇。
6.根据权利要求2所述的原位加溴制备小尺寸PdKBr@HSC的方法,其特征在于:所述步骤(4)中,PdKBr@SiO2催化剂是经超声分散至混合液中。
7.根据权利要求2所述的原位加溴制备小尺寸PdKBr@HSC的方法,其特征在于:所述步骤(4)中,是将PdKBr@SiO2催化剂分散到70ml去离子水和35ml乙醇组成的混合液中,于35℃搅拌10min,加入2.3g CTAB,并在35℃搅拌至CTAB完全分散溶解。
8.根据权利要求2所述的原位加溴制备小尺寸PdKBr@HSC的方法,其特征在于:所述步骤(5)中,是向C品中加入0.35g间苯二酚,至间苯二酚完全溶解后加入氨水,搅拌1h后加入甲醛反应12h。
9.根据权利要求2所述的原位加溴制备小尺寸PdKBr@HSC的方法,其特征在于:所述步骤(6)中,所述碳化是在氮气气氛下从室温升到140-160℃,并在该温度下保温0.5-1.5h,随后升温到550-650℃,并保温1.5-2.5h。
10.根据权利要求2所述的原位加溴制备小尺寸PdKBr@HSC的方法,其特征在于:所述步骤(6)中,碳化的产物PdKBr@SiO2@C是分散于35ml H2O中,加入5ml HF溶液,在常温刻蚀12h。
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