CN104640908A - 金属纳米粒子复合体及其制造方法 - Google Patents
金属纳米粒子复合体及其制造方法 Download PDFInfo
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- CN104640908A CN104640908A CN201380047825.2A CN201380047825A CN104640908A CN 104640908 A CN104640908 A CN 104640908A CN 201380047825 A CN201380047825 A CN 201380047825A CN 104640908 A CN104640908 A CN 104640908A
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- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims description 19
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- 239000013259 porous coordination polymer Substances 0.000 claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 24
- 239000003446 ligand Substances 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 55
- 238000010438 heat treatment Methods 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
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- 239000011777 magnesium Substances 0.000 claims description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
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- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种金属纳米粒子复合体,其特征在于,具有在有机系结构体中分散有金属纳米粒子的结构,所述有机系结构体包含有金属及可以还原金属的多价配体的多孔配位聚合物(Porous Coordination Polymer(PCP))或金属-有机物结构体(Metal-Organic Framework(MOF))的结构和碳。
Description
技术领域
本发明涉及一种金属纳米粒子复合体及其制造方法。
予以说明,在本说明书中,有时将MOF和PCP总称记载为“PCP”。
背景技术
迄今为止,开发有许多PCP/金属纳米粒子复合体,但为了有效地实现复合体那样的反应,需要金属纳米粒子在PCP内部直接连接的复合体。另外,从复合体的生产成本方面考虑,需要简单且可靠地制作PCP/金属纳米粒子复合体的方法。
为了制作PCP/金属纳米粒子,采用如下方法:合成金属纳米粒子,将其周围用PCP包覆,或在合成的PCP内(或外)进行金属纳米粒子的合成,在PCP中埋入金属纳米粒子。
就非专利文献1而言,为了在预先制作PCP之后将金属纳米粒子进行复合化,金属纳米粒子具有附着于PCP的外部或表面附近的结构,金属纳米粒子和PCP的复合效果受限制。
就非专利文献2而言,在氧化铁的存在下使金属离子(Al、Cu)和配体(bpdc、btc)作用而形成金属离子和配体的复合体,但该复合体用于药物的缓释制剂等用途,氧化铁用于利用其磁性使用磁铁输送至目标位置,仅在氧化铁纳米粒子的表面的一部分与PCP一体化,氧化铁粒子不存在于PCP的内部。
非专利文献3公开有利用CVD使钌在MOF的内部析出的技术,但该方法中,存在如下问题:在MOF的表面容易析出钌,在表面附近析出的金属的尺寸变大,且中心附近的钌金属的析出量变少。
非专利文献4公开了在介孔MOF的内部具有镍纳米粒子的复合体,将其还原催化的活性与兰尼镍(Raney Nickel)进行比较,催化活性为与兰尼镍同程度,进一步需求催化活性的提高。
现有技术文献
非专利文献
非专利文献1:Eur.J.Inorg.Chem.,2010,3701-3714
非专利文献2:ChemComm,2011,47,3075-3077
非专利文献3:J.Am.Chem.Soc.,2008,130,6119-6130
非专利文献4:ChemComm,2010,46,3086-3088
发明内容
本发明的目的在于,不使用保护剂,制作分散有金属纳米粒子的复合体。
本发明提供以下的复合体及其制造方法。
项1、一种金属纳米粒子复合体,其具有在有机系结构体中分散有金属纳米粒子的结构,所述有机系结构体包含:含有金属及可以还原金属的多价配体的多孔配位聚合物(Porous Coordination Polymer(PCP))或金属-有机物结构体(Metal-Organic Framework(MOF))的结构、和碳。
项2、如项1所述的复合体,其中,金属纳米粒子的金属为属于周期表的IA~IIB族的金属的1种或2种以上。
项3、如项2所述的复合体,其中,金属纳米粒子的金属为金、铂、银、铜、钌、锡、钯、铑、铱、锇、镍、钴、锌、铁、钇、镁、锰、钛、锆、铪或选自它们中的2种以上金属的合金。
项4、如项1~3中任一项所述的复合体,其中,有机系结构体至少部分地含有碳。
项5、如项4所述的复合体,其中,所述碳选自由玻璃碳(Glassycarbon)、石墨、碳洋葱、焦炭、碳轴(Carbon Shaft)、碳纳米墙、碳纳米线圈、碳纳米管、碳纳米螺旋(Carbon nano twist)、碳纳米纤维、碳纳米锥(Carbon nano horn)、碳纳米绳、炭黑构成的组。
项6、如项1~5中任一项所述的金属纳米粒子复合体的制造方法,所述金属纳米粒子复合体具有在有机系结构体中分散有金属纳米粒子的结构,其中,将含有金属及可以还原金属的多价配体的多孔配位聚合物(PCP)或金属-有机物结构体(MOF)进行加热而使金属纳米粒子析出。
项7、如项6所述的方法,其中,将所述加热在真空下进行。
【发明效果】
本发明的复合体可以将具有高的活性的金属纳米粒子均匀地分散在多孔的有机系结构体的内部,因此,作为有机合成的催化剂、电极催化剂等催化剂的活性高,是非常有用的。
另外,可以根据加热时间、加热温度而调节有机系结构体和金属纳米粒子的比例。即,可以通过使来自络合物的多价配体的有机系结构体和金属纳米粒子之比变化而简单地进行物性的控制。
在1个优选的实施方式中,将本发明的复合体进行加热而使有机物分解的情况下,重量减少为70重量%以下,本发明的复合体的金属纳米粒子的比例非常大,可以充分地引出金属纳米粒子的特性。
为了在PCP等络合物内导入金属纳米粒子,在现有的方法中,有合成金属纳米粒子,使其与PCP等络合物复合的方法;和合成PCP等络合物,合成金属纳米粒子的方法,二者都必需在多阶段进行反应。另外,难以得到在PCP等络合物的内部单分散有金属纳米粒子的复合体。
本发明首次将金属纳米粒子在来自PCP的有机系结构体的内部进行分散,且不使用保护剂简单地制作金属纳米粒子和来自PCP等的有机系结构体直接接触的复合体。
附图说明
图1表示实施例1中得到的Ni复合体的粉末X射线衍射的结果。250℃-12h下PCP的结构几乎完全残留,随着温度升高至300℃-12h、350℃-12h,PCP的结构仅残留一部分,400℃-12h下PCP的结构完全消失。
图2表示实施例1中得到的Ni复合体(400℃-12h)的扫描透射型电子显微镜(STEM)照片。特别是在BF STEM像中,清楚地显示洋葱碳(onioncarbon)的结构。由观察试样:400-12h XRPD,仅看到Ni的峰值。
图3表示实施例1中得到的Ni复合体(400℃-12h)的高分解能透射电子显微镜(HRTEM)照片。为与洋葱碳相似的片状的有机物。得知:Ni纳米粒子在复合体的表面及内部一样地分散。
图4表示实施例1中得到的Ni复合体(400℃-12h)和真空下的热处理前的PCP试样(Ni2(dhtp))的拉曼测定结果。由Ni复合体(400℃-12h)确认洋葱碳的峰值。
图5表示实施例1中得到的Ni复合体(250℃、300℃、350℃、400℃、6h、12h、24h)及真空下的热处理前的PCP试样(Ni2(dhtp))的拉曼测定结果。
图6表示实施例1中得到的Ni复合体的77K下的N2吸附的结果。在300℃、350℃、400℃下加热12小时而合成的复合体显示低压下的吸附量减少,MOF的结构破坏。300℃-12h的复合体观察到磁滞。
图7表示实施例2中得到的Co复合体的粉末X射线衍射的结果及高分解能透射电子显微镜(HRTEM)照片。显示:即使Co也同样地可得到一样地分散有金属纳米粒子的复合体。
图8是2K和300K的磁测定结果(左:复合体、右:Ni2(dhtp))
图9表示350-12h、400-12h(将Ni-MOF-74分别在350℃、400℃下处理12小时的本发明的复合体)、Ni粒子+碳(比较例)、未处理的Ni-MOF-74的电极催化剂:乙醇氧化反应中的循环伏安图。本发明的复合体(350-12h、400-12h)显示高的催化活性。
图10表示对制造例1中得到的Ni络合物、在大气压下(空气中)于350℃加热12小时的粉末X射线衍射的结果。显示可得到Ni氧化物(NiO)复合体。
具体实施方式
本发明的复合体为在有机系的结构体中分散有金属纳米粒子的复合体。在优选的实施方式中,为金属纳米粒子在有机系的结构体中高密度和/或均匀地分散的复合体。
本发明的复合体可以通过将络合物在减压下、不活泼气氛下、还原气氛下或氧化气氛下、优选真空下进行加热而制造。在将络合物在减压下(优选真空下)、不活泼气氛下或还原气氛下进行加热的情况下,将络合物中的金属离子还原而形成金属单体的纳米粒子。另一方面,在氧化气氛(氧等存在的气氛)下,可得到金属氧化物的纳米粒子。在本说明书中,“金属纳米粒子”包含金属单体(0价)的纳米粒子和金属氧化物的纳米粒子这两者。另外,PCP、MOF等络合物由2种以上金属构成的情况下,得到的金属纳米粒子可以成为合金。
在将络合物在减压下(优选真空下)、不活泼气氛下、还原气氛下或氧化气氛下进行加热的情况下,构成络合物的多价配体被变换为碳。向碳的变换的程度根据加热温度及加热时间而确定。例如,在实施例1所示的Ni复合体的情况下,在250℃、300℃、350℃下与碳同时残留PCP的结构,但在400℃下,PCP的结构消失而变换为碳。这样,通过调整加热温度和加热时间,可以改变有机系结构体中的PCP等络合物的结构部分或碳的部分的比例,进而可以使碳的种类(玻璃碳、石墨等)变化为目的的种类。例如,在利用PCP的结构使气体状的反应物质与金属纳米粒子(催化剂)反应的情况下,残留PCP的结构更有利,如电极催化剂等那样,在优选为作为有机系结构体的碳和金属纳米粒子紧密地聚集的结构的情况下,提高加热温度或延长反应时间,完全破坏来自PCP等的结构并提高碳的比例、减少细孔的比例即可。
在本说明书中,作为有机系结构体,可以含有构成PCP等络合物的多价配体,其至少一部分被碳等材料取代。构成络合物的多价配体将金属离子进行还原,缓慢地失去氢而变化为碳。有机系结构体只要含有有机系的多价配体的一部分至碳为止的各种有机系的材料即可。
复合体的制造原料中使用的络合物含有有机多价配体和金属离子。有机多价配体含有2价以上的有机配体,2价以上的有机配体配位于另外的(邻接的)2个的金属离子,成为以一维、二维或三维扩展的络合物。本发明的制造方法中使用的络合物需要金属络合物至少以一维聚合的、换句话说在1个有机配体上配位2个以上的金属离子。这样的络合物包括MOF、PCP等,但不包括单核络合物。
PCP通常具有由2层以上(例如2~100层、优选3~50层、更优选4~30层、特别是4~20层)的金属和配体构成的层,该层被重复。通过每层改变金属离子,可得到含有各种金属纳米粒子的复合体。
在本说明书中,作为MOF、PCP等络合物,由金属离子和有机配体构成,可以含有平衡阴离子。作为金属离子,可列举属于周期表的IA~IIB族的金属的金属离子,具体而言,可列举金、铂、银、铜、钌、锡、钯、铑、铱、锇、镍、钴、锌、铁、钇、镁、锰、钛、锆、铪、钙、镉、钒、铬、钼、钪等离子,优选镁、钙、锰、铁、钌、钴、铑、镍、钯、铜、锌、镉、钛、钒、铬、锰、铂、钼、锆、钪等离子,更优选锰、铁、钴、镍、铜、锌、银、铂、钯、钌、铑等金属的离子。金属离子可以使用单一的金属离子,也可以并用2种以上金属离子。通过使用并用有2种以上金属离子的络合物,可以得到金属纳米粒子为合金的复合体。
作为构成MOF、PCP等络合物的有机配体,可列举:在苯、萘、蒽、菲、芴、茚满、茚、芘、1,4-二氢萘、四氢化萘、亚联苯、三亚苯、苊烯、萘嵌戊烷等的芳香环上键合有2个、3个或4个羧基的化合物(所述有机配体可以被F、Cl、Br、I等卤原子、硝基、氨基、乙酰基氨基等酰基氨基、氰基、羟基、亚甲基二氧基、亚乙基二氧基、甲氧基、乙氧基等具有直链或支链的碳数1~4的烷氧基、甲基、乙基、丙基、叔丁基、异丁基等具有直链或支链的碳数1~4的烷基、SH、三氟甲基、磺酸基、氨基甲酰基、甲基氨基等烷基氨基、二甲基氨基等二烷基氨基等取代基进行1、2或3取代)、富马酸、马来酸、柠康酸、衣康酸等不饱和2元羧酸、吡嗪、4,4’-联吡啶、二氮杂芘等可由2个以上的环内氮原子配位的含氮芳香族化合物(可以由上述取代基进行1、2或3取代。)等。作为优选的2价以上的有机配体,可列举:间苯二甲酸、对苯二甲酸等。有机配体为OH、烷氧基、烷基等电子供给性基团时,容易引起加热时的金属离子的还原,因此优选。例如,2,5-二羟基对苯二甲酸的情况下,在络合物的加热时被氧化而可取得醌结构,因此,其有可能促进金属离子的还原和与其相伴的金属纳米粒子的形成。配体为中性的情况下,具有为了将金属离子进行中和而需要的平衡阴离子。作为这样的平衡阴离子,可列举:氯化物离子、溴化物离子、碘化物离子、硫酸离子、硝酸离子、磷酸离子、三氟醋酸离子、甲烷磺酸离子、甲苯磺酸离子、苯磺酸离子、高氯酸离子等。
构成MOF、PCP等络合物的有机配体可以含有单座的配体。单座的配体的比例增多时,可以缩小络合物的尺寸,可以缩小得到的复合体的尺寸。作为单座的配体,可举出含有1个苯甲酸等羧基的配体、吡啶、咪唑等含有1个可配位的氮原子的配体,但并不限定于这些。
含有上述的金属离子和有机配体的络合物包含具有片状等二维细孔或含有多个的片配位于轴向位的二座配体作为构成要素的三维细孔的PCP,也可以使用例如以下的PCP。
IRMOF-1,Zn4O(BDC)3(H2BDC=benzenedicarboxylic acid(苯二甲酸))
MOF-69C,Zn3(OH2)(BDC)2
MOF-74,M2(DOBDC)(H2DOBDC=2,5-dihydroxyterephthalic acid(2,5-二羟基对苯二甲酸),M=Zn,Co,Ni,Mg)
HKUST-1,Cu3(BTC)2(H3BTC=1,3,5-benzenetricarboxylic acid(1,3,5-苯三甲酸))
MOF-508,Zn(BDC)(bipy)0.5
Zn-BDC-DABCO,Zn2(BDC)2(DABCO),(DABCO=1,4-diazabicyclo[2.2.2]-octane(1,4-二氮杂二环[2.2.2]辛烷))
Cr-MIL-101,Cr3F(H2O)2O(BDC)3
Al-MIL-110,Al8(OH)12{(OH)3(H2O)3}[BTC]3,
Al-MIL-53,Al(OH)[BDC]
ZIF-8,Zn(MeIM)2,(H-MeIM=2-methylimidazole(2-甲基咪唑))
MIL-88B,Cr3OF(O2C-C6H4-CO2)3
MIL-88C,Fe3O(O2C-C10H6-CO2)3
MIL-88D,Cr3OF(O2C-C12H8-CO2)3
CID-1[Zn2(ip)2(bpy)2](Hip=isophthalic acid(间苯二甲酸),bpy=4,4'-bipyridine(4,4'-联吡啶))
本发明中使用的PCP记载于例如以下的文献、综述(Angew.Chem.Int.Ed.2004,43,2334-2375.;Angew.Chem.Int.Ed.2008,47,2-14.;Chem.Soc.Rev.,2008,37,191-214.;PNAS,2006,103,10186-10191.;Chem.Rev.,2011,111,688-764.;Nature,2003,423,705-714.)等,但并不限定于这些,可以广泛地使用公知的PCP或今后可制造的PCP。
在本发明的制造方法中,可以认为,构成MOF、PCP等络合物的金属离子通过加热与有机配体反应而发生氧化还原反应,金属离子变换为金属纳米粒子。因此,金属纳米粒子成为含有构成络合物的金属的纳米粒子。通过在减压下、优选在真空下进行络合物的加热,金属离子被还原而形成金属纳米粒子。金属纳米粒子在络合物的表面及内部同时且大量形成,成为分散有金属纳米粒子的复合体。通过将络合物进行加热,小的金属纳米粒子缓慢地成长,成为大的金属纳米粒子。因此,通过控制络合物的加热的条件,可以控制金属纳米粒子的尺寸。
在本说明书中,“高密度”是指:以0.1~85质量%、优选1~85质量%、更优选10~85质量%的比例含有金属纳米粒子的复合体。将络合物进行加热时,最初在络合物的表面及内部形成许多小的金属纳米粒子。这样,通过在络合物的表面及内部众多地形成金属纳米粒子,可得到均匀地分散有金属纳米粒子的复合体。通过提高加热温度或延长加热时间,金属离子变化为金属纳米粒子,因此,在加热引起的反应的初期,金属纳米粒子的重量比例变少,但形成许多小的金属纳米粒子,因此,可以说为“高密度”。
加热时的温度为100~1000℃左右,优选为150~700℃左右,更优选为200~650℃左右,进一步优选为250~650℃左右,特别优选为250~450℃左右。
络合物的加热可以在减压下、不活泼气氛下、还原气氛下、氧化气氛下、优选真空下进行。作为加热反应时的减压下的压力,为1000Pa左右以下,优选为100Pa左右以下,特别为5~100Pa左右。
加热反应的时间为1秒~30天左右,优选为1小时~7天左右。
通过在如上所述的条件下将络合物进行加热,构成络合物的金属离子被还原而成为金属单体的纳米粒子。另外,有机配体通过加热而至少一部分变化,例如变化为碳。复合体的有机系结构体来自络合物的配体。
本发明的优选的金属纳米粒子复合体的金属纳米粒子大致均匀地分散于复合体的表面及内部。金属纳米粒子大致均匀地分散可以利用TEM照片来确认。
复合体中所含的金属纳米粒子的平均粒径为1~100nm左右,优选为1~20nm左右。复合体中的金属纳米粒子的平均粒径可以利用TEM等显微镜照片来确认。金属纳米粒子的形状没有特别限定,可以为球状、楕圆体状、鳞片状等任意的形状。
本发明的复合体中的金属纳米粒子的比例为0.05~95重量%左右,优选0.1~85重量%左右,更优选1~80重量%左右,特别优选2~75重量%左右,有机系结构体为99.95~5重量%左右,优选99.9~15重量%左右,更优选99~20重量%左右,特别优选98~25重量%左右。予以说明,在络合物的加热处理的初期,构成络合物的金属离子的一部分成为金属纳米粒子,其比例通过延长反应时间或提高反应温度而增加,但在有机系结构体中可以残存来自络合物的金属或金属离子。因此,在有机系结构体中可以含有金属或金属离子、金属氧化物等无机系的成分。
金属纳米粒子由金属、合金或金属氧化物构成。
由于金属纳米粒子的金属来自MOF、PCP等金属络合物,因此可列举构成金属纳米粒子的金属。但是,在金属络合物由2种以上金属构成的情况下,含有合金,在加热时被氧化的情况下,可成为金属氧化物。
作为构成金属纳米粒子的金属,可列举属于周期表的IA~IIB族的金属或其合金或氧化物(包括复合氧化物),具体而言,可列举金、铂、银、铜、钌、锡、钯、铑、铱、锇、镍、钴、锌、铁、钇、镁、锰、钛、锆、铪或选自它们中的2种以上金属的合金、氧化物或复合氧化物,进一步优选列举金、铂、银、铜、钌、钯、铑、铱、锇、镍、钴、锌、铁、钇、镁、钛、或它们的2种以上的合金等。作为金属氧化物,可列举:PtO2、CuO、氧化钌(IV)、氧化铑、氧化钌、Fe2O3、Fe3O4、ZnO、氧化锇(IV)、或含有2种以上金属的复合氧化物等。
金属纳米粒子为铁或其氧化物的纳米粒子的情况下,可以为BCC(体心立方晶格结构)和FCC(面心立方晶格结构)的任一种。
“有机系结构体”为如下结构体:通过将PCP、MOF等由有机配体和金属构成的以一维、二维或三维扩展的结构体在减压下进行加热、有机配体的一部分或全部进行分解而残存的、来自有机配体的结构体。有机系结构体优选残留来自PCP或MOF的结构。来自PCP或MOF的结构可以通过X射线衍射等来确认。在高温和/或长时间进行减压下的加热时,来自PCP或MOF的结构缓慢地破坏,碳系的材料的比例增加。
在1个实施方式中,金属离子被还原而形成金属纳米粒子的情况下,认为金属离子被有机配体还原,该情况下,有机配体被氧化。随着反应的进行,由有机配体产生碳,其比例增加。予以说明,减压下的加热可以在不活泼气氛(含有氮、氩等不活泼气体)下进行,通过在氧化气氛(含有氧、臭氧等氧化剂)或还原气氛(含有氢等还原剂)下进行,可以使“有机系结构体”的氧化或还原的程度变化。另外,在氧化气氛下进行加热处理的情况下,也可以使金属纳米粒子作为金属氧化物析出。
作为构成有机系结构体的碳,可列举:玻璃碳、石墨、碳洋葱、焦炭、碳轴、碳纳米墙、碳纳米线圈、碳纳米管、碳纳米螺旋、碳纳米纤维、碳纳米锥、碳纳米绳、炭黑等。
有机系结构体优选为多孔。金属纳米粒子被保持在复合体的孔的中,一部分被有机系结构体支撑但活性的表面露出。由于该活性的表面的比例大,因此,本发明的复合体作为提供金属纳米粒子的材料优选。
本发明的复合体可以作为催化剂优选使用。利用本发明的复合体被催化的气体、金属纳米粒子催化剂、生成物可列举例如如下的组合。
在1个优选的实施方式中,本发明的复合体由碳和金属纳米粒子构成,为导电性,不通过粘合剂将金属纳米粒子保持在碳中,因此,作为电极催化剂是非常有用的。
【表1】
【实施例】
以下,基于实施例,对本发明更详细地进行说明,不用说,本发明并不限定于这些实施例。
制造例1:PCP络合物的制备
在3000ml梨形烧瓶中加入作为溶剂的DMF-乙醇-水(以容量计为1:1:1)2000ml、Ni(NO3)2·6H2O(23.8g)、2,5-二羟基对苯二甲酸(H4dhtp、4.8g),在100℃下搅拌5天并反应。将析出的三维结构金属络合物(Ni2(dhtp))通过抽滤回收之后,用甲醇、水清洗。接着,在25℃下在减压下干燥24小时,得到目标金属络合物(Ni2(dhtp))12g。目标金属络合物的得到通过粉末X射线结构分析来确认。以下有时将得到的金属络合物称为“Ni-MOF-74”。
制造例2:PCP络合物的制备
在300ml梨形烧瓶中加入作为溶剂的DMF-乙醇-水(以容量计为1:1:1)200ml、Co(NO3)2·6H2O(2.4g)、2,5-二羟基对苯二甲酸(H4dhtp、0.5g),在100℃下搅拌5天,使其反应。将析出的三维结构金属络合物(Co2(dhtp))通过抽滤回收之后,用甲醇、水清洗。接着,在25℃下在减压下干燥24小时,得到目标金属络合物(Co2(dhtp))0.8g。目标金属络合物的得到通过粉末X射线结构分析来确认。
实施例1
对制造例1中得到的Ni络合物,在以下的表2的反应温度及反应时间下、在使用真空泵的减压下(真空下)进行加热,制造本发明的Ni复合体。
【表2】
合成条件和批次名称
6小时 | 12小时 | 24小时 | 3天 | 7天 | |
250℃ | 250-6h | 250-12h | 250-24h | 250-7d | |
300℃ | 300-6h | 300-12h | 300-24h | 300-3d | |
350℃ | 350-6h | 350-12h | 350-24h | ||
400℃ | 400-6h | 400-12h | 400-24h |
对得到的Ni复合体,将粉末X射线衍射的结果示于图1,将扫描透射型电子显微镜(STEM)照片示于图2,将高分解能透射电子显微镜(HRTEM)照片示于图3,将拉曼测定结果示于图4、图5,将77K下的N2吸附的结果示于图6。
实施例2
对制造例2中得到的Co络合物,在400℃下在使用真空泵的减压下(真空下)加热18小时,制造本发明的Co复合体。
对得到的Co复合体,将粉末X射线衍射的结果及高分解能透射电子显微镜(HRTEM)照片示于图7。
实施例3
对实施例1中得到的Ni复合体(400℃-12h),实施磁测定。将复合体4.5mg装入明胶胶囊内,将进一步使用PVP的乙醇溶液固化的材料安装在SQUID测定用杆上,测定2K及300K中的磁场依赖性。对MOF,用保鲜膜包裹Ni2(dhtp)3.1mg,与复合体同样地测定磁场依赖性。将结果示于图8。
对于复合体而言,2K下观测到磁滞,但在Ni2(dhtp)的情况下,在任何温度下都未观测到该现象,可知:通过进行与Ni纳米粒子的复合化反应,对磁铁的应答产生变化。通过改变反应条件并改变Ni纳米粒子的比率,可以自由地控制磁特性,因此,该结果显示:用使用热分解的方法制作的复合体具有作为新的磁性材料的可能性。
实施例4
将实施例1中得到的Ni复合体(350℃-12h、400℃-12h)用作电极催化剂,实施乙醇氧化反应。在乙醇2ml和“Nafion(注册商标)”[杜邦社制、固体成分浓度5质量%的十倍稀释样品]100μl的混合溶剂中添加复合体10mg,照射超声波并做成悬浮液。将该悬浮液30μL涂布于玻碳电极[3mm直径、电极面积为7.1mm2]并进行干燥,由此得到修饰电极。将该修饰电极浸渍于浓度1.0M的氢氧化钠及0.5M乙醇的混合溶液中,在室温、大气压下、氩气氛下相对于银氯化银电极电位在-0.45~1.00V的扫描范围内、以50mV/s的扫描速度使电位循环。将结果示于图9。
取代上述复合体(350℃-12h、400℃-12h),将原料的Ni-MOF-74、使Ni粒子吸附于碳而形成的复合体(Ni+碳;比较例)作为电极催化剂,进行同样地循环伏安图。将这些结果同时示于图9。
予以说明,在300℃-12h下进行了加热处理的复合体,Ni纳米粒子的生成量少,但在循环伏安图中,充分地观测到对应于乙醇的氧化反应的催化电流,本发明人等确认:与使Ni粒子吸附于碳而形成的复合体相比,每单位重量的催化活性优异。
与文献1(Materials Letters,2011,65,3396-3398.)同样,在0.6V附近可以确认对应于乙醇的氧化反应的电流峰值。在复合体中也观测到对应于乙醇的氧化反应的催化电流,因此,得知:该复合体具有催化活性。进而,关于350℃-12h、400℃-12h的样品,得知:与使用Ni粉末的样品相比,乙醇氧化电流值高,显示高的催化活性。
实施例5
对制造例1中得到的Ni络合物,在以下的表2的反应温度及反应时间下、在大气压下(空气中)于350℃加热12小时,制造本发明的Ni复合体。Ni纳米粒子成为Ni氧化物(NiO)。
对得到的Ni复合体,将粉末X射线衍射的结果示于图10。
Claims (7)
1.一种金属纳米粒子复合体,其特征在于,具有在有机系结构体中分散有金属纳米粒子的结构,
所述有机系结构体包含:含有金属及可以还原金属的多价配体的、多孔配位聚合物(Porous Coordination Polymer(PCP))或金属-有机物结构体(Metal-Organic Framework(MOF))的结构,和碳。
2.如权利要求1所述的复合体,其中,金属纳米粒子的金属为属于周期表的IA~IIB族的金属的1种或2种以上。
3.如权利要求2所述的复合体,其中,金属纳米粒子的金属为金、铂、银、铜、钌、锡、钯、铑、铱、锇、镍、钴、锌、铁、钇、镁、锰、钛、锆、铪或选自它们中的2种以上金属的合金。
4.如权利要求1~3中任一项所述的复合体,其中,有机系结构体至少部分地含有碳。
5.如权利要求4所述的复合体,其中,所述碳选自由玻璃碳、石墨、碳洋葱、焦炭、碳轴、碳纳米墙、碳纳米线圈、碳纳米管、碳纳米螺旋、碳纳米纤维、碳纳米锥、碳纳米绳、炭黑构成的组。
6.如权利要求1~5中任一项所述的金属纳米粒子复合体的制造方法,所述金属纳米粒子复合体具有在有机系结构体中分散有金属纳米粒子的结构,其中,将含有金属及可以还原金属的多价配体的、多孔配位聚合物(PCP)或金属-有机物结构体(MOF)进行加热而使金属纳米粒子析出。
7.如权利要求6所述的方法,其中,将所述加热在真空下进行。
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