CN102115094B - 硼氮氢化合物脱氢及制备结晶态多聚硼氮化合物的方法 - Google Patents
硼氮氢化合物脱氢及制备结晶态多聚硼氮化合物的方法 Download PDFInfo
- Publication number
- CN102115094B CN102115094B CN200910248936.5A CN200910248936A CN102115094B CN 102115094 B CN102115094 B CN 102115094B CN 200910248936 A CN200910248936 A CN 200910248936A CN 102115094 B CN102115094 B CN 102115094B
- Authority
- CN
- China
- Prior art keywords
- boron
- borine
- transition metal
- nitrogen
- hydrogen
- 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.)
- Expired - Fee Related
Links
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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
本发明涉及硼氮氢化合物脱氢及制备结晶态多聚硼氮化合物的方法,利用催化分解硼氮氢化合物放氢合成结晶态多聚硼氮化合物,其中硼氮化合物分子式为:[NRR’BH2]n或[R(NHBH2)2]n n为≥2的正整数。催化剂为过渡金属、过渡金属的盐、合金。结晶态多聚硼氮化合物的合成温度为-100~300℃。
Description
技术领域
本发明涉及结晶态多聚化合物合成的方法及催化硼氮氢化合物脱氢方法。
背景技术
近年来,随着“氢经济”的发展,氨硼烷(NH3BH3)以其高氢含量(19.6wt.%)越来越受到人们的重视。氨硼烷脱氢分为三步,每一步脱出一分子的氢气。在第一步中,多聚胺基硼烷([NH2BH2]n)为主要产物,如下式:
然而,多聚胺基硼烷实际上一种是由直链、支链或环状组成的二聚及多聚无定形的混合物。研究人员利用过渡金属、酸、碱及离子液体在溶液中催化氨硼烷分解放氢。但是,产物的结晶状态要么是无定形,要么没有提及。Heinekey等人利用(POCOP)Ir(H)2在四氢呋喃溶液中催化分解氨硼烷放氢,得到了五元环胺基硼烷([NH2B2]5)。但是(POCOP)Ir(H)2催化剂是一种复杂的不易得到的金属有机化合物。除此之外,没有关于结晶态的多聚胺基硼烷的报道。
作为氨硼烷的衍生物,金属代氨硼烷(metal amidoboranes)和胺基硼烷(amine boranes)也可以在一定的条件下脱氢。但是到目前为止,还没有关于他们在固相反应中脱氢产物的结晶性的报道。
发明内容
本发明利用廉价易得的化合物来催化氨硼烷、金属代氨硼烷和胺基硼烷分解放氢,得到了结晶态的多聚胺基硼烷。本发明中所选用的催化剂为过渡金属、过渡金属盐以及合金。
硼氮氢化合物是一种高氢含量的材料,因此操作过程中应该在惰性气体下进行,例如:氩气或氮气等。
硼氮氢化合物在催化条件下脱氢生成结晶态的硼氮化合物;
硼氮氢化合物为:氨硼烷(ammonia borane)、金属代氨硼烷(metalamidoboranes)或胺基硼烷(amine boranes),最好为氨硼烷。
硼氮化合物分子式为:[NRR’BH2]n、n≥2,或[R(NHBH2)2]n、n≥2。其中,R或R’为H、Li、Na、K、Mg、Ca、或有机基团:-Me、-Cy、-Pr、-Ph或-Et等。
催化氨硼烷分解放氢过程可以在固态或液态下进行,固态催化过程效果更好。
在固相催化脱氢过程中,催化剂或催化剂前驱体通过搅拌、球磨或“共 沉淀”法分散到氨硼烷中,其中,“共沉淀”法效果更好。
催化剂是由过渡金属、过渡金属盐及合金制得的。过渡金属为IB、IIB、IIIB、IVB、VB、VIB、VIIB或VIIIB族元素中的一种或多种,其中,最好为Fe、Co、Ni、Cu、Ru、Rh、Pd、Ag、Pt或Au等一种或几种。过渡金属的盐为:有机金属盐、Cl-、SO4 2-、NO3 -、NO2 -、F-、Br-、PO4 3-、或CH3COO-的盐中的一种或多种。合金为Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Rh、Pd、Ag、Ir、Pt、Au、P、C、B或N之间形成的两元或多元合金,最好为一种过渡金属和B、N、或C之间形成的合金。
结晶态多聚胺基硼烷是通过催化分解氨硼烷形成的,如下式:
其中n最好为2、3、4、5或6。
催化分解氨硼烷的温度为-100~300℃之间,最好为-20~150℃之间。氨硼烷与催化剂或催化剂前驱体的摩尔比为10000∶1~1∶1,最好为1000∶5∶1.
氨硼烷催化放氢过程应该在一充满惰性气体或真空密闭系统下进行。放氢量为0.5mol/氨硼烷~1.5mol/氨硼烷。反应时间为0.01小时~100小时。
产物结晶态的多聚胺基硼烷由X射线衍射和红外来检测。
附图说明
图160℃下,4.8mol%FeCl2掺杂的氨硼烷分解放氢曲线。
图280℃下,2.0mol%FeCl2掺杂的氨硼烷分解放氢曲线。
图360℃下,5.0mol%CoCl2掺杂的氨硼烷分解放氢曲线。
图460℃下,5.0mol%NiCl2掺杂的氨硼烷分解放氢曲线。
图6脱氢后5.0mol%FeCl2参杂的氨硼烷样品的红外谱图。
具体实施方式
实施例1
于手套箱中称取31.8mg的FeCl2,转移到10ml THF溶液中,将该溶液超声20分钟。称取159.8mg氨硼烷,加入到上述FeCl2的THF溶液或悬浊液中。于旋转蒸发仪中减压蒸馏除去溶剂THF。4.8mol%FeCl2掺杂的氨硼烷样品准备完毕。样品应保存于低于10℃的冰箱内,防止自分解。
将制得的4.8mol%FeCl2氨硼烷置于一充满氩气的不锈钢反应器中,同时保持温度为60℃。经过40小时,大约1mol/氨硼烷的氢气从氨硼烷中放出如图1所示。产物由X射线衍射确定为五元环结晶态胺基硼烷[NH2BH2]5如图5。
实施例2
2.0mol%FeCl2掺杂的氨硼烷依据实施例1中的方法制得。其余条件同实施例1;反应放氢温度设为80℃。经过12小时,大约1mol/氨硼烷的氢 气从氨硼烷中放出如图2所示。产物由X射线衍射确定为五元环结晶态胺基硼烷[NH2BH2]5如图5。
实施例3
5.0mol%CoCl2掺杂的氨硼烷依据实施例1中的方法制得。其余条件同实施例1;反应放氢温度设为60℃。经过20小时,大约1mol/氨硼烷的氢气从氨硼烷中放出如图3所示。产物由X射线衍射确定为五元环结晶态胺基硼烷[NH2BH2]5如图5。
实施例4
5.0mol%NiCl2掺杂的氨硼烷依据实施例1中的方法制得。其余条件同实施例1;反应放氢温度设为60℃。经过40小时,大约1mol/氨硼烷的氢气从氨硼烷中放出如图4所示。产物由X射线衍射确定为五元环结晶态胺基硼烷[NH2BH2]5如图5。
Claims (6)
1.硼氮氢化合物脱氢及制备结晶态多聚硼氮化合物的方法,其特征在于:利用催化分解硼氮氢化合物放氢合成结晶态多聚硼氮化合物,
所述的硼氮氢化合物为氨硼烷、金属代氨硼烷或胺基硼烷;硼氮氢化合物放氢过程中采用的催化剂为过渡金属、过渡金属的盐或合金;
所述硼氮氢化合物与催化剂的摩尔比为100000∶1~1∶1;催化反应温度为-100~300℃之间;
硼氮氢化合物催化放氢过程在充满惰性气体或真空密闭系统下进行;
所述过渡金属为Fe、Co、Ni或Cu中的一种或几种;
所述合金为Ti、V、Cr、Mn、Fe、Co、Ni、Cu、P、C、B或N之间形成的两元或多元合金;
所述过渡金属的盐的阴离子为:Cl-、SO4 2-、NO3 -、NO2 -、F-、Br-、PO4 3-、或CH3COO-中的一种或多种;
催化过程的反应是在固相中进行的。
2.按照权利1所述的方法,其特征在于:所述多聚硼氮化合物具有如下的分子式:[NRR’BH2]n或者[R(NHBH2)2]n,n为≥2的正整数;R、R’为H、Li、Na、K、Mg、Ca、或有机基团:-Me、-Cy、-Pr、-Ph或-Et中的一种。
3.按照权利2所述的方法,其特征在于:所述n为2-10正整数。
4.按照权利2所述的方法,其特征在于:所述n为2、3、4、5或6。
5.按照权利1所述的方法,其特征在于:所述催化反应时间为0.01小时~100小时。
6.按照权利1所述的方法,其特征在于:所述硼氮氢化合物与催化剂的摩尔比为1000∶1~5∶1,反应温度为-20~150℃之间。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200910248936.5A CN102115094B (zh) | 2009-12-30 | 2009-12-30 | 硼氮氢化合物脱氢及制备结晶态多聚硼氮化合物的方法 |
US12/840,157 US8329130B2 (en) | 2009-12-30 | 2010-07-20 | Method of synthesizing crystalline polymeric boron-nitrogen compound and dehydrogenation of boron-nitrogen-hydrogen complex |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200910248936.5A CN102115094B (zh) | 2009-12-30 | 2009-12-30 | 硼氮氢化合物脱氢及制备结晶态多聚硼氮化合物的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102115094A CN102115094A (zh) | 2011-07-06 |
CN102115094B true CN102115094B (zh) | 2012-12-05 |
Family
ID=44187811
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200910248936.5A Expired - Fee Related CN102115094B (zh) | 2009-12-30 | 2009-12-30 | 硼氮氢化合物脱氢及制备结晶态多聚硼氮化合物的方法 |
Country Status (2)
Country | Link |
---|---|
US (1) | US8329130B2 (zh) |
CN (1) | CN102115094B (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB201223264D0 (en) * | 2012-12-21 | 2013-02-06 | Cella Energy Ltd | A hydrogen-storage-material |
US9005562B2 (en) | 2012-12-28 | 2015-04-14 | Boroscience International, Inc. | Ammonia borane purification method |
US9604850B2 (en) | 2013-12-27 | 2017-03-28 | Weylchem Sustainable Materials, Llc | Ammonia borane purification method |
CN109607558A (zh) * | 2019-01-07 | 2019-04-12 | 河南师范大学 | 一种质子酸诱导的硼氮链环化反应制备环状硼氮氢化合物的方法 |
CN112062135B (zh) * | 2020-08-10 | 2023-09-15 | 河南师范大学 | 一种链状硼氮氢化合物的合成方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8518368B2 (en) * | 2007-05-18 | 2013-08-27 | Kanata Chemical Technologies Inc. | Method for the production of hydrogen from ammonia borane |
US8038980B2 (en) * | 2009-07-08 | 2011-10-18 | Ford Motor Company | Hydrogen storage materials containing ammonia borane |
-
2009
- 2009-12-30 CN CN200910248936.5A patent/CN102115094B/zh not_active Expired - Fee Related
-
2010
- 2010-07-20 US US12/840,157 patent/US8329130B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
Title |
---|
Martin E. Bluhm et al..Amineborane-Based Chemical Hydrogen Storage: Enhanced Ammonia Borane Dehydrogenation in Ionic Liquids.《J. AM. CHEM. SOC.》.2006,第128卷(第24期),7748-7749. * |
Melanie C. Denney et al..Efficient Catalysis of Ammonia Borane Dehydrogenation.《J. AM. CHEM. SOC.》.2006,第128卷(第37期),12048-12089,S1-S6. * |
Also Published As
Publication number | Publication date |
---|---|
US8329130B2 (en) | 2012-12-11 |
US20110158881A1 (en) | 2011-06-30 |
CN102115094A (zh) | 2011-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Laassiri et al. | The potential of manganese nitride based materials as nitrogen transfer reagents for nitrogen chemical looping | |
Han et al. | Ambient N2 fixation to NH3 at ambient conditions: Using Nb2O5 nanofiber as a high-performance electrocatalyst | |
WO2015085623A1 (zh) | 用于氨合成及氨分解的催化剂 | |
Ramachandran et al. | Preparation of ammonia borane in high yield and purity, methanolysis, and regeneration | |
Redshaw | Coordination chemistry of the larger calixarenes | |
CN102115094B (zh) | 硼氮氢化合物脱氢及制备结晶态多聚硼氮化合物的方法 | |
US9067957B2 (en) | Metal nickel-imidazolate chiral nano clathrate complex and preparation method thereof | |
US8536358B2 (en) | Scaffold materials-transition metal hydride complexes, intermediates therefor and method for preparing the same | |
KR101617053B1 (ko) | 연속 반응기를 이용한 1,3-부타디엔의 제조방법 | |
Yu et al. | Effects of alkaline earth metal amides on Ru in catalytic ammonia decomposition | |
Choi et al. | Three-dimensional cobalt (II) and cadmium (II) MOFs containing 1, 4-naphthalenedicarboxylate: Catalytic activity of Cd-MOF | |
Demirci | Mechanistic insights into the thermal decomposition of ammonia borane, a material studied for chemical hydrogen storage | |
Wang et al. | The impact of alkali and alkaline earth metals on green ammonia synthesis | |
Wang et al. | Transition metal-modified mesoporous Mg-Al mixed oxides: Stable base catalysts for the synthesis of diethyl carbonate from ethyl carbamate and ethanol | |
Khan et al. | CoCo-PBA/tetrabutylammonium bromide as highly efficient catalyst for CO2 and epoxides coupling reaction under mild conditions | |
Rahman et al. | Hydrogen sorption properties of Ternary Mg–Nb–O phases synthesized by solid–state reaction | |
Mujmule et al. | Synergetic effect of ZnCo2O4/inorganic salt as a sustainable catalyst system for CO2 utilization | |
Yang et al. | Highly active La0. 35Sr0. 35Ba0. 3Fe1-xCoxO3 oxygen carriers with the anchored nanoparticles for chemical looping dry reforming of methane | |
CN102060264A (zh) | 过渡金属催化硼氮多元化合物分解放氢的储放氢体系及其应用 | |
Luo et al. | Li2 (NH2BH3)(BH4)/LiNH2BH3: the first metal amidoborane borohydride complex with inseparable amidoborane precursor for hydrogen storage | |
CN1431049A (zh) | 一种由合成气制低碳混合醇的催化剂及其制备方法 | |
Luo et al. | An ultralong single-crystalline nanoporous 3D transition metal-oxo framework nanowire family | |
CN109954510A (zh) | 一种铬基氨合成与氨分解催化剂及应用 | |
Qi et al. | Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd (phen) 2} 2V4O12]· 5H2O and [Ni (phen) 3] 2 [V4O12]· 17.5 H2O | |
Stein et al. | Mechanochemical synthesis of new coordination polymers with acetylenedicarboxylate as bridging ligand |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121205 Termination date: 20151230 |
|
EXPY | Termination of patent right or utility model |