CN104761485A - 一种新型的储氢材料及氢的解析方法 - Google Patents

一种新型的储氢材料及氢的解析方法 Download PDF

Info

Publication number
CN104761485A
CN104761485A CN201510102611.1A CN201510102611A CN104761485A CN 104761485 A CN104761485 A CN 104761485A CN 201510102611 A CN201510102611 A CN 201510102611A CN 104761485 A CN104761485 A CN 104761485A
Authority
CN
China
Prior art keywords
acid
hydrogen
storage material
aryl
alkyl
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.)
Pending
Application number
CN201510102611.1A
Other languages
English (en)
Inventor
吴志军
方冬梅
蒋艳
戚华溢
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu Institute of Biology of CAS
Original Assignee
Chengdu Institute of Biology of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chengdu Institute of Biology of CAS filed Critical Chengdu Institute of Biology of CAS
Priority to CN201510102611.1A priority Critical patent/CN104761485A/zh
Publication of CN104761485A publication Critical patent/CN104761485A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0015—Organic compounds; Solutions thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • 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
    • Y02E60/32—Hydrogen storage

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

本发明属于材料能源领域，涉及到一种新型的有机储氢材料的结构以及氢的解析方法。该有机储氢材料中含有非常温和的氢负离子，在常温下加入酸，氢负离子与酸中的质子结合，然后释放氢气。通过质谱的方法对溶液进行检测，质谱图的变化反应了该释放过程。释放的气体点燃后可以使无水硫酸铜变蓝，证明为氢气。该有机材料相对便宜、易得、稳定，氢气释放条件温和、安全，在常温下、正常大气压下即可完成。

Description

一种新型的储氢材料及氢的解析方法
技术领域
本发明属于材料能源领域，涉及到一种新型的有机储氢材料的结构以及氢的解析方法。该有机储氢材料中含有非常温和的氢负离子，在常温下加入酸即可以释放氢气。
背景技术
随着石化燃料消耗的逐渐增大以及储量的减少，人们生活的环境变得越来越恶劣，因此，环境友好且能再生的能源受到了越来越多的重视。氢由于燃烧后只有水，成为了最具潜力的能源。发展氢能，首先需要解决氢的存储问题。目前，固体吸附储氢是主要的储氢方法，例如碳纳米管储氢(Dillon A.C.,et al.,nature,1997,377.),但是该方法需要大的压力，并且脱氢也十分困难。另外一种是矿物储氢(Weitkamp J.,et al.,J.Hydrogen Energy,1995,967.)，一般这种矿物多集中在石墨以及沸石等矿物上，与碳纳米管相比，这种储氢方法通量相对较低，脱氢的温度比较高。
发明内容
本发明的目的是提供一种新型的有机储氢材料以及氢的解析方法。
(1)本发明提供的有机储氢材料的结构如下：
1.1对于材料a，与碳1直接连接的R1为苯环、吡咯、噻吩、吲哚或他们的衍生物，R2为芳基或烷基，R3为芳基或烷基。
1.2对于材料b，与碳1直接连接的R1为苯环、吡咯、噻吩、吲哚或他们的衍生物，R2为芳基或烷基，R3为芳基或烷基。
(2)氢的解析方法：在常温下，将此材料溶于有机溶剂，加入酸即可产生氢气。
2.1溶剂为有机溶剂，包括：①芳香烃类：苯、甲苯、二甲苯等；②脂肪烃类：戊烷、己烷、辛烷等；③脂环烃类：环己烷、环己酮、甲苯环己酮等；④卤化烃类：氯苯、二氯苯、二氯甲烷等；⑤醇类：甲醇、乙醇、异丙醇、正丁醇等；⑥醚类：乙醚、环氧丙烷等；⑦酯类：醋酸甲酯、醋酸乙酯、醋酸丙酯等；⑧酮类：丙酮、甲基丁酮、甲基异丁酮等；⑨二醇衍生物:乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚等；⑩其他：乙腈、吡啶、苯酚。
2.2用于释放氢气的酸为有机酸或无机酸，包括：甲酸、乙酸、三氟乙酸、草酸、磺酸、氢卤酸、卤系含氧酸、硫酸等硫系无机酸、硝酸、亚硝酸、磷酸、焦磷酸、碳酸等。
本发明具有以下优点：
1.材料相对便宜、易得、稳定。
2.氢气释放条件温和、安全。
附图说明
图1是实例1加入酸前(a)后(b)质谱图；
图2是实例2加入酸前(a)后(b)质谱图。
具体实施方式
以下结合实施例详细地说明本发明。实施方案为便于更好的理解本发明，但并非对本发明的限制。
实施例1：
(1).有机储氢材料的合成
有机储氢材料如Xu等在Angew.Chem.Int.Ed.2012,51,1059–1062.中描述的那样。具体结构如下的分子量为530的物质。
(2).氢气的解析
将材料溶入二氯甲烷中，加入等摩尔三氟乙酸后，材料中的氢负离子与酸中的质子结合产生氢气。用质谱检测该溶液，在加入酸之前，检测到的是常规的[M+H]+，[M+Na]+与[M+K]+离子，加入酸以后，只有[M-H]-离子，说明该材料中的氢负离子已经与质子结合(图1)。
实施例2：
(1).有机储氢材料的合成
有机储氢材料如Xu等在Angew.Chem.Int.Ed.2012,51,1059–1062.中描述的那样。具体结构如下的分子量为528的物质。
(2).氢气的解析
将材料溶入二氯甲烷中，加入等摩尔乙酸后，材料中的氢负离子与酸中的质子结合产生氢气。用质谱检测该溶液，在加入酸之前，检测到的是常规的[M+H]+，[M+Na]+与[M+K]+加入酸以后，只有[M-H]-离子，说明该材料中的氢负离子已经与质子结合(图2)。释放的气体点燃后可以使无水硫酸铜变蓝，证明释放的气体为氢气。

Claims (2)

1.一种新型的有机储氢材料及氢的解析方法，其结构特征如下：
对于材料a，其特征在于与碳1直接连接的R1为苯环、吡咯、噻吩、吲哚或他们的衍生物，R2为芳基或烷基，R3为芳基或烷基；
对于材料b，其特征在于与碳1直接连接的R1为苯环、吡咯、噻吩、吲哚或他们的衍生物，R2为芳基或烷基，R3为芳基或烷基。
2.一种新型的有机储氢材料，氢的解析方法如下：在常温下，将此材料溶于有机溶剂，加入酸即可产生氢气。其特征在于有机溶剂的选择，包括：①芳香烃类：苯、甲苯、二甲苯等；②脂肪烃类：戊烷、己烷、辛烷等；③脂环烃类：环己烷、环己酮、甲苯环己酮等；④卤化烃类：氯苯、二氯苯、二氯甲烷等；⑤醇类：甲醇、乙醇、异丙醇、正丁醇等；⑥醚类：乙醚、环氧丙烷等；⑦酯类：醋酸甲酯、醋酸乙酯、醋酸丙酯等；⑧酮类：丙酮、甲基丁酮、甲基异丁酮等；⑨二醇衍生物:乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚等；⑩其他：乙腈、吡啶、苯酚。其特征在于酸的选择，包括：甲酸、乙酸、三氟乙酸、草酸、磺酸、氢卤酸、卤系含氧酸、硫酸等硫系无机酸、硝酸、亚硝酸、磷酸、焦磷酸、碳酸等。
CN201510102611.1A 2015-03-09 2015-03-09 一种新型的储氢材料及氢的解析方法 Pending CN104761485A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510102611.1A CN104761485A (zh) 2015-03-09 2015-03-09 一种新型的储氢材料及氢的解析方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510102611.1A CN104761485A (zh) 2015-03-09 2015-03-09 一种新型的储氢材料及氢的解析方法

Publications (1)

Publication Number Publication Date
CN104761485A true CN104761485A (zh) 2015-07-08

Family

ID=53643634

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510102611.1A Pending CN104761485A (zh) 2015-03-09 2015-03-09 一种新型的储氢材料及氢的解析方法

Country Status (1)

Country Link
CN (1) CN104761485A (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005000457A2 (en) * 2003-05-06 2005-01-06 Air Products And Chemicals, Inc. Hydrogen storage reversible hydrogenated of pi-conjugated substrates
CN1659174A (zh) * 2002-06-19 2005-08-24 栗田工业株式会社 储氢方法,氢笼形物及其制备方法
CN1809505A (zh) * 2003-05-06 2006-07-26 空气化工产品公司 通过π－共轭基质的可逆氢化的氢气存储
US7351395B1 (en) * 2003-05-06 2008-04-01 Air Products And Chemicals, Inc. Hydrogen storage by reversible hydrogenation of pi-conjugated substrates
CN102115461A (zh) * 2009-12-31 2011-07-06 中国科学院理化技术研究所 由二氢苯并咪唑化合物制备苯并咪唑阳离子化合物和氢气的方法
CN103833729A (zh) * 2012-11-21 2014-06-04 中国科学院理化技术研究所 一种可见光催化交叉偶联制备偶联产物并放氢的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1659174A (zh) * 2002-06-19 2005-08-24 栗田工业株式会社 储氢方法,氢笼形物及其制备方法
WO2005000457A2 (en) * 2003-05-06 2005-01-06 Air Products And Chemicals, Inc. Hydrogen storage reversible hydrogenated of pi-conjugated substrates
CN1809505A (zh) * 2003-05-06 2006-07-26 空气化工产品公司 通过π－共轭基质的可逆氢化的氢气存储
US7351395B1 (en) * 2003-05-06 2008-04-01 Air Products And Chemicals, Inc. Hydrogen storage by reversible hydrogenation of pi-conjugated substrates
CN102115461A (zh) * 2009-12-31 2011-07-06 中国科学院理化技术研究所 由二氢苯并咪唑化合物制备苯并咪唑阳离子化合物和氢气的方法
CN103833729A (zh) * 2012-11-21 2014-06-04 中国科学院理化技术研究所 一种可见光催化交叉偶联制备偶联产物并放氢的方法

Non-Patent Citations (20)

* Cited by examiner, † Cited by third party
Title
BEI-SIH LIAO，等: "An efficient preparation of bis(indolyl)methanes catalyzed by tetrakis[3,5-bis(trifluoromethyl)phenyl]borate salts in aqueous medium", 《SYNTHESIS》 *
BIAO XU，等: "Multistep One-Pot Synthesis of Enantioenriched Polysubstituted Cyclopenta[b]indoles", 《ANGEW.CHEM.INT.ED》 *
J. S. YADAV，等: "InBr3 as a versatile and highly efficient catalyst for the synthesis of 3-allyl- and 3-benzylindoles", 《TETRAHEDRON LETTERS》 *
JIANGUO YANG，等: "CuBr-catalyzed selective oxidation of N-azomethine: highly efficient synthesis of methine-bridged bis-indole compounds", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 *
JOHN S. MAGEE，等: "《石油加工催化剂》", 31 July 2010, 石油工业出版社 *
K. RAMACHANDIRAN，等: "Palladium catalyzed alkylation of indole via aliphatic C-H bond activation of tertiary amine", 《TETRAHEDRON LETTERS》 *
MATEO ALAJARIN，等: "Intramolecular addition of benzylic radicals onto ketenimines. Synthesis of 2-alkylindoles", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 *
MOHIT L. DEB，等: "A novel and efficient method for the synthesis of unsymmetrical diindolylmethanes and heterocyclic(indolyl)alkanes", 《SYNTHESIS》 *
NINGBO LI，等: "Strong Lewis acid air-stable cationic titanocene perfluoroalkyl(aryl)sulfonate complexes as highly efficient and recyclable catalysts for C-C bond forming reactions", 《DALTON TRANSACTIONS》 *
TAKUMI ABE，等: "One-Pot Construction of 3,3’-Bisindolylmethanes through Bartoli Indole Synthesis", 《ORGANIC LETTERS》 *
TEJAS P. PATHAK，等: "Synthesis and preliminary biological study of bisindolylmethanes accessed by an acid-catalyzed hydroarylation of vinyl indoles", 《TETRAHEDRON》 *
TOMOMI NOGUCHI-YACHIDE，等: "Enhancement of chemically-induced HL-60 cell differentiation by 3,3’-diindolylmethane derivatives", 《CHEMICAL & PHARMACEUTICAL BULLETIN》 *
XIA-FEI XU，等: "A practical synthesis of bis(indolyl)methanescatalyzed by BF3 Et2O", 《CHINESE CHEMICAL LETTERS》 *
XIAO-FEI ZENG，等: "Novel method for synthesis of unsymmetrical bis(indolyl)alkanes catalyzed by ceric ammonium nitrate (CAN) under ultrasonic irradiation", 《TETRAHEDRON》 *
XIAOHONG ZHANG，等: "Synthesis and structure of an air-stable binuclear complex of bis(ethylcyclopentadienyl)zirconium perfluorooctanesulfonate and its catalytic application in one-pot three-component aza-Friedel-Crafts reactions", 《TETRAHEDRON LETTERS》 *
ZHAOBIN WANG，等: "Organocatalytic Asymmetric Synthesis of 1,1-Diarylethanes by Transfer Hydrogenation", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 *
ZHENG-LE ZHAO，等: "Pd(0)-catalyzed benzylation of indole through 3-benzyl palladium intermediate", 《CHINESE JOURNAL OF CATALYSIS》 *
ZHENG-LE ZHAO，等: "Pd(0)-catalyzed benzylation of indole through 3-benzyl palladium intermediate", 《CHINESE JOURNAL OF CATALYSIS》 *
刘博，等: "氢气储存材料", 《实验科学与技术》 *
周鹏，等: "化学储氢研究进展", 《化工进展》 *

Similar Documents

Publication Publication Date Title
Chen et al. Bu4NI‐Catalyzed C O Bond Formation by Using a Cross‐Dehydrogenative Coupling (CDC) Reaction
Jud et al. Catalyst‐free oxytrifluoromethylation of alkenes through paired electrolysis in organic‐aqueous media
Xu et al. Perylene‐Containing Conjugated Microporous Polymers for Photocatalytic Hydrogen Evolution
Wang et al. Graphene oxide catalyzed dehydration of fructose into 5‐hydroxymethylfurfural with isopropanol as cosolvent
Zhou et al. One‐pot Reductive Amination of carbonyl Compounds with Nitro Compounds by Transfer Hydrogenation over Co–Nx as catalyst
Wang et al. Stabilizing the imidazolium cation in hydroxide‐exchange membranes for fuel cells
Battin‐Leclerc et al. Experimental confirmation of the low‐temperature oxidation scheme of alkanes
Ge et al. Aerobic Multicomponent Tandem Synthesis of 3‐Sulfenylimidazo [1, 2‐a] pyridines from Ketones, 2‐Aminopyridines, and Disulfides
Wang et al. Conversion of platform chemical glycerol to cyclic acetals promoted by acidic ionic liquids
Huo et al. Catalytic amounts of CBr 4 mediated dehydrogenative coupling of isochromans with aromatic ketones
Chen et al. Rhodium (III)‐Catalyzed Synthesis of Cinnolinium Salts from Azobenzenes and Diazo Compounds
Gui et al. Brønsted acid ionic liquids (BAILs) as efficient and recyclable catalysts in the conversion of glycerol to solketal at room temperature
Gu et al. Hyper‐cross‐linked polymer based carbonaceous materials as efficient catalysts for ethyl levulinate production from carbohydrates
Ballini et al. A Two‐Step Synthesis of Unsymmetrical 1, 4‐Disubstituted Carbazoles from Sulfonylindoles Under Heterogeneous Catalysis
Li et al. The promotion effect of NaCl on the conversion of xylose to furfural
Wen et al. Metal‐Free Direct Alkylation of Ketene Dithioacetals by Oxidative C (sp2)− H/C (sp3)− H Cross‐Coupling
Liu et al. Catalytic One‐Pot Conversion of Renewable Platform Chemicals to Hydrocarbon and Ether Biofuels through Tandem Hf (OTf) 4+ Pd/C Catalysis
Lyu et al. Simultaneous conversion of C5 and C6 sugars into methyl levulinate with the addition of 1, 3, 5‐trioxane
Saulnier et al. Brønsted Acid Promoted Cyclization of Cross‐Conjugated Enynones into Dihydropyran‐4‐ones
Qian et al. Iron‐Catalyzed Alkenylation of Isochroman Acetals with Simple Alkenes
You et al. Photoionization Mass Spectrometry for Online Detection of Reactive and Unstable Gas‐Phase Intermediates in Heterogeneous Catalytic Reactions
CN104761485A (zh) 一种新型的储氢材料及氢的解析方法
Rostami et al. Double Brønsted Acidic Media Immobilized on Carbonized Sugarcane Bagasse (CSCB) as a New and Efficient Solid Acid Catalyst for the Synthesis of Coumarins, Dicoumarols and Xanthenes
Luo et al. K2S2O8‐Mediated Oxysulfonylation of Vinyl Azides with Sodium Sulfinates to Access β‐Keto Sulfones in Water
Hasan et al. Sterically Congested Chiral 7, 8‐Dioxa [6] helicene and Its Dihydro Analogues: Synthesis, Regioselective Functionalization, and Unexpected Domino Prins Reaction

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20150708

WD01 Invention patent application deemed withdrawn after publication