DE102008009432A1 - Hetero-oligonuclear compounds for use as highly active photocatalysts - Google Patents
Hetero-oligonuclear compounds for use as highly active photocatalysts Download PDFInfo
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- DE102008009432A1 DE102008009432A1 DE102008009432A DE102008009432A DE102008009432A1 DE 102008009432 A1 DE102008009432 A1 DE 102008009432A1 DE 102008009432 A DE102008009432 A DE 102008009432A DE 102008009432 A DE102008009432 A DE 102008009432A DE 102008009432 A1 DE102008009432 A1 DE 102008009432A1
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- chromophoric
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 4
- 239000003446 ligand Substances 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ULNRPVHOORAZAN-UHFFFAOYSA-L 4-methyl-2-(4-methylpyridin-2-yl)pyridine;platinum(2+);dichloride Chemical compound [Cl-].[Cl-].[Pt+2].CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 ULNRPVHOORAZAN-UHFFFAOYSA-L 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 238000001212 derivatisation Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 150000004033 porphyrin derivatives Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000000624 total reflection X-ray fluorescence spectroscopy Methods 0.000 description 2
- BUHVIAUBTBOHAG-FOYDDCNASA-N (2r,3r,4s,5r)-2-[6-[[2-(3,5-dimethoxyphenyl)-2-(2-methylphenyl)ethyl]amino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound COC1=CC(OC)=CC(C(CNC=2C=3N=CN(C=3N=CN=2)[C@H]2[C@@H]([C@H](O)[C@@H](CO)O2)O)C=2C(=CC=CC=2)C)=C1 BUHVIAUBTBOHAG-FOYDDCNASA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical compound CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 description 1
- 0 Cc1cc(-c2cc(C)cc*2*2(N)N)*2cc1 Chemical compound Cc1cc(-c2cc(C)cc*2*2(N)N)*2cc1 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- -1 organic compound 4,4'-dimethyl-2,2'-bipyridine-platinum dichloride Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
Abstract
Aufgabe war es, hochaktive und beständige Photokatalysatoren gemäß Hauptpatentanmeldung DE 102007025424.7, insbesondere für einen Multielektronentransfer, zur schaffen, die noch aufwandgeringer und kostengünstiger herstellbar sowie besser und umweltverträglicher abbaubar sind. Erfindungsgemäß weist zumindest eine chromophore Einheit der heterooligonuklearen Verbindung anstelle eines Metall- oder Halbmetallzentrums wenigstens eine organische Verbindung, beispielsweise $F1 auf. Die vorgeschlagenen Verbindungen dienen zur Verwendung als hochaktive Photokatalysatoren, beispielsweise zur Methangewinnung oder zur Wasserstoffbildung.The object was to provide highly active and stable photocatalysts according to the main patent application DE 102007025424.7, in particular for a multi-electron transfer, which are still less expensive and less expensive to produce and better and more environmentally friendly degradable. According to the invention, at least one chromophoric unit of the hetero-oligonuclear compound has at least one organic compound, for example $ F1, instead of a metal or semimetal center. The proposed compounds are for use as highly active photocatalysts, for example for methane recovery or for hydrogen generation.
Description
Die
Erfindung betrifft heterooligonukleare Verbindungen gemäß der
in der Hauptpatentanmeldung
M
= chromophore Einheit,
M' = katalytische Einheit,
CL =
Collectorligand,
A = Anion
n, Y, Z = Anzahl 1, 2, 3 ...
(n, Y, Z ≥ 1)
m = Anzahl 0, 1, 2, 3 ... (m ≥ 0),
1 = Art des Anions (1 ≥ 0)
i = Art der chromophoren
Einheit M mit X = Anzahl 1, 2, 3 ... [i ≥ 1, ΣX(i) ≥ 2]
j
= Art der katalytischen Einheit M' mit Z = Anzahl 1, 2, 3 ... [j ≥ 1,
Z(j) ≥ 1]
k = Art der multinuclearen Einheit Y = Anzahl
1, 2, 3 ... [k ≥ 1, Y(k) ≥ 1]
sind,
zur
Verwendung als hochaktive Photokatalysatoren.The invention relates to heterooligonuclear compounds according to the in the main patent application
M = chromophoric unit,
M '= catalytic unit,
CL = collector ligand,
A = anion
n, Y, Z = number 1, 2, 3 ... (n, Y, Z ≥ 1)
m = number 0, 1, 2, 3 ... (m ≥ 0), 1 = type of anion (1 ≥ 0)
i = type of chromophoric unit M with X = number 1, 2, 3 ... [i ≥ 1, ΣX (i) ≥ 2]
j = type of catalytic unit M 'with Z = number 1, 2, 3 ... [j ≥ 1, Z (j) ≥ 1]
k = type of multinuclear unit Y = number 1, 2, 3 ... [k ≥ 1, Y (k) ≥ 1]
are,
for use as highly active photocatalysts.
Mit diesen Verbindungen der allgemeinen Formell wurden oligonucleare Systeme geschaffen, die in der Lage sind, mehrere Elektronen aus mehreren chromophoren Zentren auf ein Katalysatormetall zu übertragen oder umgekehrt mehrere Elektronen von einem katalytischen Zentrum abzuziehen. Dabei kann ein Elektronenfluss von den chromophoren Einheiten zur katalytischen Einheit oder umgekehrt erfolgen. Auf diese Weise werden hochaktive Katalysatoren erzeugt, welche z. B. in der Lage sind, Wasserstoff aus geeigneten Substraten, wie Wasser, zu erzeugen oder diesen hochselektiv auf andere Substrate zu übertragen (beispielsweise auf Tolan oder CO2), und deren Aktivität signifikant größer ist als die bisher erreichten. Sie sind durch die Multielektronenübertragung in der Lage, Licht energie zu nutzen, um selektiv entweder a) Stoffe zu oxidieren oder b) Stoffe zu reduzieren. Aber auch jede andere Katalyse, wie Cycloadditionen, metallorganische Kopplungsreaktionen, Polymerisationen oder andere sind möglich. Dabei handelt es sich im einfachsten Fall um einen heterotrinuclearen Komplex bei dem zwei Chromophore, z. B. Ruthenium (II) mit einem katalytisch aktiven Metall, z. B. Pt(II) über einen gemeinsamen Collectorliganden verknüpft sind. Die Richtung des photoinduzierten Elektronentransfers kann beispielsweise durch Variation an den terminalen Liganden des Chromophorsystems, des Collectorliganden und des katalytischen Zentrums gesteuert werden.With these compounds of the general formula, oligonuclear systems have been created which are capable of transferring several electrons from several chromophoric centers to a catalyst metal or, conversely, withdrawing several electrons from a catalytic center. In this case, an electron flow from the chromophoric units to the catalytic unit or vice versa can take place. In this way, highly active catalysts are generated which z. B. are able to generate hydrogen from suitable substrates, such as water, or to transfer this highly selectively to other substrates (for example, tolane or CO 2 ), and their activity is significantly greater than those achieved so far. The multi-electron transfer enables them to use light energy to selectively either a) oxidize substances or b) reduce substances. But any other catalysis, such as cycloadditions, organometallic coupling reactions, polymerizations or others are possible. In the simplest case this is a heterotrinuclear complex in which two chromophores, z. B. ruthenium (II) with a catalytically active metal, for. B. Pt (II) are linked via a common collector ligands. The direction of photoinduced electron transfer can be controlled, for example, by variation at the terminal ligands of the chromophore system, the collector ligand and the catalytic site.
Der Collectorligand CL verknüpft mindestens zwei chromophore Einheiten M mit der katalytisch aktiven Einheit M'. Beim Collectorligand CL handelt es sich um einen Liganden, der über mindestens drei separate Koordinationssphären verfügt, welche für die Verknüpfung der chromophoren Einheiten M mit der oder den katalytischen Einheiten M' zur Verfügung stehen. Er kann entweder bereits als solcher Ligand vor der Komplexierung synthetisiert worden sein oder als Precursor in Form von Collectorligandfragmenten an den chromophoren Einheiten vorhanden sein, die in weiteren Reaktionen erst zu den Collectorliganden CL umgesetzt werden. Die Synthese über die Precursor stellt ein besonderes Verfahren dar, da sie erlaubt, selektiv unterschiedliche Chromophore an einen Collectorliganden CL zu knüpfen aber auch durch einfache Variation des Precursors, den Abstand der einzelnen Komponenten (chromophore Einheiten M, katalytische Einheit M') hochselektiv einzustellen. Alle Koordinationsstellen des Collectorliganden CL können aus einem Donoratom oder aus mehreren Donoratomen, wie beispielsweise N, S, O, Se, P, bestehen oder funktionellen Gruppen, wie z. B COOH, NH2, SH, CONH2, Zucker-, DNA/RNA-, Basen- und Porphyrinderivate enthalten, aber auch schwache Wechselwirkungen, wie Wasserstoffbrücken, sind möglich. Die aufgezählten Koordinationsmöglichkeiten und Atome stellen Beispiele dar und können beliebig erweitert werden. Der Collektorligand kann (nicht zwingend erforderlich) weitere funktionelle Gruppen, wie z. B. COOH, NH2, SH, CONH2, Zucker-, DNA/RNA-, Basen- und Porphyrinderivate, und/oder ein oder mehrere Heteroatome, wie beispielsweise N, S, O, Se, P, aufweisen.The collector ligand CL links at least two chromophoric units M to the catalytically active unit M '. The collector ligand CL is a ligand having at least three separate coordination spheres available for linking the chromophore moieties M to the one or more catalytic moieties M '. It may either have already been synthesized as such a ligand prior to complexation or be present as a precursor in the form of collector ligand fragments on the chromophoric units, which in further reactions are first converted to the collector ligands CL. Synthesis via the precursors represents a special method, since it allows to selectively link different chromophores to a collector ligand CL, but also to adjust the distance of the individual components (chromophore units M, catalytic unit M ') in a highly selective manner by simple variation of the precursor. All coordination sites of the collector ligand CL can consist of one donor atom or of several donor atoms, such as N, S, O, Se, P, or functional groups, such as. B COOH, NH 2 , SH, CONH 2 , sugar, DNA / RNA, base and porphyrin derivatives, but also weak interactions, such as hydrogen bonding, are possible. The enumerated coordination possibilities and atoms are examples and can be extended as desired. The Collektorligand may (not necessarily) other functional groups, such. As COOH, NH 2 , SH, CONH 2 , sugar, DNA / RNA, base and porphyrin derivatives, and / or one or more heteroatoms, such as N, S, O, Se, P, have.
Die chromophoren Einheiten M bestehen aus Metall- oder Halbmetallzentren MCh die von terminalen Liganden L umgeben sind und an den Collectorliganden koordiniert sind. Die chromophoren Einheiten M können, müssen jedoch nicht gleich sein. Es können mehrere jeweils unterschiedliche chromophore Einheiten M über den Collectorliganden CL mit der katalytischen Einheit M' verknüpft werden.The chromophoric units M consist of metal or metalloid centers M Ch which are surrounded by terminal ligands L and coordinated to the collector ligands. The chromophoric units M can, but need not be the same. Several different chromophore units M can be linked to the catalytic unit M 'via the collector ligand CL.
Die Metallzentren MCh sind definiert als Metalle oder Halbmetalle, die in der Lage sind, über photo- und/oder thermische Induktion ein Elektron abzugeben oder aufzunehmen. Dieses ist z. B. für Fe, Ru, Os, Iridium oder Platin in unterschiedlichen Oxidationsstufen gegeben. Ru(II) kann beispielsweise – photoinduziert – ein Elektron abgeben und zu Ru(III) oxidiert werden. Die aufgezählten chromophoren Metalle stellen Beispiele dar und können beliebig erweitert werden. Eine chromophore Einheit M kann an der Peripherie von einer oder mehreren weiteren Metall- oder Halbmetalleinheiten umgeben sein.The metal centers M Ch are defined as metals or semimetals which are capable of donating or taking up an electron via photo- and / or thermal induction. This is z. B. for Fe, Ru, Os, iridium or platinum in different oxidation states. For example, Ru (II) can be - photoinduced - donate an electron and be oxidized to Ru (III). The enumerated chromophoric metals are examples and can be extended as desired. A chromophoric moiety M may be surrounded at the periphery by one or more other metal or semimetal moieties.
Mit
den für die chromophoren Einheiten M erforderlichen Metall-
oder Halbmetallzentren MCh sind allerdings
ein relativ hoher Syntheseaufwand sowie hohe Herstellungskosten
verbunden. Des Weiteren sind diese Metalle oder Halbmetalle nicht
umweltverträglich entsorgungsfähig, was deren
Verwendungsaufwand zusätzlich erhöht. Es wäre
deshalb wünschenswert, diesen Aufwand zu reduzieren, um
die Verwendung der heterooligonuklearen Verbindungen gemäß Hauptpatentanmeldung
Der
Erfindung liegt deshalb die Aufgabe zu Grunde, hochaktive und beständige
Photokatalysatoren gemäß der Hauptpatentanmeldung
Erfindungsgemäß werden
Verbindungen gemäß der in der Hauptpatentanmeldung 
Es
wurde gefunden, dass derartige Photokatalysatoren, die insbesondere
sehr vorteilhaft zur Derivatisierung und zum Abbau funktioneller
organischer Substrate, wie funktionalisierten Kohlenwasserstoffen,
zur Gewinnung von Methan sowie zur Herstellung von Wasserstoff,
beispielsweise aus Wasser, verwendbar sind, eine hinreichend hohe
katalytische Wirkung aufweisen. Wenngleich diese nicht gänzlich
an die Wirkung der in der Hauptpatentanmeldung
Der
große Vorteil ist, dass die vorgeschlagenen Verbindungen
einerseits aufwandgeringer und mit niedrigeren Kosten herstellbar
sind und andererseits umweltverträglicher und besser abbaubar
sind, so dass die Verwendungen dieser Photokatalysatoren gegenüber
dem Einsatz der in der Hauptpatentanmeldung
Die Erfindung soll nachstehend anhand von zwei Ausführungsbeispielen zur Methangewinnung und für die Wasserstoffbildung näher erläutert werden.The Invention will be described below with reference to two embodiments for methane production and hydrogen production be explained.
Vorschlagsgemäß werden
Verbindungen gemäß der in der Hauptpatentanmeldung
Anstelle
dieses Metall- oder Halbmetallzentrum findet bei den nachfolgenden
Ausführungsbeispielen die organische Verbindung 4,4'-Dimethyl-2,2'-bipyridin-Platindichlorid: 
Zu
deren Synthese wurden 100 mg (0,54 mmol) 4,4'-Dimethyl-2,2'-bipyridin
in 20 ml THF (Tetrahydrofuran) gelöst und zu einer salzsauren
Lösung von 225 mg K2PtCl4 getropft. Die Reaktionslösung
wurde einen Tag lang bei Raumtemperatur gerührt. Der gelbe
Niederschlag wurde abfiltriert und im Vakuum getrocknet. Platin
konnte mittels TRFA (Totalreflexions-Röntgenfluoreszenzanalyse)
nachgewiesen wurden.
Ausbeute: 201 mg (83%)
MS (EI): 448
[M]; 413 [M-Cl]; 377 [M-2Cl]; 183 [4,4'-Dimethylbpy]
1H-NMR (200 MHz) in DMSO: 9,267 [d, 2H, C];
8,334 [s, 2H, A]; 7,608 [dd, 2H, B]; 3,090 [s, 6H, CH3]For their synthesis, 100 mg (0.54 mmol) of 4,4'-dimethyl-2,2'-bipyridine were dissolved in 20 ml of THF (tetrahydrofuran) and added dropwise to a hydrochloric acid solution of 225 mg of K 2 PtCl 4 . The reaction solution was stirred for one day at room temperature. The yellow precipitate was filtered off and dried in vacuo. Platinum could be detected by TRFA (total reflection X-ray fluorescence analysis).
Yield: 201 mg (83%)
MS (EI): 448 [M]; 413 [M-Cl]; 377 [M-2Cl]; 183 [4,4'-dimethylbpy]
1 H-NMR (200 MHz) in DMSO: 9.267 [d, 2H, C]; 8,334 [s, 2H, A]; 7.608 [dd, 2H, B]; 3.090 [s, 6H, CH 3 ]
Ausführungsbeispiel 1:Embodiment 1
Verwendung als Photokatalysator für die Herstellung von Methan:Use as photocatalyst for the production of methane:
Anstelle
eines Metall- oder Halbmetallzentrums weisen die Photokatalysator-Verbindungen
gemäß Hauptpatentanmeldung
3 mg des 4,4'-Dimethyl-2,2'-bipyridin-Platindichlorids werden in einem Methylenchlorid/Wassergemisch (2,5 Vol% Wasser) mit 2 molarer TEA (Triethylamin) fünf Stunden lang mit Licht (470 nm Wellenlänge) bestrahlt. Anschließend erfolgte die Methandetektion mittels Gaschromatographie. Als Nebenprodukt entstehen Wasserstoff, Ethan und Ethen.3 mg of 4,4'-dimethyl-2,2'-bipyridine platinum dichloride are in a Methylene chloride / water mixture (2.5% by volume water) with 2 molar TEA (Triethylamine) irradiated with light (470 nm wavelength) for five hours. Subsequently, the methane detection was carried out by gas chromatography. The by-product is hydrogen, ethane and ethene.
Ausführungsbeispiel 2:Embodiment 2:
Verwendung als Photokatalysator für die Herstellung von Methan:Use as photocatalyst for the production of methane:
Anstelle
eines Metall- oder Halbmetallzentrums weisen die Photokatalysator-Verbindungen
gemäß Hauptpatentanmeldung
3 mg des 4,4'-Dimethyl-2,2'-bipyridin-Platindichlorids werden in einem Chloroform/Wassergemisch (2,5 Vol% Wasser) mit 2 molarer TEA (Triethylamin) 20 Stunden lang mit Licht (470 nm Wellenlänge) bestrahlt. Anschließend erfolgte die Methandetektion mittels Gaschromatographie.3 mg of 4,4'-dimethyl-2,2'-bipyridine platinum dichloride are in a Chloroform / water mixture (2.5% by volume water) with 2 molar TEA (triethylamine) Irradiated with light (470 nm wavelength) for 20 hours. Subsequently the methane detection was carried out by gas chromatography.
Ausführungsbeispiel 3:Embodiment 3
Verwendung als Photokatalysator für die Wasserstoffbildung:Use as photocatalyst for the hydrogen formation:
Anstelle
eines Metall- oder Halbmetallzentrums weisen die Photokatalysator-Verbindungen
gemäß Hauptpatentanmeldung
3 mg des 4,4'-Dimethyl-2,2'-bipyridin-Platindichlorids werden in einem ACN/Wassergemisch (2,5 Vol% Wasser) mit 2 molarer TEA (Triethylamin) fünf Stunden lang mit Licht (470 nm Wellenlänge) bestrahlt. Anschließend erfolgt die Wasserstoffdetektion mittels Gaschromatographie.3 mg of 4,4'-dimethyl-2,2'-bipyridine platinum dichloride are in a ACN / water mixture (2.5% by volume water) with 2 molar TEA (triethylamine) five hours with light (470 nm wavelength) irradiated. Subsequently, the hydrogen detection takes place by gas chromatography.
ZITATE ENTHALTEN IN DER BESCHREIBUNGQUOTES INCLUDE IN THE DESCRIPTION
Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.
Zitierte PatentliteraturCited patent literature
- - DE 102007025424 [0001, 0006, 0007, 0008, 0009, 0010, 0012, 0015, 0017, 0019] - DE 102007025424 [0001, 0006, 0007, 0008, 0009, 0010, 0012, 0015, 0017, 0019]
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| DE102008009432A DE102008009432A1 (en) | 2007-05-30 | 2008-02-12 | Hetero-oligonuclear compounds for use as highly active photocatalysts |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102007025424A DE102007025424A1 (en) | 2007-05-30 | 2007-05-30 | New heterooligonuclear compound useful as a highly active photo catalyst for multielectron transfer reaction |
| DE102008009432A DE102008009432A1 (en) | 2007-05-30 | 2008-02-12 | Hetero-oligonuclear compounds for use as highly active photocatalysts |
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| Publication Number | Publication Date |
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| DE102008009432A1 true DE102008009432A1 (en) | 2009-08-13 |
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| DE102007025424A Ceased DE102007025424A1 (en) | 2007-05-30 | 2007-05-30 | New heterooligonuclear compound useful as a highly active photo catalyst for multielectron transfer reaction |
| DE102008009432A Ceased DE102008009432A1 (en) | 2007-05-30 | 2008-02-12 | Hetero-oligonuclear compounds for use as highly active photocatalysts |
| DE102008009433A Withdrawn DE102008009433A1 (en) | 2007-05-30 | 2008-02-12 | Hetero-oligonuclear compounds for use as highly active photocatalysts |
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| DE102007025424A1 (en) | 2007-05-30 | 2008-12-04 | Friedrich-Schiller-Universität Jena | New heterooligonuclear compound useful as a highly active photo catalyst for multielectron transfer reaction |
| US10392395B2 (en) | 2009-10-30 | 2019-08-27 | Sumitomo Chemical Company, Limited | Nitrogen-containing aromatic compounds and metal complexes |
| CN115845922B (en) * | 2022-11-30 | 2023-11-21 | 中山大学 | Visible light catalytic CO 2 Metal-organic framework composite material with cycloaddition reaction and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102007025424A1 (en) | 2007-05-30 | 2008-12-04 | Friedrich-Schiller-Universität Jena | New heterooligonuclear compound useful as a highly active photo catalyst for multielectron transfer reaction |
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| US7122171B2 (en) | 2004-12-02 | 2006-10-17 | Virginia Tech Intellectual Properties, Inc. | Supramolecular complexes as photocatylysts for the production of hydrogen from water |
-
2007
- 2007-05-30 DE DE102007025424A patent/DE102007025424A1/en not_active Ceased
-
2008
- 2008-02-12 DE DE102008009432A patent/DE102008009432A1/en not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102007025424A1 (en) | 2007-05-30 | 2008-12-04 | Friedrich-Schiller-Universität Jena | New heterooligonuclear compound useful as a highly active photo catalyst for multielectron transfer reaction |
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| Publication number | Publication date |
|---|---|
| DE102007025424A1 (en) | 2008-12-04 |
| DE102008009433A1 (en) | 2009-08-13 |
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