GB2494298A - Bond activation and coupling reactions on anisotropic surfaces - Google Patents
Bond activation and coupling reactions on anisotropic surfaces Download PDFInfo
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- 230000004913 activation Effects 0.000 title claims abstract description 14
- 239000010931 gold Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 35
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052737 gold Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000009792 diffusion process Methods 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 238000006664 bond formation reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000009878 intermolecular interaction Effects 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- 239000000376 reactant Substances 0.000 abstract description 7
- 238000006471 dimerization reaction Methods 0.000 abstract description 5
- QHMGJGNTMQDRQA-UHFFFAOYSA-N dotriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC QHMGJGNTMQDRQA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- RFYDYEACDMPIQG-UHFFFAOYSA-N 9-dodecylpurin-6-amine Chemical compound N1=CN=C2N(CCCCCCCCCCCC)C=NC2=C1N RFYDYEACDMPIQG-UHFFFAOYSA-N 0.000 abstract description 2
- LXWAVCFSFAULCW-UHFFFAOYSA-N 5-methyl-1-octadecylpyrimidine-2,4-dione Chemical compound CCCCCCCCCCCCCCCCCCN1C=C(C)C(=O)NC1=O LXWAVCFSFAULCW-UHFFFAOYSA-N 0.000 abstract 1
- WKCLQJTXFDPDGJ-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCCCC)C1=C(C=CC=C1)CCCCCCCCCCCCCCCCCCCC Chemical compound C(CCCCCCCCCCCCCCCCCCC)C1=C(C=CC=C1)CCCCCCCCCCCCCCCCCCCC WKCLQJTXFDPDGJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 238000004574 scanning tunneling microscopy Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 15
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- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
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- 239000010937 tungsten Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
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- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 3
- 238000000004 low energy electron diffraction Methods 0.000 description 3
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- 125000004429 atom Chemical group 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
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- 238000006317 isomerization reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- KKBTYRLQZHAIHC-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCCCC)C1=CC=C(C=C1)CCCCCCCCCCCCCCCCCCCC Chemical compound C(CCCCCCCCCCCCCCCCCCC)C1=CC=C(C=C1)CCCCCCCCCCCCCCCCCCCC KKBTYRLQZHAIHC-UHFFFAOYSA-N 0.000 description 1
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 1
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N adenyl group Chemical group N1=CN=C2N=CNC2=C1N GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B01J35/60—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B33/00—Oxidation in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
A method for activating covalent bonds (including alkyl C H bond) and coupling reactions at specific sites of the reactant molecules by surface conÂstraint. In said method an anisotropic surface with a one-dimensional constraint is used as the platform and catalyst for the reactions. The reactions include dimerization and. polymerization, depending on the structure of the respective molecules. The surface may be gold {110}, platinum{110}, iridium {110}, or iron {211}, or alloys thereof, but is preferably gold {110}. More preferably, the gold {110} surface has a missing-row construction induced by organic molecules, most preferably having a 1x2 and 1x3 reconstruction. Preferred reactant molecules include alyl-containing molecules, more preferably alaknes, most preferably dotriacontane, di(eicosanyl)benzene (DEB), eicosanylbenzene (EB), 1-(octadecyl)thymine and/or 9-(dodecyl)adenine. The activation and coupling reactions are preferably performed at temperatures up to 300 degrees Celsius.
Description
Title: Bond activation and couplinu reaction
Description
FILED OF THE INVENTION
[0001] This invention relates to bond activation and coupling reactions.
BACKGROUND OF THE INVENTION
[00021 Alkanes are the principal component in petroleum, natural gas and biogas. Since an alkyl C-H bond is one of the most stable bonds in organics, the controllable activation of alkyl C-I-I bond has long been a challenge in organic chemistry and chemical engineering.
[0003] C-Fl bonds can be activated under mild conditions and with high selectivity at metal centers, followed by bond formation between the metal centers and alkane carbons.
However, a multi-step process is usually required to achieve C-C coupling reaction. The well-known Frischer-Tropsch process, which is applied for achieving C-C coupling reac-tion for synthesis of a variety of hydrocarbons from syngas (CO + H2) in industry, is a relatively expensive process. Other heterogeneous catalysis processes were investigated in the last decades and involved hydrocarbons as the starting material reacted at a transition metal surface such as Platinum. Such processes result in various reaction pathways simul- taneously with poor selectivity, including dehydrogenation, hydrogenation, hydrogenoly-sis, isomerization, dehydrocyelization, etc. [0004] A direct C-C coupling reaction resulting in the conversion of low molecular weight hydrocarbons to higher molecular weight hydrocarbons can also be achieved by using cer-tain catalysts such as boron compounds at very high process temperatures (> 1000 0(1) But such processes are not energetically economic.
SUMMARY OF TUE INVENTION
[00051 The present invention provides a method for bond activation and coupling reactions of molecules comprising the steps of: a. adsorbing the molecules on anisotropic surfaces with one dimensional con-straint to allow intermolecular interactions between neighboring molecules in the easy-diffusion direction, b. activating bond formation by heating, c. initializing coupling reactions between neighboring molecules in the easy-diffusion direction at elevated temperatures.
[0006] The material of the surfaces may comprise transition metals or transition metal-containing alloys or the material of the surfaces is chosen from the group comprising gold, platinum, iridium and alloys comprising gold, platinum and iridium with [1 1OF orienta-tion.
[0007] It is further intended that the surface can be a gold { 1 10} surface with missing-row reconstruction induced by organic molecules, wherein the missing row reconstruction might be a 1x2 and 1x3 reconstruction and a reconstructed gold {110} surface shall con-strain molecules and allows one-dimensional reactions.
[0008] According to the present invention the material of the surfaces may comprises iron or an alloy containing iron with {21 I) orientation.
[0009] The reaction temperature for the activation and coupling reaction shall be up to 300 CC.
[0010] Alkyl-containing molecules are intended for use in a method of the present inven-tion, wherein said alkyl-containing molecules arc hydrocarbons or alkanes.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The invention provides a method for activating covalent bonds (including alkyl C-H bond) and coupling reactions at specific sites of the reactant molecules by surface constraint. In said method an anisotropic surface with a one-dimensional constraint is used as the platform and catalyst for the reactions. The reactions include dimerization and polymerization, depending on the structure of the respective molecules. The method com-prises the following steps: a. Adsorption of the molecules on the anisotropic surface: The diffusion ability of the molecules in one direction is larger than in the perpendicular direction, due to the anisotropy of the surface with one dimensional constraint. As a result, the mole- cules only interact with the neighboring molecules on both sides in the easy- diffusion direction while the interaction from the neighboring molecules in the per-pendicular direction is negligible.
b. Bond activation by heating: Bond activation takes place at specific sites, usually on both sides of the easy-diffusion direction, at elevated temperatures (< 300 °C). X, which is a covalently bonded atom (e.g. C-X, X = hydrogen) or a functional group, is dissociated from the main part of the molecule.
c. Coupling reaction: The coupling reaction takes place exclusively between the neighboring molecules in the easy-diffusion direction. In ease that each molecule contains one activated bond, the coupling reaction results in dimerization of the re- actant molecules. In case that each molecule contains two activated bonds, the cou-pling reaction results in polymerization. The process can be described as follows: i. R-X -F X'-R' 3 R-R' (general) ii. X-R-Y -F X_RJYI 3 -(R)n-(R)m-(polymerization) iii. R-CI-13 + I-13C-R' 3 R-(CH2)2-R' (aRcyl C-H activation and C-C cou-pling) iv. H3C-R-CH3 + H3C-W-CH3 3 -[H2C-R-CH2]n-[H2C-R-CH2]m- (polymerization) [0012] The disclosed method comprises the steps of using a metallic surface with aniso- tropic property as a platform and a heterogeneous catalyst for the bond activation and cou-pling reaction, providing suitable surface-active molecules which can be constrained by the anisotropic surface and the conditions under which the bond activation and coupling reac-tion take place.
[0013] The key point of the present invention is the anisotropic surface with one- dimensional constraint, which acts as the platform and heterogeneous cata'yst for the pro- cess. Such anisotropic property with one-dimensional constraint exists on certain crystal-line surfaces with specific azimuth. Among the low-Miller-index facets of metals (or metal alloys) with fee lattice, the 1 10} facets are better, while the { 111} facets have no aniso-tropic property as the { 110) facets and are not used in a method according to the invention.
[0014] In particular, the {110 facets of iridium, platinum, and gold crystals, on which missing row 1x2 reconstruction is formed, strengthening the anisotropic property, are pre-ferred. The reconstruction grooves with the atomic rows as borders efficiently confine the diffusion of adsorbed molecules and constrain the molecules to interact only with the neighboring molecules in the easy-diffusion direction.
[00151 In case of metals with bce crystal structure, (2111 facets instead of (1101 facets show similar anisotropic property as the fcc-{ 110) facets and are also preferred for use in a method according to the present invention. In particular, a Fe { 211} surface shows lx 2 reconstruction induced by hydrogen. I-ugh-Miller-index vicinal surfaces exhibiting succes-sions of atomic steps and narrow terraces (< 10 nm) have a similar ability to constrain the adsorbed molecules with anisotropic diffusion probability and specific bond activation sites. Nevertheless, the surfaces that possess such anisotropic property are not limited in bee and fcc crystals.
[00161 Although the above anisotropic facets are usually not the most energy favorable facets, such surfaces can be obtained by cutting a bulk crystal in a specific azimuth. In or-der to obtain a clean surface with atomic flatness, the known sputtering-annealing process is used under ultrahigh vacuum conditions. The anisotropic surfaces can also be obtained by depositing one or a few layers of one type of metal on a substrate of another material.
Nanoparticles and nanobelts of certain transition metals including gold with anisotropic 1 10} facets, which are suitable for constraint of the reactant molecules, can be prepared.
[0017] The molecules adsorbed on the surface possess substantial diffusion ability at the reaction temperature (<300 °C). The diffusion ability is anisotropic due to the spatial con-straint by the surface. The molecules can move freely in the easy-diffusion direction, while the movement in the perpendicular direction is limited by the atomic rows in case of sur-faces with missing-row reconstruction or by step edges in case of vicinal surfaces. As a result, the molecules can exclusively contact/interact with their neighbors in the easy-diffusion direction. The molecules possess intermediate interaction with the surface and the anisotropic property of the surface is kept or strengthened with the adsorbed molecules.
[0018] The molecules used as reactant in the inventive strategy have the formula R-X or X-R-Y. Generally, R is the backbone of the molecule which is mainly responsible for the adsorption behavior on the said anisotropic surface with specific orientation. The compati-Nc size of the reactant is preferential, and the shape and size of the reactants arc ninable. X and Y (X = Y or X!= Y) are the reactive part of the molecule. After reaction, X (and Y) could be a suitable leaving group, which can be readily desorbed from the surface under the used reaction conditions. Preferentially, X is a hydrogen atom, therefore X-R-Y and R-X are hydrocarbons.
[0019] The following reactions take place on the anisotropic surface generally at elevated temperatures (<300 °C): a. R-X + X'-R' 3 R-R' (general) b. X-R-Y -I-X'-R'-Y 3 -(R)n-(R')m-(polymerization c. R-CH3 -F H3C-R' 3 R-(Cl-12)2-R' (alkyl C-H activation and C-C cou-pling) d. FI3C-R-CH3 + H3C-R'-CFI3 3 -[H2C-R-CH2]n-[H2C--R'-CH2]m- (polymerization) [0020] Since the molecule is spatially constrained into a one-dimensional pathway, only the two ends in the easy-diffusion direction can be activated. The reactive part of the mole-cule X (or X') will be dissociated form the major part of the molecule R (or R') and may be desorbed from the surface. Bond formation reaction then takes place between both R/R' fragments. The constraint from the surface keeps the backbone fragments of the mo1ccucs and prevents other reactions such as dehydrogenation, hydrogenation, hydrogenolysis, isomerization, dchydrocyclization, etc., which are the possible reactions catalyzed by the isotropic surfaces (fcc-(111) and bce-110).
[00211 In case that only one site of the two possible sites in the easy-diffusion direction is activated, the coupling reaction results in dimerization (comp. i and iii). In case that both sites are activated, the coupling reaction results in polymerization reaction (eomp ii and iv). For polymerization, the step edges of the surface have no obvious effect on the reac-tion and the polymer chains can spread though the step edges.
EXAMPLES
[0022] The invention will be illustrated by examples and figures without being limited to the described embodiments.
Example I
[0023] Repeated Ar+-sputtering and annealing processes under ultrahigh vacuum cleaned the single crystal line gold { 110 surface with a diameter of 10 mm. Dotriacontane (C2Ho5; X-R-X, X = H) was deposited onto the gold {1 I O} surface at room temperature from a quartz crucible heated to 105 °C. The deposition rate was about 0.1 monolayer per minute (1 monolayer corresponds to about 0.7 molecule per nm2). The as-grown sample was heat-ed to 160 °C for 3 hours by a direct current tungsten filament located on the backside of the sample. The as-prepared sample was analyzed by scanning tunneling microscopy IS (STM) at 78 K and by low energy electron diffraction (LEED) at room temperature. The results are shown in figure 1.
[0024] The deposition of the molecules on the surface did not change the missing-row 1x2 reconstruction of thc gold (ll0} surface and the molecules adsorbed on the surface with their longitudinal axis along the atomic gold rows. The molecules were covalently bonded together by their ends when the sample was annealed at a temperature in the range from to 240 °C, accompanied by the formation of the I x3 reconstruction of the gold { 1101 surface.
[0025] The polymerized (CH2)11 chains, located in the 1 x3 reconstruction grooves, could cross through the step edges of the substrate surface. By STM tip manipulation, sections of the polymer chains could be released from the grooves (comp. Fig. lc). The lengths of the released sections of the polymer chains are up to several hundred nanometers. The frill length of the polymer chains depends on both the size and quality (orientation accuracy, purity, etc.) of the substrate surface. The periodicities of the gold atomic rows and the pol- ymer chains arc 0.28 nm and 0.25 nm, respectively. The mismatch between the two pcrio-dicities results in a Morié pattern with a larger periodicity (6 times of the periodicity of gold atomic rows or 7 times of polymer chains), as observed by STM and LEED.
Example II
[0026] Repeated Ar+-sputtering and annealing processes under ultrahigh vacuum cleaned the single crystalline gold 110} surface with a diameter of 10 mm. 1,4-di(eicosanyl)benzene (DEB, C20H41(C5H4)C20H41, X-R--X, X = H) was deposited onto the gold (l10} surface at room temperature from a quartz crucible heated to 185 °C. The dep-osition rate was about 0.25 monolayer per minute (1 monolayer corresponds to about 0.5 molecule per nm2). The as-grown sample was heated to 147 °C for 10 hours by a direct current tungsten filament located on the back side of the sample. The sample was analyzed by STIVI at 78 K. The results are shown in figure 2.
[0027] Compared with the side alkyl chains, the phenyl groups at the center of the DEB molecules showed bright protrusions in the STM images of the as-deposited sample before annealing. The alkyl chains were along the gold atomic rows of the 1x2 reconstruction.
The molecules were mainly linear polymerized by end/end C-C coupling by annealing the sample at a temperature in the range from 140 to 240 °C. The polymer chains located in the grooves of the 1 x3 reconstmctcd substrate surface. The phcnyl rings were distributed on the polymer chains with equal distance (about S nm). Most molecules bonded via the terminal C atoms and a few via the second to last C atoms, resulting in the formation of a branched methyl group at the soldered sites. The branched methyl groups exhibited a half circle feature in the STM image.
Example III
[0028] Repeated Ar+-sputtering and annealing processes under ultrahigh vacuum cleaned the single crystalline gold {1 10) surface with a diameter of 10mm. Eicosanylbenzenc (EB, (C6H5)C20H41, R-X, X = H) was deposited onto the gold 110 surface at room tempera-ture from a quartz crucible heated to 60 °C. The deposition rate was about 0.1 monolayer per minute (1 monolayer corresponds to about 1 molecule per nm2). The as-grown sample was heated to 205 °C for 20 minutes by a direct current tungsten filament located on the backside of the sample. The sample was analyzed by scanning tunneling microscopy at 78 K. The results are shown in figure 3.
[0029] The phenyl group is inert at the used reaction conditions. Dimerization of EB mole-cules took place at a temperature at the range from 140 to 240 °C, accompanied with the formation of gold {110}-1x3 reconstruction. There are two main dimers: type cx. dimer by C-C coupling between the terminal C atoms of two EB molecules, and type fI dimer by C-C coupling between the terminal C atom of one molecule and the carbon atom connect-ed to the terminal C atom of another molecule. These two types of C-C coupling were also observed in example II (Fig. 2c)
Example IV
[0030] Repeated Ar+-sputtering and annealing processes under ultrahigh vacuum cleaned the single crystalline gold (11 0} surface with a diameter of 10 mm. I -(octadeeyl)thymine (Thy-C13H37, X-R-Y, X = Thy. Y = H) was deposited onto the gold 1l0 surface at room temperature from a quartz crucible heated to 120 °C. The deposition rate was about 0.1 monolayer per minute (1 monolayer corresponds to about I molecule per nm2). The as-grown sample was heated to 170 °C for 20 minutes by a direct current tungsten filament located on the backside of the sample. The sample was analyzed by scanning tunneling microscopy at 78 K. The results are shown in figure 4.
[00311 The Thymine head groups werc cleaved at the C-N bond and desorbed from the surface by annealing. The remaining alkyl chains along the atomic gold rows located in the I x3 grooves were polymerized through the terminal cabon atoms.
Example V
[0032] Repeated Ar+-sputtering and annealing processes under ultrahigh vacuum cleaned the single crystalline gold (110) surface with a diameter of 10 mm. 9-(dodecyl)adenine (Ade-C12H25, X-R-Y, X = Me, Y = H) molecules were deposited onto the gold {110} surface at room temperature from a quartz crucible heated to 90 °C. The deposition rate was about 0.1 monolayer per minute (1 monolayer corresponds to about 1 molecule per nm2). The as-grown sample was heated to 170 °C for 20 minutes by a direct current tung-sten filament located on the backside of the sample. The sample was analyzed by scanning tunneling microscopy at 78 K. The results are shown in figures.
[0033] The adenine head groups were cleaved at the C-N bond and desorbed from the sur-face by annealing. The remaining alkyl chains along the atomic gold rows located in the 1 x3 grooves were polymerized through the terminal carbon atoms.
DESCRIPTION OF THE FIGURES
[0034j Figure 1 shows in (a) scanning tunneling microscopy image (STM) of polymerized (CH2)11 chains in Au{110J_1x3 grooves. (lOxlS nm2, -0.02 V, 2 nA) and (b) large-scale STM image of polymerized (CH2)n chains in Au{ 1 1O}-1x3 grooves. A few chains are released from the grooves by the STM tip. (50x70 nm2, -1 V, 0.3 nA) In (c) low energy electron diffraction patterns of bare Au { 11 0} -I x2 reconstruction (left) and polymerized (CH2)11 chains in Au{110}_1x3 grooves (right) are showm The Moriê pattern resulting from the mismatch between the Au atomic rows and the (CH2)1, chains is shown. Beam energy, 40 eV.
IS [0035] Figure 2 shows in (a) STM image of DEB monomers on Au{ 1 10}-1 x2. (lox 16 nm2, -0.5 V, 0.5 nA). Bright dots are assigned to phenyl rings and in (b) scanning tunnel-ing microscopy image of DEB polymers on Au{110)1x3 is shown. Dotted circles denote the phenyl rings on one polymer chain. (6x17.5 rnn2,-1 V. 2nA) [00361 Figure 3 shows in scanning tunneling microscopy image of EB dimers on Au110}-lx3. (8x14.6 nm2, -IV, 0.5 nA).
[0037] Figure 4 shows in (a) STM image of polymerized (Cl-12)n chains in Au{1 10}-l x3 grooves. (16.9x 10.4 nm2, -0.1 V, 2 nA).
[0038] Fig. 5 shows in (a) STM image ofpolymerized (Cl-12)n chains in Au{110}lx3 grooves. (50x50 nm2, -0.1 V, 2 nA).
Claims (1)
- <claim-text>Claims 1. A method for bond activation and coupling reactions of molecules comprising the steps of: a. adsorbing thc molecules on anisotropic surfaces with one dimensional con-straint to allow intermolecular interactions between neighboring molecules in the easy-diffusion direction, b. activating bond formation by heating, c. initializing coupling reactions between neighboring molecules in the easy-diffision direction at elevated temperatures.</claim-text> <claim-text>2. The method of claim 1, wherein the material of the surfaces comprises transition metals or transition metal-containing alloys.</claim-text> <claim-text>3. The method of any of claims I or 2, wherein the material of the surfaces is chosen from the group comprising gold, platinum, iridium and alloys comprising gold, platinum and iridium with {ll0} orientation.</claim-text> <claim-text>4. The method of any of claims 1 to 3, wherein the surface is a gold {110} surface with missing-row reconstruction induced by organic molecules.</claim-text> <claim-text>5. The method of claim 4, wherein the missing row reconstmction is a 1x2 and]x3 reconstruction.</claim-text> <claim-text>6. The method of claims 4 or 5, wherein a reconstructed gold [1 10} surface constrains molecules and allows one-dimensional reactions.</claim-text> <claim-text>7. The method of claims 1 to 3, wherein the material of the surfaces comprises iron or an alloy containing iron with [211} orientation.</claim-text> <claim-text>8. The method of any of claims 1 to 7, wherein the activation and coupling reaction are performed at temperatures up to 300 °C.9. The method of claims ito 8 using alkyl-containing molecules.1 0. The method of claim 9, wherein said alkyl-containing molecules are hydrocarbons or alkanes.</claim-text>
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| J. Am. Chem. Soc. Vol. 116, 1994, (Deborah M. Jaffey and Robert J. Madix), 'Reactivity of Sulfur-contaning Molecules on Noble Metal Surfaces. 2. tert-Butyl Thioalcohol on Au(110)', pages 3012-3019 * |
| J. Am. Chem. Soc. Vol. 116, 1994, (Deborah M. Jaffey and Robert J. Madix), 'Reactivity of Sulfur-contaning Molecules on Noble Metal Surfaces. 4. Benzenethiol on Au(110)', pages 3020-3027 * |
| Science (Washington, DC, United States), Vol. 334(6053), October 14 2011, (Zhong, Dingyong et al), 'Linear Alkane Polymerization on a Gold Surface', pages 213-216, ISSN: 0036-8075 * |
| Small, Vol. 8(3), 2012 (published online December 15 2011), (Jiang, Lin et al), 'Chemical Reaction on a Solid Surface with Nanoconfined Geometry', pages 333-335, ISSN: 1613-6810 * |
| Surface Science, Vol. 311, 1994, (Deborah M. Jaffey; Robert J. Madix), 'The reactivity of sulfur-contaning molecules on noble metal surfaces III. Ethanethiol on Au(110) and Ag(110)', pages 159-171 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107501026A (en) * | 2017-07-18 | 2017-12-22 | 中山大学 | A kind of method for preparing long chain alkane using aliphatic acid annealing decarboxylation |
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