[e-mail]

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• ???????
• ??????????
• 3600435(???)
• huangwx_at_ustc.edu.cn
• http//staff.ustc.edu.cn/huang
  wx

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• ltlt??????gtgt ???,???,??? ??
• ltlt????gtgt ?? ?
• ltlt??????gtgt ??? ? ?
• ltltHandbook of Heterogeneous Catalysisgtgt Edited by
  G. Ertl, H. Knözinger, J. Weitkamp

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??? ??

• ??????????
• ??(catalysis)????,??????????
• ?????????????
• ???????????????
• ???????????,????????
• The economic contribution of catalysis is as
• remarkable as the phenomenon itself.
• Approximately one third of material gross
  national
• product in the US involves a catalytic process
• somewhere in the production chain. Confining
• analysis to the chemical industry, the proportion
  of
• processes using catalysts is 80 and increasing.
• Chemistry Industry, Jan 21, 2002, Page 22

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????????
???? ???
??? Fe-Al2O3-K2O
???? SiO2-Al2O3,??
???? Pt, Pt-Re
???? H3PO4/???
???? PdCl2-CuCl2
?????? V2O5/???
??? Pt
????? P-Mo-Bi?
???? ?-TiCl3-AlEt3
?????? Pt/Al2O3
??? Ni/Al2O3
F-T?? Fe,Co,Ni
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1997????????4????????2020??????????????????????
?,??????????????????,??????????2020??????? 1997?
,IUPAC?????21?????????????????????? 2001?3?,??
???????????????????????,???????????????,????????2
002?5????????????????,??????????2005?????????????(
PNNL)?????????(http//iic.pnl.gov/),??????????????
???????????? 2003?3?,science??????????????7?
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• ???????, ?????
• ???????---??---??---??
• 2.1 History before 1940
• 1834? Berzelius, ??catalysis??
• 1814? Kirchhoff, ??????????
• 1817? Humphry Davy, ???????????????????
• 1824? Henry, ???????????? ??????H2?O2?Pt????
  ????????,CO,???????????
• 1824? Döbereiner, ????????-tinderbox
• 1834? Michael Faraday???????????????

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• 1845? Grove,??????????????????
• 1860??? Phillips, ?????SO2????? SO3???
• 1871? ???????(Deacon process)HCl???????
• 1877? Lemoine, ??HI????????????????????????(19_at_3
  50?C)
• 1879? Bertholet, ???????????????, ????????????
• 1900??? ??????
• 
  foodstuffs
• Oils, fats waxes
  vitamins
• 
  medicines,
• 
  soap

Ni-based catalysts
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• 1909?7?2? Fritz Haber, ??????Fe3O4????,
  ????????N2?H2????????(BASF???)
• 1923? BASF??, ????????????(400?C, 200bar,Zn-Cr
  Oxides????)
• 1937? Union Carbide??, ?????????????????
• Late 1930s ????(catalytic cracking)
• Fixed-bed catalytic cracking
  reactors
• Fluid-bed/Fluidized catalytic
  cracking (FCC)
• 1930s Ipatieff Pines, ?????????(solid
  phosphoric acid, SPA)

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• 2.2 Applied catalysis since the 1940s
• ?????(synthetic zeolite)???????
• 1960? ?????
• 1964? ????
• 1974?? ZSM-5????
• MTG (methanol to
  gasoline)
• Xylene isomerization

HR-TEM of ZSM-5
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• ??????(dual-function catalysts)????????
• ????
• ?????????????????????
• ????????-??
• ???????

Pt/Al2O3 dual-function catalyst MCP
methylcyclopentane He n-hexane
i-He isohexane CH cyclopentane
CHde cyclohexadiene B benzene
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• ????/???? Co/MoS2, Ni/WS2 supported on Al2O3
• ???? catalytic hydrocarbon reforming catalytic
  steam-reforming
• ???????/????
• ???????
• ??????? Ziegler-Natta ???(TiCl3/MgCl2)

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• 2.3 Current Trends in Applied Catalysis
• Auto-Exhaust Catalysts (Three-way catalysts)
• Pt-Rh/CeO2-Al2O3/Mg2Si5Al4O18

The effects of air/fuel ratio on the emission in
auto-exhaust of HC, NO, and CO
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• Catalysts in Electrochemistry
  Photoelectrochemistry
• ????? ???, CO2?????, ?????

Photosynthesis
Photoelectrolysis
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• Asymmetric Sites on Heterogeneous Catalysts
• Modifying the solid surfaces to function
  enantioselectively
• Homogeneous catalysis 3-D solutions
• Heterogeneous catalysis 2-D surface
• 2-D STEREOSELECTIVITY Chemical engeneering
  News, 2002, 80 (12) 43-46

Immobilized Transition Metals homogeneous/enzyme
catalysts high selectivity heterogeneous
catalysts ease of separation of products
and reactants
from catalysts
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• Immobilized Enzymes and Cells

• Schematic representations of
• Immobilized enzyme systems
• Covalently bonded enzyme-Polymer conjugate
• (b) Covalently bonded inter-molecularly
  crosslinked enzyme conjugate
• (c) Adsorbed enzyme-polymer conjugate
• (d) Polymer lattice-entrapped enzyme conjugate
• (e) Microencapsulated enzyme

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??????, ???????????????,??????????????????????.

• Catalytic Antibodies
• (?????)
• Ribozymes (???RNA)

Catalytic Oxidation of Methane the Centrepiece
of Future Power Sources (1) Catalytic combustion
of methane (2) Partial oxidation of methane
(POM) (3) Oxidative coupling of methane (OCM) (4)
Methane Dehydroaromatization
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• 2.4 21?????????

A selection of environmental challenges
Development of zero-waste processes
Minimization of hazardous products and
greenhouse gases Replacement of
corrosive liquid acid catalysts by benign solid
acid catalysts Evolution of sustainable
systems Reduction in volume of
by-product Development of processes
requiring less consumption of catalysts
Elimination of voluminous by-products
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A selection of technological challenges
Reformulated transport fuels
Development of catalytic automobiles operating on
methanol dissociation Single-step
synthesis of desirable products
Development of processes using CO2 as reactants
Cheaper and safer methods of generating
hydrogen New catalytic membranes
Fischer-Tropsch catalysts for sharply defined
reaction products Efficient, safe
methods of generating hydrogen peroxide (from H2
and O2) Engineered proteins for
pharmaceutical use


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?????????????????????
????????????? Schematic illustrations of the
multi-disciplinary nature of heterogeneous
catalysis science
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• ??????
• 4.1 ????????
• ???(Catalyst) a substance that increases the
  rate of attainment of chemical equilibrium
  without itself undergoing chemical change.
• ??????????, ???????????????,??????????????
• ????????????????????,????????????????????????,???
  ?????????????
• ?? (1)V2O5????SO2?SO3
• (2)?????????????????
• (3)???????????

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• 4.2 ???????
• ?????
• (1)??????(Heterogeneous catalysis)
  ????????????????????????????
• (2)??????(Homogeneous catalysis)?????????????????
  ???????????????????
• (3)???(Enzymes catalysis)????????????????????????
  ??,??????????

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4.3 ????????? ????????????,????????????
????????????
??? ?????(????)/ ???????(????)/
SO2 0.002 8.19
SO2 0.068 8.34
SO2 0.079 8.20
ZnSO4 2.7 8.13
HCl 0.15 8.15
?? 0.52 8.27
?? 0.54 8.10
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4.4 ?????????
E??ltE???
??????????????

• ????????????, ?????????????,
• ????????.

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(No Transcript)
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4.5 ?????????????
1?????(catalytic activity)??????????

?????
???????????(conversion)
????(reaction rate)
????(turn-over frequency, TOF)
???(activation energy)
???????????
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• TOF???????????

TOF (s-1)
??????????(????100-500?C, ??????bar)(?????????)
10-2-102 s-1
?????(?????????)
???? ???????? ?????
103 104 107
ZSM-5 (450?C) (???(???)??????)
500 ?107
1-???? 1-?????
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2????(selectivity)?????????????,
??????????????
???

• ???????

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???????????,???????????????
??????? ?????? ????????????????
3???????(yield)???????????????
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????????
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4.6 ?????????
??????????????????,??????,???????
??????
?? ??
?? ??,?? Ni, Pd, Pt (Cu)
?? ?? Ag, Pt
?? ????? Pt/????
?? ?? Pd/??
????? ???? ???????
????? ?? Fe2O3,ZnO,Cr2O3/Fe2O3
?? ?? ????????
?? ?? H3PO4/??
?? ??,???,?? SiO2-Al2O3????
??????? ???? ?-TiCl3 Al(C2H5)2Cl
??????? ???,??? RhCl(CO)(PPh3)2
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• ????????????

??,???????? (1)??????lt1cm2??????lt0.01ML????? (2)
??????????????????????????????????? (3)??????????
??????????????? (4)????????????,??????????.
????????? gt10?s ???????? ps ?fs
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???????????

• ltltAdvance in Catalysisgtgt (Review)
• ltltCatalysis Reviewsgtgt (Review)
• ltltJournal of Catalysisgtgt
• ltltApplied Catalysisgtgt A B
• ltltJournal of Molecular Catalysisgtgt A B
• ltltTopics in Catalysisgtgt
• ltltCatalysis Todaygtgt
• ltltCatalysis Lettersgtgt
• ltltCatalysis Communicationsgtgt
• ltlt????gtgt, ltlt????gtgt, ltlt????gtgt?
• ????
• ??????