local

1
??? ?????????????????
????????????
??????local??
????? ??????????,???????????????
?,????,?????
??????????????
2
1.1 ???????????
1????????????????Zn???ZnO
???Zn??eZn,e??????? ??????ZnO?????????ZnO?n?????
????eZn?????
3
2????????????????????????,????????????
3??????????????Ni2???NiO
??Ni2?????????Ni3Ni2?, ? ???????? ??????NiO???
??????NiO?p?????
4
4??????????????????V2O5
O2-???,?????????????? ,????V5??V4???????
??F??,????????????????????,??V2O5?n????? F?????
?????,????????
5
5???????????
?Li?NiO?????,NiO????,?????
????????,????,??????
6
1.2 ?????
?Fe3O4?Co3O4?,???????O2-???????,M2??1/8?????,M3
??1/2??????? ?????????????
1.3 ????????
????????,????????,????????????,??????????????,???
?????????????,????????????????????????,???????????
??????
7
??2n???
??6n???
n??????????
????????????????????????????,???????????????????
?????????????????????????????????????? ??????????
???,???????????,??1eV?
8
??????,??? ??? ?????,?????????????????,???????,
?????????????
n??????????? p????????????
9
?????????????????, ??A???????????????????,?????
???????????????????n????? ??B???????O???????????
,??????????????????,????????,????????????????????p
?????
10
Fermi??Ef?????????????????????? ????????????????
??????????????????????Fermi????????????
???????????Ei?????fE?? ni????Ei??????????Ni
????????????
11
T 0 K?,Ei lt Ef,fE 1 Ei lt
Ef,fE 0 T gt 0 K?, Ei Ef,fE 1/2
12
????????????????,??????Ef,???????fE?????Ef??,?fE??
??,???Ef??fE???
?????
?????
13
1.4 ???????????
??????????????????????,?????????? ????????????????
???????????????????????????,???????200-240 kJ/mol?
14
H2?ZnO(n????)????,???????Zn2,??????????,Zn2??Zn
?Zn?ZnO???Zn2????,???????? H2?NiO(p????)????,???
?Ni3?????,???Ni3??Ni2?????Ni3????,????????? ??
?????????????????????????
15
???????????????????????????????
16
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20
1.5 ???????????????????
1?N2O???
????
????????
??????
p????????,????,??????,n????????,?????
21
N2O?p????(?NiO)????,?p???????????n????(?ZnO)????,
?p???????????????????????????????,????O-????? ????
??????????????????????n????????????,p???????(?????
?)?????,????,???????????????????n??????????p??????
????,??p?????n???????????,???????????
2??????????p????????,??n????,????????Mn2O3 gt
PbO gt Ag2O gt CoO gt Cu2O gt CdO gtgt ZnO MgO gt
?-Al2O3
22
3?CO?????
1)p????NiO????CO????????????
23
2)n????ZnO????O2?????????????
24
3)??????,?????????????????,???????????????????????
?
4)?????,?????????????????????NH3?CuO?NiO????,?????
????????????
25
1.6 ???????????????????
??????????????,??????????????????,????????????????
??,???????????
CuO?????????????????????????????,???CO2???????????
?
26
???CuO??????
27
?????? ??
28
????????????????????????????????????????????????
?????????????? ??????????????IV?V?VI?????????,??
??V?VI???????,??????????????(?V2O5?MoO3?WO3?)?
29
2.1 ??-????MVK??
??V2O5?????? 1)???????,????,?????? 2)???????????
????????? MVK??????????????????
MVK?????????1)????????,????????????,?????????????
????2)???????????????????????,?MoO3-Bi2O3,MoO3-Sn
O2?,??????????????????
30
??MVK??,??V2O5????????
??????
??????????
???????
?????????v????,????
??
????,???????? ???????,???????????
???????,????????????
31
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33
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34
2.2 ????????
????MAB?A?,?????? ?????? B?B?,???????????? A?B?
?????????
??????????????????????????????????????????????????
????????????????????
35
????????????????????????????????????????,?????????
????? ?????????????????????????????,??????????????
????????????????MoO3-P2O5(P/Mo0.2)???Bi2O3,??????
??,??Bi/(BiMo)0.1?????,???Bi?,???????,??P2O5?V2
O5????,??????????????SnO2,P2O5,V2O5?TiO2?MoO3????,
?????20-60,MoO3????,????????,??????
36
2.3 ?????????
?????????????????????????????O2,ad???????????????
???(O2-?O-?O2-)?
??????????????????? ??????????ESR
??????????????
?H
-83 kJ/mol
248 kJ/mol
-148 kJ/mol
844 kJ/mol
944 kJ/mol
37
??????????????????,???????????????????,?O2(g)?????
??????????
38
2.4 ????????????
???????? 1)????????????,?O2-?O-??????????,???????
????????????????,??????????????????????,?????????,
????????????????????,????????????,????????? 2)????
??????????,?????O2-?????,???????,????????,????????
??????????,????????
39
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40
????????,????????? 1)??????????????????????????,?
??????????O-??????????????????????????????????????
??????????,?????p???????,?NiO?MnO?CoO?Co3O4? 2)??
????????????????????,????????????O2-??,????n????,?
ZnO?SnO2?TiO2????V2O5?????????????????????????????
???,?CoO-MgO,MnO-MgO?? 3)??????????????????,??????
????????????????????????????,??MoO3?WO3?Nb2O3?????
?,?????
41
????????????,????????? ????????????,???????????
??????,??-??????,????????????,???????
??-???(MO)????900 1000 cm-1
??-???(M-O-M)???? 800 900 cm-1 ????????????????
????,?????????????????,?????????
42
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43
???O2-??????????,???????????????,???????????????
I
V2O5???V5????O2-,???????,??????O2- V-OI0.154
nm - 1025 cm-1 V-OII0.202 nm?0.188
nm V-OIII0.177 nm? OI?????,??????????????,?SO2??
????
II
III
I
44
V2O5???MoO3?K???VO?,??????????????????V2O5???????
?VO???????????
45
2.5 ??????
??????????????????
???????????????????????? ??????????????????????
??
????????????????,?Co2?Ni2?Fe2?Mo6?????,???????
??????????,????????????Mg2???????,???????,??????
????
46
????????????????????????????????
Bi2Mo3O12?Fe2Mo3O12???-???????,?Bi2Mo3O12?????????
??????????????????????????Bi3?Fe3????????? Fe3?
??????d??,??????????????,????????? Bi3??????d??,
????????????,??????????????
47
??????????????????????????????,?1-??????1)???????
?????????,?Fe2Mo3O12?Fe3O42)???????????????????,?
FeSbO4?Sb2O4-SnO2?3)????????????,??????,?FePO4?
48
???????????????
3.1 ?????????
1?????? ???????????,??????,?????? ???(????)Cl?S
?P????????????? ??????,??????????? ????CaO?BaO?
MgO??????????????????????????????????? ????(??)?
???????,?SiC??-Al2O3??
2???????????????,?????????????????????
49
3?????
1)?????
2)?????????????ESR?????????
50
4????????????
????????,?????????????70,?????75???????CO2?
51
??????
k1k2 0.08 k3k1 0.04 k3k2 5
CO2????????????????????CO2?????????????CO2?
???????????????????????????
???????????????????80?
52
????????,Voge?????????
Ag O2 ? Ag?O2a Ag?O2a C2H4,a ? C2H4O
Ag?Oa 4Ag?O2a C2H4,a ? 2CO 2H2O 4Ag 2CO
Ag?O2a ? 2CO2 Ag
5??????????????
Bukhtiyarov V.I. _at_ Boreskov Institute of
Catalysis 1) electrophilic oxygen species active
species for epoxidation 2) nucleophilic oxygen
species active species for combustion
53
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54
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55
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56
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58
6?????????????
59
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60
3.2 ????????-?H??
??-H???,?C-H(?)???????C-H???63-82kJ/mol?????,?????
??C-H(?)?????,?????????????Bi2O3-MoO3?????????????
61
1??????
Di-????????1?C??
????????3?C??
?????????????
62
2?????????????????????14C??????Mo-Bi??????????,??
????????14C?????????
1)?CH2CH-14CH3????,????C2H4?CO???????? 2)?14CH2
CH-CH3????,????C2H4?CO???????? 3)?CH214CH-CH3???
?,???C2H4????,?CO????,???????????14C? ???????????
??Mo-Bi??????????H??????????????????
63
3????????????????C-H?????????????????????????????
?????D???,???D????????????D?????????
??????,??????C-H????,???????????,?????????????????
???????????????
64
1-??-3D??????
?????????????????????
??????z????D?????H??????kD/kH0.55/1?
4???????????????Co?Mg???????,??????????,?????????
????????
65
??I????????????0.195nm????????????? ??I?????????
??????????? ??II???C-H???????????? ??III???O-H??
??????????
66
5??????????O2-?
???????????????????,????????? ?????????????????
,????????,???????
?????????????????????????????????????????????????
??????????????????????????????????????????????????
???
67
6?18O2??????18O2?,??????????CH2CH-CH18O(?????54
.6?1.6 kJ/mol)?CH2CH-CH16O(?????100.8?1.6
kJ/mol),??????????????1)????????????2)??????????
???
???
68
Bi2O3-MoO3????,M1?Bi3(????),????????????H???,????
??Bi2O3?????1,5-????M2?Mo6(????),???????????????
Haber?????Mo-O????????????,M2m?????????,?????????
?????
??????????????,??????M1?M2???????????????????????
??????????????????????????????
69
3.3 ???????-???????
????????????,???????????????????MoO3???????????,?
Co3O4?TiO2?Fe2O3?Cr2O3?SnO2????????????SnO2-MoO3(S
nMo9)?? ????388-403 K ?????????3-9?????90
?????1-???2-???????????,???????????
?????????,???????????????,??????,??????,??????????
???????????????????,???????????????
70
?????????????????,????????????????
H218O?????????,?????????,??CH3C18OCH3,????????????
????
71
?????,?????????
? ½ O2- H2O ? 2 OH-
??????,????????B??,OH-???????????,????????