Bowker M., Davies P.R. (Eds.) Scanning Tunneling Microscopy in Surface Science, Nanoscience and Catalysis

Подождите немного. Документ загружается.

that sits in the vacancy is connected to two Ti

3 þ

ions. In contrast, the adjacent OH

group formed by the hydrogen that splits from HOH is bound to only one Ti

3 þ

ion

and a Ti

4 þ

ion. It is important to note that this is a simpliﬁed description of the charge

distribution, since scanned angle PhD measurements clearly show that the charge

distribution around O

-vacs is rather complex [64] and one would expect a similar

situation for OH

Arrhenius analysis of OH

diffusion in the temperature range 300–410 K, for

already separated OH

, gives E

¼0.75 eV [63]. DFT calculations predict a much

higher barrierof 1.29 eV.Even when considering an intermediate relay point whereby

the OH

diffuses to an in-plane O atom before the next O

site [65], E

is reduced only

to 1.19 eV [63]. This is still much higher than the experimental value. In light of this

large discrepancy, Li et al. tentatively propose a two-stage diffusion mechanism

whereby electronic charge associated with the OH

diffuses ﬁrst followed by

diffusion of the OH

itself.

8.7

Tuning the Densities of Oxygen Vacancies and Surface Hydroxyl on TiO

(1 1 0)

The engineering of surfaces is an idea that has come to the fore recently. This is

related to the drive to build nanodevices, but such especially prepared surfaces are

also valuable in providing controlled surfaces for reactivity tests, as described in

Sections 8.3 and 8.4.

Experience shows that the density of O

-vacs can be varied by changing the anneal

temperature or the anneal time [66]. Wendt et al. [18] assessed this systematically by

demonstrating a linear dependence of the O

-vac density (measured by STM) on the

sample history, the latter being deﬁned as the anneal temperature anneal time.

The defect density can be controlled in a more ﬂexible manner by the use of

electron bombardment. For some time [44, 45, 67], this method has been used to

introduce O

-vacs at the surface. Until recently, however, evidence for O

-vac

formation has come only from the spectroscopic signature. Pang et al. used STM

to assess the atomic-scale surface structure of TiO

(1 1 0) following electron

bombardment [17]. Figure 8.14a shows an image of the TiO

(1 1 0) surface following

electron bombardment at 75 eV with an emission current of approximately 0.1 mA

(0.03 mA cm

2

) and a duration of 7 s. The image appears similar to those recorded

from sputter/annealed TiO

(1 1 0) surfaces but with a rather high O

-vac concen-

tration of approximately 11% ML and a low OH

concentration of approximately 1.5%

ML. Figure 8.14b contains an image of the surface measured prior to electron

bombardment that shows the surface was covered with approximately 12% ML OH

and only approximately 0.4% ML O

-vacs. This clearly shows that electron bom-

bardment does indeed introduce O

-vacs. It is equally clear that the OH

density is

greatly reduced by the electron bombardment.

Electron bombardment for longer durations and higher energies led to more

severe surface modiﬁcations, such as surface pitting and disordered 1 n recon-

structed areas [17]. This means that the introduction of O

-vacs by electron bom-

234

8 Point Defects on Rutile TiO

(1 1 0): Reactivity, Dynamics, and Tunability

bardment has to be carefully controlled to avoid the formation of these other

structures. While electron bombardment can be used to introduce O

-vacs, there

is also considerable interest in preparing pseudoperfect surfaces where the only

defects are step edges. Such pseudoperfect surfaces allow processes on normal

surface sites to be separated from the often more reactive defect sites.

Figure 8.14 (a) (345 Å)

STM image of

TiO

(1 1 0) following electron bombardment

at 75 eV and 0.1 mA (0.03 mA cm

2

) for

7 s. The surface contains 11% O

-vacs and

1.5% OH

. Some OH

and O

-vac defects

are indicated with red and blue crosses,

respectively. The circles surround electron

bombardment-induced pits. (b) (220 Å 140 Å)

STM image taken prior to electron bom-

bardment. The surface contains 12% ML

and 0.4% ML O

-vacs. The image is color

contoured so that OH

appear yellow, OH

pairs appear red, and O

-vacs appear green.

Squares are drawn around some of the

-vacs. (Modified with permission from

Ref. [17].)

8.7 Tuning the Densities of Oxygen Vacancies and Surface Hydroxyl on TiO

(1 1 0)

235

In Section 8.3, we already hint at how pseudoperfect surfaces can be created locally.

By scanning a surface at approximately þ3 V, hydrogen from OH

can be desorbed

leaving O

-vacs intact but, of course, if the O

-vacs are already removed by exposure to

water, then a pseudoperfect part of the surface can be created. Gan et al. [68] suggest a

way to make pseudoperfect surfaces not restricted to local areas. They annealed their

sample ﬁrst in an oxygen plasma at 1073 K, then in UHV at 773 K. High-resolution

STM images show no evidence of point defects, although this in itself cannot

necessarily be taken as evidence for a pseudoperfect surface. This is because point

defects often become invisible in STM images depending on the nature of the tip.

Valence band photoelectron spectroscopy would be useful here because if the surface

is devoid of O

-vacs, no bandgap states should be detected.

8.8

Outlook

Over the past decade or so, our understanding of oxide surfaces has markedly

improved, especially in the case of the model oxide surface – TiO

(1 1 0). In particular,

the inﬂuence of defects such as oxygen vacancies on the surface reactivity has been

demonstrated in exquisite detail and it is clear that they play a crucial role in many

surface reactions. As we have shown in this chapter, scanning probes have been

instrumental in evaluating the surface reactivity as they allow individual defects,

reactants, and products to be imaged on relatively short timescales (seconds or

minutes).

High-resolution STM and NC-AFM images have appeared both at elevated

pressures and in liquids, and one would expect a great deal of attention to be focused

in this direction over the coming years. An area of particular topical interest is the

interface between light harvesting surfaces (e.g., TiO

) and liquid water in connection

with photocatalysis.

Despite the enormous impact that scanning probe methods have had on our

understanding of reactions at oxide surfaces, both STMand AFM suffer from the lack

of chemical speciﬁcity. The application of STM–inelastic electron tunneling spec-

troscopy is a potential solution as it can be used to measure the vibrational spectrum

of individual molecules at the surface [69, 70].

References

1 Fujishima, A. and Honda, K. (1972)

Nature, 238, 37.

2 Gr

€

atzel, M. (2001) Nature, 414, 338.

3 Yoon, B., H

€

akkinen, H., Landman, U.,

€

orz, A.S., Antonietti, J.-M., Abbet, S.,

Judai, K., and Heiz, U. (2005) Science,

307, 403.

4 Tauster, S.J. (1987) Acc. Chem. Res., 20, 389.

5 Diebold, U. (2003) Surf. Sci. Rep., 48, 53.

6 Komiyama, M. and Gu, M. (1997)

Appl. Surf. Sci., 120, 125.

7 Sasahara, A., Kitamura, S., Uetsuka, H.,

and Onishi, H. (2004) J. Phys. Chem. B,

108, 15735.

236

8 Point Defects on Rutile TiO

(1 1 0): Reactivity, Dynamics, and Tunability

8 Kolmakov, A. and Goodman, D.W. (2003)

Rev. Sci. Instrum., 74, 2444.

9 Henrich, V.E. and Cox, P.A. (1994)

The Surface Science of Metal Oxides,

Cambridge University Press, Cambridge.

10 Freund, H.-J. (1999) Faraday Discuss.,

114,1.

11 Diebold, U., Anderson, J.F., Ng, K.-O., and

Vanderbilt, D. (1996) Phys. Rev. Lett., 77,

1322.

12 Diebold, U., Lehman, J., Mahmoud, T.,

Kuhn,M., Leonardelli,G., Hebenstreit,W.,

Schmid, M., and Varga, P. (1998) Surf. Sci.,

411, 137.

13 Suzuki, S., Fukui, K., Onishi, H., and

Iwasawa, Y. (2000) Phys. Rev. Lett., 84, 2156.

14 Brookes, I.M., Muryn, C.A., and Thornton,

G. (2001) Phys, Rev. Lett., 87, 266103.

15 Schaub, R., Thostrup, P., Lopez, N.,

Laegsgaard, E., Stensgaard, I., Nørskov,

J.K., and Besenbacher, F. (2001) Phys. Rev.

Lett., 87, 266104.

16 Bikondoa, O., Pang, C.L., Ithnin, R.,

Muryn, C.A., Onishi, H., and Thornton, G.

(2006) Nat. Mater., 5, 189.

17 Pang, C.L., Bikondoa, O., Humphrey, D.S.,

Papageorgiou, A.C., Cabailh, G., Ithnin,

R., Chen, Q., Muryn, C.A., Onishi, H.,

and Thornton, G. (2006) Nanotechnology,

17, 5397.

18 Wendt, S., Schaub, R., Matthiesen, J.,

Vestergaard, E.K., Wahlstr

€

om, E.,

Rasmussen, M.D., Thostrup, P., Molina,

L.M., Lægsgaard, E., Stensgaard, I.,

Hammer, B., and Besenbacher, F. (2005)

Surf. Sci., 598, 226.

19 Wendt, S., Matthiesen, J., Schaub, R.,

Vestergaard, E.K., Lægsgaard, E.,

Besenbacher, F., and Hammer, B. (2006)

Phys. Rev. Lett., 96, 066107.

20 Zhang, Z., Bondarchuk, O., Kay, B.D.,

White, J.M., and Dohn



alek, Z. (2006)

J. Phys. Chem. B, 110, 21840.

21 Fischer, S., Munz, A.W., Schierbaum, K.-

D., and G

€

opel, W. (1995) Surf. Sci., 337, 17.

22 Lindsay, R., Wander, A., Ernst, A.,

Montanari, B., Thornton, G., and

Harrison, N.M. (2005) Phys. Rev. Lett., 94,

246102.

23 Cabailh, G., Torrelles, X., Lindsay, R.,

Bikondoa, O., Joumard, I., Zegenhagen, J.,

and Thornton, G. (2007) Phys. Rev. B, 75,

241403(R).

24 Allegretti, F., OBrien, S., Polcik, M.,

Sayago, D.I., and Woodruff, D.P. (2005)

Phys. Rev. Lett., 95, 226104.

25 Hugenschmidt, M.B., Gamble, L., and

Campbell, C.T. (1994) Surf. Sci., 302, 329.

26 Henderson,M.A. (1998) Surf. Sci., 400,203.

27 Henderson, M.A. (2002) Surf. Sci. Rep.,

46,1.

28 Onda, K., Li, B., Zhao, J., Jordan, K.D.,

Yang, J., and Petek, H. (2005) Science,

308, 1154.

29 Henderson, M.A., Epling, W.S., Peden,

C.H.F., and Perkins, C.L. (2003) J. Phys.

Chem. B, 107, 534.

30 Teobaldi, G., Hofer, W.A., Bikondoa, O.,

Pang, C.L., Cabailh, G., and Thornton, G.

(2007) Chem. Phys. Lett., 437, 73.

31 Di Valentin, C. (2007) J. Chem. Phys., 127,

154705.

32 Schaub, R., Thostrup, P., Lopez, N.,

Laegsgaard, E., Stensgaard, I., Nørskov,

J.K., and Besenbacher, F. (2001) Phys. Rev.

Lett., 87, 266104.

33 Schaub, R. (2006) Science, 314, 5801.

34 Thompson, T.L., Diwald, O., and Yates,

J.T., Jr. (2004) Chem. Phys. Lett., 393, 28.

35 Fukui, K., Onishi, H., and Iwasawa, Y.

(1997) Phys. Rev. Lett., 79, 4202.

36 Fukui, K., Onishi, H., and Iwasawa, Y.

(1997) Chem. Phys. Lett., 280, 296.

37 Pang, C.L., Raza, H., Haycock, S.A., and

Thornton, G. (2000) Appl. Surf. Sci., 157,

233.

38 Pang, C.L., Sasahara, A., Onishi, H., Chen,

Q., and Thornton, G. (2006) Phys. Rev. B,

74, 073411.

39 Lauritsen, J.V., Foster, A.S., Olesen, G.H.,

Christensen, M.C., K

€

uhnle, A., Helveg, S.,

Rostrup-Nielsen, J.R., Clausen, B.S.,

Reichling, M., and Besenbacher, F. (2006)

Nanotechnology, 17, 3436.

40 Fukui, K. and Iwasawa, Y. (2002)

Noncontact Atomic Force Microscopy

(eds S. Morita, E. Meyer, and R. Wiesen-

danger), Springer, Berlin.

References

237

41 Enevoldsen, G.H., Foster, A.S.,

Christensen, M.C., Lauritsen, J.V., and

Besenbacher, F. (2007) Phys. Rev. B, 76,

205415.

42 Kurtz, R.L., Stockbauer, R., Madey, T.E.,

Rom



an, E., and De Segovia, J.L. (1989)

Surf. Sci., 218, 178.

43 Pan, J.M., Maschhoff, B.L., Diebold, U.,

and Madey, T.E. (1992) J. Vac. Sci. Technol.

A, 10, 2470.

44 Wang, L.Q., Shultz, A.N., Baer, D.R., and

Engelhard, M.H. (1996) J. Vac. Sci. Technol.

A, 14, 1532.

45 Onda, K., Li, B., and Petek, H. (2004)

Phys. Rev. B, 70, 045415.

46 Perkins, C.L. and Henderson, M.A. (2001)

J. Phys. Chem. B, 105, 3856.

47 Epling, W.S., Peden, C.H.F., Henderson,

M.A., and Diebold, U. (1998) Surf. Sci.,

412/413, 333.

48 Rasmussen, M.D., Molina, L.M., and

Hammer, B. (2004) J. Chem. Phys., 120,

988.

49 Wu, X., Selloni, A., Lazzeri, M., and Nayak,

S.K. (2003) Phys. Rev. B, 68, 241402(R).

50 Du, Y., Dohn



alek, Z., and Lyubinetsky, I.

(2008) J. Phys. Chem. B, 112, 2649.

51 Diebold, U., Hebenstreit, W., Leonardelli,

G., Schmid, M., and Varga, P. (1998) Phys.

Rev. Lett., 81, 405.

52 Henderson, M.A., Otero-Tapia, S., and

Castro, M.E. (1999) Faraday Discuss.,

114, 313.

53 Henderson, M.A., Otero-Tapia, S., and

Castro,M.E. (1998) Surf. Sci., 412/413, 252.

54 S



anchez de Armas, R., Oviedo, J., San

Miguel, M.A., and Sanz, J.F. (2007) J. Phys.

Chem. C, 111, 10023.

55 Li, B., Zhao, J., Onda, K., Jordan, K.D.,

Yang, J., and Petek, H. (2006) Science, 311,

1437.

56 Gamble, L., Jung, L.S., and Campbell, C.T.

(1996) Surf. Sci., 348,1.

57 Kim, Y.K., Kay, B.D., White, J.M., and

Dohn



alek, Z. (2007) J. Phys. Chem. C, 111,

18236.

58 Bondarchuk, O., Kim, Y.K., White, J.M.,

Kim, J., Kay, B.D., and Dohnalek, Z. (2007)

J. Phys. Chem. C, 111, 11059.

59 Zhang, Z., Bondarchuk, O., White, J.M.,

Kay, B.D., and Dohn



alek, Z. (2006) J. Am.

Chem. Soc, 128, 4198.

60 Zhang, Z., Bondarchuk, O., Kay, B.D.,

White, J.M., and Dohn



alek, Z. (2007)

J. Phys. Chem. C, 111, 3021.

61 Zhang, Z., Ge, Q.F., Li, S.-C., Kay, B.D.,

White, J.M., and Dohn



alek, Z. (2007)

Phys. Rev. Lett., 99, 126105.

62 Vijay, A., Mills, G., and Metiu, H. (2003)

J. Chem. Phys., 118, 6536.

63 Li, S.-C., Zhang, Z., Sheppard, D., Kay,

B.D., White, J.M., Du, Y., Lyubinetsky, I.,

Henkelman, G., and Dohn



alek, Z. (2008)

J. Am. Chem. Soc., 130, 9080.

64 Kr

€

uger, P., Bourgeois, S., Domenichi, B.,

Magnan, H., Chandesris, D., Le F



evew, P.,

Flank, A.M., Jupille, J., Floreano, L.,

Cossaro, A., Verdini, A., and Morgante, A.

(2008) Phys. Rev. Lett., 100, 055501.

65 Kajita, S., Minato,T., Kato, H.S., Kawai, M.,

and Nakayama, T. (2007) J. Chem. Phys.

127, 104709.

66 Thompson, T.L., Diwald, O., and Yates, J.T.

(2003) J. Phys. Chem. B, 107, 11700.

67 Farfan-Arribas, E. and Madix, R.J. (2002)

J. Phys. Chem. B, 106, 10680.

68 Gan, S., Liang, Y., and Baer, D.R. (2000)

Surf. Sci., 459, L498.

69 Stipe, B.C., Rezaei, M.A., and Ho, W.

(1998) Science, 280, 1732.

70 Leung, L., Muryn, C.A., and Thornton, G.

(2004) Surf. Sci., 566–568, 671.

238

8 Point Defects on Rutile TiO

(1 1 0): Reactivity, Dynamics, and Tunability

Index

ab initio investigation 115ff

achiral 4ff

– species 19ff

– surface 12ff

adenine 22ff

adsorbate

– mobility 206

– overlayer 61

adsorption of cysteine on Au 22

/Ni

Al(1 1 1) 38

153

alloy model catalyst 86

p-allyl 210

Ambient pressure

– pd cluster 89

– X-ray photoelectron

– spectroscopy (APXPS) 189

amino acid building blocks 2

anatase (0 0 1) bilayer 158

anion adlayer 130

anisotropy 8

Apiezon 125

Arrhenius relation 213

atom mobility 33

atomic

– adsorber 4

– force microscopy (AFM) 99

– layers 39

– resolution 35

– spacing 169

– substituents 2

autocatalyic cycle 72

azimuthal orientation 10

B3LYP real-space distribution 112

band

– edge 37ff

– gap 43

benzene 214

bias

– dependence 36

– voltage 35ff

bimetallic cluster 51

binding energy 45, 151

biomolecular reactions 207

bipotentiostat 122

p-bonding 209

bSKAN code 108

bulk-oxide 148

bulk-terminated surfaces 148

butanol 67, 231

1-butyl-3-methyl-imidazolium 144

c(22) structure 103ff

Cahn-Ingold-Prelog system 2ff

cantilevers 220

capacitance manometer 198

capillary forces 138

catalytic

– model system 106

– oxidation 73, 103

– reaction 55, 59

– water production 101

cerium oxide 177

charge distribution 112, 198, 233

chemisorption 12, 56ff

chiral 1ff

– ampliﬁcation 3–19

– building blocks 3

– dopant 19

– etching 16

– heterogeneous catalysis 18

– ligand 3

– molecules 1

– recognition 21

239

– switching 20

CO/NO coadsorption on Rh(1 1 1) 213

coalescence 89

cohesive energy 141

conductance 103

conduction band 35f

conformation LR/RL 20

constant current mode STM 120

constant current STM image of CeO2 on

Rh(1 1 1) 180

contamination, surface 128

contour plots of TiO

[0 1 1]-averaged

– charged densities 107f

contrast, image 149

convolution effects 39

CO-oxidation 150

coronene 9

corundum structure 167

cross-link reconstruction 48

cross-talk 138

crystallographic shear planes

current proﬁle 105

cyclic hydrocarbons 209

cyclic voltammetry 121

cyclohexene 209ff

(S)-cysteine dimer 16

damping 127

defect on TiO

dehydrogenation 169

delamination 158

delineating 91

delocalization 113

density

– functional theory (DFT) 222

– functional theory (DFT) calculation 7

– of primitive surface unit cell 219

– of state (DOS) 41ff

depletion of O

atoms 72

deprotonated thiolate surface 22

deprotonation 14ff

desorption 224

determining site for chemisorption 64

dextrorotatory 2

diastereoreoisomeric interaction 8ff

diffusion barrier 67, 152

dihydrogen 222

dipeptide 22

direct manipulation of atoms 31

dissociative adsorption 63ff

distance tunneling microscopy 121

dot structure 45

Ehrlich-Schwoebel barrier 134

electric circuit in situ STM 124

electrical

– breakdown 59

– pulse 223

electrocatalysis 119

electrochemical cell 126

electrochemical nanostructure 135

electrochemistry 101

electrolyte 122

electron

– afﬁnity 111

– bombardment 64

– cyclotron resonance (ECR)

– plasma oxygen 150

– density 131

– microscopy 197

– scattering quantum chemistry (ESQC)

170

electronic

– state 44

– structure 37–44

electrostatic interaction 175

emission current 233

enantiomer 1ff

enantioselective homogeneous catalyst 3

encapsulation 88

entropy 199

epitaxtial

– ﬁlm 172

– growth 173

equidistant space constant I

contours 108

etching 125

ethylene hydrogenation on Pt(1 1 1) 207

faceting 132ff

reactivity of fcc(1 1 0) metals 76

feedback

– control 140

– loop 38

femtolaser 55

FeO bilayer on Pt(1 1 1) 150ff

Fermi

– edge 34

– energy 111

– level 98ff

ﬁeld emission 165

– microscopy 197

ﬂame annealing 128

ﬂexible surface 92

(S)-form methamphetamine molecule 4

240

Index

geometric distortion 40

Gibbs Energy 3

glancing incidence X-ray diffraction (GIXD)

174

glutamic acid 18

growth kinetics supported model catalyst 85

growth temperature 33

Hartree-Fock terms 100

heterochiral (32) unit cell 7

heterogenous

– enantioselective catalysis 147

– nucleation kinetics 47

hexagonal closed-pack 169

hexagonal superstructure 45

2,5,8,11, 14,17-hexa-tert-buthylhexabenzo

[bc, ef, hi, kl, no, qr]coronene (HtB-HBC)

hierarchy of cluster rubene on Au{1 1 1} 6

high-energy

– barrier 207

– electron bombardment 220

highly ordered pyrolitic graphite

(HOPG) 190

high-pressure

– high-temperature STM reactor 192

– scanning tunneling microscopy

(STM) 189–191

high-resolution

– AFM image of alumina ﬁlm on Ni

Al 45

– energy loss spectroscopy (HREELS) 161

– image of V

162

– STM-AFM image of alumina ﬁlm on

Al 45

homogeneous

– catalyst 1

– nucleation 46

hopping 232

HSEO3 subsurface delocalization 113

HtB-HBC adsorption on

– Cu{1 1 0}, STM-UHV 13

hybrid

– DFT 101

– exchange density 175

hybridization 166

hydrogen oxidation 71

image formation in STM 98

imaging

– adsorbates intermediate reaction 59ff

– chemisorption on metals 61

– oxide ﬁlm 34

– single-crystal surfaces 128

in situ

– STM investigation 56

– STM study of model catalyst 55

– study supported model catalyst 85

– tip regeneration 57f

inductive heating setup 129

instrumentation 56

interdigitation 9ff

interface 88, 148

interfacial

– contacts 193

– lattice mismatch 179

– proximity effect 147

– strain 163–182

intermediate stage reaction of c(24)-O 102

intermolecular

– bonding 23

– interaction 33

– separation 8

interstitial, defects 69ff

ion

– scattering spectroscopy 179

– sputtering 64, 110

iron oxide 169

island density 34

jump-to-contact 137

kagomé-phase 156

kinetic Monte Carlo simulation 33

lateral

– force 195

– interaction of molecular carboxylate 19

– lattice constant 172

– lattice expansion 171

– resolution 121

– tip position 35

lattice

– constant 46

– matching 8

– mismatch 163–174

– spacing 169

line proﬁle analysis 205

linear ﬁt, reaction rate 75

liquid helium bath cryostat STM 220

lithography 31ff

Index

241

local electronic density of states (LDOS)

150

lock-key model 22

long-range order 149

low temperature STM 57ff

low-energy electron diffraction (LEED)

7, 106

L-phe-L-phe 23

map of W[1 1 0] tunneling current 108

Mars-van-Krevelen mechanism 83

material gap 56ff

metal surface at high pressure 81

metal-on-oxide system 30ff

metal-oxide interface 175

methamphetamine 4

methanol adsorption 67, 231

(R)-methyl-3-hydroxybutyrate 25

methylacetoacetate (MAA) 24

(R)-3-methylcyclohexanone 16

microcantilever 139

microfaceted surface 203

microprocessor 140

Miller index surfaces 199

miniaturization 139

mirror domain 5–11

mobility 70, 73

model

– catalyst 30ff

– TiO

surface 65

modeling surface reactivity 97

modiﬁed template 50

Moiré pattern 208

molecular

– adsorption 4

– beam scattering 189

– model enantiomer 5

– model of glycinate {1 1 0} 7

monoatomic steps 206

monodisperse metal cluster 155

monolayer 130

monomer migration 89

nanocatalyst 155

nanocluster 139ff

nanodecoration 141

nanodot array, Cu 136

nanofabrication 30

nanofacet 174

nanoisland 80

nanolayer 148

nanophase 148

nanoscale hybrid structure 182

nanosheet 158

nanostructure 29

nanostructure by self-organization 32

near-edge X-ray absorption

ﬁne structure (NEXAFS) 160

Nernst potential 137

network structure 45

nickel oxide nanolayers 173

nomenclature of chirality 2

noncontact AFM 178ff

nucleation

– density 44

– site 32ff

number density 44

one dimensional-Ag-O-chain 76

optoelectronics 159

oscillatory 122

Ostwald ripening 89f

oxidation-reduction cycle 132

oxide as template 44

oxidizing agent 126

oxygen-mediated diffusion 224

paramagnetic triple state 113

particle on oxide ﬁlm 39

Pd hydrogenation 62

periodicity 48

PES spectra 70

phase

– boundary 80, 148

– transition 82

phenylglycine 8–23ff

phonon spectrum 161

photo-assisted oxidation 155

photocatalysis 64, 229ff

photoelectron

– diffraction (PED) 112

– spectroscopy (PES) 69

photoreactive molecule 69

piezoelectric

– plates 193

– scanning tube 195

platinum particles on oxidized silicon,

STM 31

plot number density of cluster 47

point defect 219

polycrystalline 127

polyisocyanate copolymers 20

polymorphism 160

positive bias 221

242

Index

postoxidation 150

pressure gap 29ff

prochiral

– carboxylic acid 17

– molecules interaction with chiral

surfaces 24

– reagent 3

pseudodissociate state 109

pseudomorphic phase 175

pseudoperfect surfaces 235

pseudohexagonal lattice in fcc {1 1 0} 11f

p-type semiconductor 173

puriﬁcation, reactant gas 59

PVBA structure 17

QMS signal O

quadruple mass spectrometer (QMS) 82

quartz 15

quasi-hexagonal 153

quasi-zero-dimensional V-oxide clusters 164

racemic mixture 3ff

reaction

– kinetics of CO oxidation 73

– rate plot CO 75

reactive

– evaporation (RE) method 150

– metal 142

real-space distribution, electronic states 114

resolution limitation 44

resonant frequency 220

saturated calomel electrode (SCE) 126

scanning

– electrochemical microscopy 120

– tunneling microscopy (STM) 1, 7ff

– tunneling spectroscopy (STS) 97

schematic, continuous cluster

generation 140

segmentation of AgO chains 76

self-assembled nanostructures 165

self-recognition 21

semilocal (CGA ) approximation 110

sequential image of TiO

(1 1 0)

– showing the splitting of an Oh

226

shadowing technique 57

schematic model point defect 227

simulating

– chemical reactivity 100

– tunneling current 99

single-crystal surface 29–178

sintering kinetics of Au 89

spatial

– conﬁnement 34

– limit 55

spectroscopic signature 233

spin density 111

p-stacking 209

static secondary ion mass spectrometry 229

step edge 86ff

step-kink arrangement fcc{6 4 3}R 16

stereocenter 2

stereochemistry 2ff

STM image of

– Ag(1 1 0)(n·1)-O surface 78, 80

– alumina ﬁlm on Ni

Al 37

– r-aminobenzoic acid on Cu 18

– anionic adlayer 131

– at oxygen spillover 89

– Au cluster 91

– CO molecule 74

– CO oxidation 84

– cocrystalline 1:1 structure 25

– Cu clusters on Al

/Ni

Al(1 1 1), Ag 46

– 1,4 cyclohexadiene 212

– decamer of 1-nitroaphthalene 6

– electrodeposited Pt cluster 133

– Fe nanoparticle on FeO

ﬁlm on

MgO(1 0 0) 50

– growing Pd monolayer 132

– H-vacancy clusters 63

– lifted Pt(1 0 0) 201

– methanol adsorption 68

– Ni-oxide on Pd(1 0 0) 176

– O-covered Pt(1 1 1) 72

– oxidation cycle 168

– oxidation-reduction 135

– Pd cluster on Al

/Ni

Al 46ff

– Pd(1 1 1) in H

130

– Pt(1 1 0) 83

– PVBA-induced 19

– reduction of Ag(1 1 1)-p(4·4) 79

– sequential image Rh(1 1 1) 215

– single Fe cluster 41

– stoichiometric 1x1 TiO

107

– TiO

66ff

– TiOx structure 157

– V cluster on Al

/Ni

Al 48

– V

island 81f

– water saturated surface 103

STM image with CO-terminated tip 60f

stoichiometry 70

strong metal support interaction effect 88

STS alumina ﬁlm spectra 36

STS differential conductance spectra 166

Index

243