bunsho ohtani ohtani@cat.hokudai.ac.jp...

ohtani@cat.hokudai.ac.jpBunsho OHTANI大谷文章

2

uniqueユニーク

3

ICATInstitute for Catalysis, Hokkaido UniversitySapporo 001-0021, Japan

founded originally in 1943

Hokkaido University• one of the former 8 imperial universities• founded as Sapporo Agricultural College in 1876

Boys be ambitious!(BBA)

William S. Clerk

The first principal of Sapporo

Agricultural College, the former of

Hokkaido University

clerk@sapporo-agri.ac.jp

ambitious

ambi- environmental/both sides

ambient completely enveloping/surroundingambivalent uncertain or unable to decide about what

course to followambidextrous equally skillful with each handambitious having a strong desire for success or

achievement

ambiguous = not clearはっきりしない（あいまい）

unambiguous = not not-clear「はっきりしない（あいまい）」じゃない

≠ clearはっきり

science/科学

unambiguousness + textあいまいじゃない + ことばであらわす

A Novel Concept of Identification of Metal-oxide Powders by Energy-resolved Density

of Electron Traps

Bunsho OHTANI (Hokkaido University, Japan)

identification fingerprint coincidence correlation

Professor Mai TAKASE (Muroran Institute of Technology) and Mr. Akio

NITTA (Ph. D. student in Graduate School of Environmental Science,

Hokkaido University)Awarded "Best Poster Award" at 55th

Aurora Seminar at Numata (July 26-27, 2015)

Professor Mai

TAKASHIMA (Institute for

Catalysis, Hokkaido

University)

Professor Naoya

MURAKAMI (Kyushu

Institute of Technology)

Mr. Masanori NAGAO (MC in

Graduate School of

Environmental Science,

Hokkaido University))

Awarded "The 12th Honda-Fujishima

Prize" (March 2016)

Awarded "The 7th Honda-

Fujishima Prize" (2011)

11

photocatalysis industries in Japan = ca. 350 million USD (2015)

58%

3%1%

30%

7%

1%

exterior

interior

road related

purifier

living ware

12

Fujishima, A.; Honda, K., Nature 238, 37 (1972).

13

Checked by several electrochemists:

63) A. Nozik, Nature, 257, 383 (1975). 64) M. S. Wrighton, D. S. Ginley, P. T. Wolczanski, A. B. Ellis, D. L. Morse, and A.

Linz, Proc. Natl. Acad. Sci. U.S.A., 72, 1518 (1975).

14

TiO2 Pt

↑O2 ↑Ｈ2

e-

UV

TiO2

↑O2

e-

↑Ｈ2

UV

Pt

high pH low pH

H: Honda-Fujishima effecthidden message

requirement of BIAS potential, i.e., electric FIELD in the BULK to separate photoexcited electron and positive hole (= charge separation) to drive the reactions of positive Gibbs energy change

J. Photochem. Photobiol. C: Photochem. Rev., 11, 157 (2010)

15

(1) thermodynamics = no kinetics(2) single electron transfer only

J. Photochem. Photobiol. C: Photochem. Rev., 11, 157 (2010)

16

no IDENTIFICATION of photocatalyst powders

J. Photochem. Photobiol. C: Photochem. Rev., 11, 157 (2010)

「もうダマされないための『科学』講義」菊池誠・松永和紀・伊勢田哲治・平川秀幸・片瀬久美子・飯田泰・SYNODOS，光文社新書（2011）

aver

age

life

time

of Ja

pane

se w

omen

(age)

reac

tivity

/act

ivity

Xnumber of TV sets per 100 families(number of TV sets per 100 families) like sth

Xe.g., titania particles

composition: TiO2

crystalline form: anatase/rutile ...particle sizespecific surface area?

identification物質の同定

20

benzene

structure (purity)構造（純度）

science/科学

unambiguousness + textあいまいじゃない + ことばであらわす

23

identification of organic compounds

e.g., J. Org. Chem. (ACS) requests identification by at least:

elemental analysis data within 0.3% errorcomposition and purity

nuclear magnetic resonance patternskeleton Friderik Pregl (1869-1930)

Wienbibliothek, Tagblattarchiv, photos collection, TF-008286

24

identification of organic compoundsOhtani, B.; Tsuru, S.; Nishimoto, S.-i.; Kagiya, T.; Izawa, K. J. Org. Chem. 1990, 55, 5551-5553. [64]

5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5chemical shift / ppm

NMR spectrum of photoirradiated sample after separation of photocatalyst powder

authentic sample of proline

NH

COOHH2NNH 2

COOH TiO 2-Pt

> 300 nm

25

26

(2S,3R,5R,8R,9S,E)-10-((2R,3R,4R,5S,6R)-6-((1S,2R,3S,4S,5R,11S)-12-((1R,3S,5S,7R)-5-((S)-9-((2R,3R,4R,5R,6S)-6-((2S,3S,6S,9R,10R,E)-10-((2S,4R,5S,6R)-6-((2R,3R)-4-((2R,3S,4R,5R,6S)-6-((2S,3Z,5E,8R,9S,10R,12Z,17S,18R,19R,20R)-21-((2R,3R,4R,5S,6R)-6-((3R,4R,Z)-5-((1S,3R,5R,7R)-7-(2-((2R,3R,5S)-5-(aminomethyl)-3-hydroxytetrahydrofuran-2-yl)ethyl)-2,6-dioxabicyclo[3.2.1]octan-3-yl)-3,4-dihydroxypent-1-en-1-yl)-3,4,5-trihydroxytetrahydro-2H-pyran-2-yl)-2,8,9,10,17,18,19-heptahydroxy-20-methyl-14-methylenehenicosa-3,5,12-trien-1-yl)-3,4,5-trihydroxytetrahydro-2H-pyran-2-yl)-2,3-dihydroxybutyl)-4,5-dihydroxytetrahydro-2H-pyran-2-yl)-2,6,9,10-tetrahydroxy-3-methyldec-4-en-1-yl)-3,4,5,6-tetrahydroxytetrahydro-2H-pyran-2-yl)-8-hydroxynonyl)-1,3-dimethyl-6,8-dioxabicyclo[3.2.1]octan-7-yl)-1,2,3,4,5-pentahydroxy-11-methyldodecyl)-3,4,5-trihydroxytetrahydro-2H-pyran-2-yl)-2,5,8,9-tetrahydroxy-N-((E)-3-((3-hydroxypropyl)amino)-3-oxoprop-1-en-1-yl)-3,7-dimethyldec-6-enamide

27

unique（ユニーク）/phonetic（電話で伝えられる）

identification

to be named reflecting structure(unambiguous text)

＝

titanium(IV) oxide ＝ TiO2

30

IUPAC recommendation on inorganic compounds

IR-11 SolidIR-11.1.1 GeneralThis chapter deals with some aspects of terminology, nomenclature and notation for (inorganic) solids. However, in cases where detailed structural information is to be conveyed, fully systematic names can be difficult to construct.

Nomenclature of Inorganic Chemistry, IUPAC Recommendations 2005, The Royal Society of Chemistry (2005) p. 236.

science/科学

unambiguousness + textあいまいじゃない + ことばであらわす

32

bulk (crystal lattice) surface<size>

33

reconstruction of P25 from componentsOhtani, B.; Prieto-Mahaney, O.-O.; Li, D.; Abe, R. J. Photochem. Photobiol. A Chem. 2010, 216, 179-182. [178]

fluffy/white bulky/slightly yellow

fluffy/whiteP-25

rutile (14%)

anatase (78%)

(Wako Pure Chemical)amorphous (8%)

white

34

• sample supplied in "1-kg package"• re-packed in several bottles• sampling ... how? top/middle/bottom

crystal composition depending on the collection point

• presumably due to anatase, rutile and amorphous domains are produced in the "flame-synthesis" procedure

• no guarantee for:samples taken from the same bottle has 78:14:8 ratio

your P25 sample has the crystal content of 78:14:8.

inhomogeneous composition of P25Ohtani, B.; Prieto-Mahaney, O.-O.; Li, D.; Abe, R. J. Photochem. Photobiol. A

Chem. 2010, 216, 179-182. [178]

crystalline phaseprimary particle sizesecondary particle sizespecific surface area

(thin) hairwire-frame glasses(gray) beard and mustachering on left third (ring) fingerblack turtle-neck sweaterhandsome!fingerprint

from "Steve Jobs"KodanshaLtd. 2013

crystalline phaseprimary particle sizesecondary particle sizespecific surface area

ERDT/CBB pattern

38

energy-resolved density of electron-traps (ERDT)/conduction-

band bottom (CBB)

as a

finger printfor identification of metal-oxide

powders

39

identification of organic compoundsOhtani, B.; Tsuru, S.; Nishimoto, S.-i.; Kagiya, T.; Izawa, K. J. Org. Chem. 1990, 55, 5551-5553. [64]

5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5chemical shift / ppm

NMR spectrum of photoirradiated sample after separation of photocatalyst powder

authentic sample of proline

NH

COOHH2NNH 2

COOH TiO 2-Pt

> 300 nm

40

650～1300 cm-1 = fingerprint region

infrared absorption spectroscopy

41

150100500

0

0.1

0.2

0.3

0.4

0.5

ET density/μmol g-1 eV-1

ener

gy fr

om C

B bo

ttom

/eV TIO-2

(anatase)

CR-EL(rutile rich)

e-

h+

CB

VB

Ti4+→Ti3+ MV2+→MV+•

deaeratedcondition

electron donor

low energy resolution limitation of trap-energy range

photochemical method for ERDT measurementIkeda, S.; Sugiyama, N.; Murakami, S.-y.; Kominami, H.; Kera, Y.; Noguchi, H.; Uosaki, K.;

Torimoto, T.; Ohtani, B. Phys. Chem. Chem. Phys. 2003, 5, 778-783. [ 118]

42

♪

modulated light continuous light

methanol saturatedargon gas atmosphere

625 nm80 Hz

scanning

CB

VB

direct excitation

filling electron traps selectively from deeper side

reversed double-beam photoacoustic spectroscopy (RDB-PAS)

44

TIO-1(anatase)

0

0

reversed double-beam photoacoustic spectroscopy (RDB-PAS)

ener

gy fr

om v

alen

ce-

band

(VB)

top/

eV

45

ET density/μmol g-1

3.4en

ergy

from

VB

top/

eV

3.2

3.0

2.8

2.6

2.4

2.2

2.0

20100

<97>TIO-1

anatase

CB

20100

<15>TIO-5

rutile rich

CB

20100

<155>TIO-11

anatase rich

CB

20100

CB

<98>TIO-3rutile

46

47

TIO-2(anatase)

CR-EL(rutile rich)

RDB-PAS

photochemical method

higher energy resolution and wider energy range

48surface >> crystalline bulk

○ anatase, ● anatase rich, ■ rutile rich, □ rutile

0

50

100

150

200

250

0 100 200 300 400

tota

l den

sity

of E

Ts/μ

mol

g-1

specific surface area/m2 g-1

49

ERDT: energy-resolved distribution of traps

ET density/μmol g-1

anatase anatase rutile rutileonly > rutile > anatase only

ET density/μmol g-1 ET density/μmol g-1ET density/μmol g-1

finger print of titaniaslike NMR patterns for organic molecules

50ζ = ζ(a) × ζ(b)1/2 ×ζ(c)2

ζ(a): ERDT-pattern matching (f)

ζ(b): total density of ETs (D)

ζ(c): CB bottom position (CBB )

= 1 - ( ∫ f (1) – α f (2) / f (1) )α = ∫ ( f (1) – α f (2) )2

∫f (1) < ∫f (2)

= D (1) / D (2) [D (1) ≤ D (2)]

= CBB (1) / CBB( 2)[CBB (1) < CBB (2)]

standard deviation for degree of coincidence (ζ)

ζ > 0.88

51

ζ

52

TIO-1TIO-2

TIO-13TIO-4TIO-11ST-F1ST-F5MerckTIO-5CR-ELST-G2TIO-3TIO-6MT-150AFP-6P25TIO-12AMT-100TKP-101TIO-8ST-01Wako634662

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8TI

O-2

TIO

-13

TIO

-4TI

O-1

1ST

-F1

ST-F

5M

erck

TIO

-5C

E-EL

ST-G

2TI

O-3

TIO

-6M

T-15

0AFP

-6P2

5TI

O-1

2AM

T-10

0TK

P-10

1TI

O-8

ST-0

1w

ako

6346

62ST

-G1

(1) TIO-4/Wako(2) TIO-4/P25

(3) TIO-8/ST-01

(4) P25/Wako(5) TIO-6/MT-150A

(7) TIO-11/FP-6

(6) TIO-13/FP-6

ζ

53

TIO-1TIO-2TIO-13TIO-4TIO-11ST-F1ST-F5MerckTIO-5CR-ELST-G2TIO-3TIO-6MT-150AFP-6P25TIO-12AMT-100TKP-101TIO-8ST-01Wako634662

00.10.20.30.40.50.60.70.8

TIO

-2TI

O-1

3TI

O-4

TIO

-11

ST-F

1ST

-F5

Mer

ckTI

O-5

CE-

ELST

-G2

TIO

-3TI

O-6

MT-

150A

FP-6

P25

TIO

-12

AMT-

100

TKP-

101

TIO

-8ST

-01

wak

o63

4662

ST-G

1

(1) TIO-4/Wako(2) TIO-4/P25

(3) TIO-8/ST-01

(4) P25/Wako(5) TIO-6/MT-150A

(7) TIO-11/FP-6

(6) TIO-13/FP-6

identification of

powders (metal oxide particles with band gap and ETs)

bulk composition CBB bulk size (surface size) total ET density surface structure ERDT pattern

XRD patternnitrogen ads. (BET)-----

55

ERD

T an

d CB

B fo

r met

al o

xide

s oth

er th

an ti

tani

a

56electron-trap density/μmol g-1

CB

NBO1<29>

194 m2 g-1

2.0

2.2

2.4

2.6

2.8

3.0

3.2

3.4

ener

gy fr

om V

BT/e

V 0 5 10

CB

NBO-673<91>

106 m2 g-1

0 5 10CB

NBO-723<81>

104 m2 g-1

0 5 10CB

NBO-773<13>

48 m2 g-1

0 5 10CB

NBO-873<5>

31 m2 g-1

0 5 10CB

NBO2<57>

3 m2 g-1

0 5 10

CB

NAS-0<0.6>

215 m2 g-1

2.0

2.2

2.4

2.6

2.8

3.0

3.2

3.4

0 5 10

ener

gy fr

om V

BT/e

V

CB

NAS-673<49>

122 m2 g-1

0 5 10

CB

NAS-723<86>

104 m2 g-1

0 5 10

CB

NAS-773<37>

76 m2 g-1

0 5 10

CB

NAS-873<6>

48 m2 g-1

0 5 10

CB

NAS-1073<6>

10 m2 g-1

0 5 10

CB

NBO-1073<3>

3 m2 g-1

0 5 10

am0 am0 am0TT TT T+H

am1am0 am0 TT TT

T

T NAS-0

SoekawaChemical

"niobic acid

hydrate"

niobia = niobium(V) oxide

Xe.g., titania particles

composition: TiO2

crystalline form: anatase/rutile ...particle sizespecific surface area?

58

replotting of data withseven-point non-weightedmoving average

ERDT/CBB pattern = decisive factor for photocatalytic activity

● CH3OH → HCHO + H2● CH3COOH + 2O2 → 2CO2 + 2H2O● 4Ag+ + 2H2O → 4Ag + O2 + 4H+

degree of coincidence

0

0.2

0.4

0.6

0.8

1

0 0.2 0.4 0.6 0.8 1

ζpc

ζ

0

0.2

0.4

0.6

0.8

1

0 0.2 0.4 0.6 0.8 1

ζpc

ζ

59

O2

CO2

H2

CH3OH → HCHO + H2(in-situ platinum deposition)

CH3COOH + 2O2 → 2CO2 + 2H2O

4Ag+ + 2H2O → 4Ag + O2 + 4H+

DOI: 10.1039/C6CC04999K

A Novel Concept of Identification of Metal-oxide Powders by Energy-resolved Density of Electron Traps

metal-oxide powders

organic compounds

Wikipedia

logic in science 62Catalysts 2016, 6(12), 192; doi:10.3390/catal6120192

分子環境学特論II/III 63

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分子環境学特論II/III 64

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提出期限： 2018年1月6日（約4週間）課題： つぎの2つのいずれか（1）化学物質の同定をあやまった例とその原因（2）誤った論理的推論によってあやまった結論がみちびか

れた例とその原因

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