bunsho ohtani [email protected]...
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[email protected] 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
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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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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