Personal Account DOI: 10.1002/tcr.

201900023

NH3-Driven Benzene C H Activation

THE
CHEMICAL
with O2 that Opens a New Way for
RECORD Selective Phenol Synthesis

Shankha S. Acharyya,[a, b] Shilpi Ghosh,[a, b] Yusuke Yoshida,[a] Takuma Kaneko,[a]

Takehiko Sasaki,*[c] and Yasuhiro Iwasawa*[a, b]

Chem. Rec. 2019, 19, 1 – 14 © 2019 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 1
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Abstract: Catalytic benzene C H activation toward selective phenol synthesis with O2 remains a
stimulating challenge to be tackled. Phenol is currently produced industrially by the three-steps
cumene process in liquid phase, which is energy-intensive and not environmentally friendly.
Hence, there is a strong demand for an alternative gas-phase single-path reaction process. This
account documents the pivotal confined single metal ion site platform with a sufficiently large
coordination sphere in β zeolite pores, which promotes the unprecedented catalysis for the
selective benzene hydroxylation with O2 under coexisting NH3 by the new inter-ligand concerted
mechanism. Among alkali and alkaline-earth metal ions and transition and precious metal ions,
single Cs + and Rb + sites with ion diameters > 0.300 nm in the β pores exhibited good
performances for the direct phenol synthesis in a gas-phase single-path reaction process. The
single Cs + and Rb + sites that possess neither significant Lewis acidic basic property nor redox
property, cannot activate benzene, O2, and NH3, respectively, whereas when they coadsorbed
together, the reaction of the inter-coadsorbates on the single alkali-metal ion site proceeds
concertedly (the inter-ligand concerted mechanism), bringing about the benzene C H activation
toward phenol synthesis. The NH3-driven benzene C H activation with O2 was compared to
the switchover of the reaction pathways from the deep oxidation to selective oxidation of benzene
by coexisting NH3 on Pt6 metallic cluster/β and Ni4O4 oxide cluster/β. The NH3-driven selective
oxidation mechanism observed with the Cs + /β and Rb + /β differs from the traditional redox
catalysis (Mars-van Krevelen) mechanism, simple Langmuir-Hinshelwood mechanism, and
acid base catalysis mechanism involving clearly defined interaction modes. The present catalysis
concept opens a new way for catalytic selective oxidation processes involving direct phenol
synthesis.
Keywords: Benzene C H activation toward selective phenol synthesis, Single Cs + and Rb +
site/β zeolite catalysis, Indispensable NH3 effect, Confined single-sites, Inter-ligand concerted
mechanism

also kinetically inert.[3–7] Major worldwide production of

1. Introduction
Activation of C H bonds and thereby selective functionaliza-
tion to industrially important products have been a subject of
increasing interests.[1] Among them, hydroxylation of benzene
C H bond to produce phenol has received much attention
because phenol is a chemical used as precursor for many
industrially important materials, including polymers, drugs
and herbicides.[2,3] Its production currently exceeds 9 megatons
per year. In spite of significant development of C H
functionalization chemistry in the past few decades,[1,2] catalytic
hydroxylation of benzene still remains a stimulating challenge
since C H bonds are not only thermodynamically strong but
[a] Dr. S. S. Acharyya, Dr. S. Ghosh, Dr. Y. Yoshida, Dr. T. Kaneko,
Prof. Dr. Y. Iwasawa
Innovation Research Center for Fuel Cells, The University of Electro-
Communications, Chofu, Tokyo 182 8585, Japan
E-mail: iwasawa@pc.uec.ac.jp
[b] Dr. S. S. Acharyya, Dr. S. Ghosh, Prof. Dr. Y. Iwasawa
Graduate School of Informatics and Engineering, The University of
Electro-Communications, Chofu, Tokyo 182 8585, Japan
[c] Dr. T. Sasaki
Graduate School of Frontier Science, The University of Tokyo,
Kashiwa, Chiba 277-8561, Japan
E-mail: takehiko@k.u-tokyo.ac.jp
Supporting information for this article is available on the WWW
under https://doi.org/10.1002/tcr.201900023
phenol is carried out by the three-step cumene process (one of
the steps is explosive), which is energy-intensive and environ-
mentally unfavorable, producing unnecessary α-methylstyrene
byproduct and lots of acetone equimolar to phenol product.[6,7]
It would be highly desirable to find an efficient and less
environmentally harmful way to produce phenol, and the best
option would be to synthesize phenol directly starting from
benzene and O2 in a gas-phase single-path catalytic process on
a solid catalyst, which would make the reaction efficient and
result in reduced resource consumption and easy-to-separate
products. Many researchers have come forward to overcome
this difficulty and reported benzene hydroxylation reactions
using different oxidants such as N2O,[8] H2O2,[9] H2 + O2[10]
O2 + NH3,[11] air + CO,[12] O2,[13] etc. In light of the desir-
ability of sustainable green chemistry, catalytic oxidation of
benzene with molecular oxygen as an ideal oxidant is of high
potential interest.[14] However, catalytic aerobic oxidation of
benzene via O2 activation is not an easy task, since the O2
molecule possesses a double bond with 0.1208 nm length and
497 kJ mol 1 dissociation energy.[15] In its ground state, the O2
molecule resides in its triplet state and is reluctant to undergo
the formation of highly reactive oxygen radicals, hydroxyl
radicals, hydroperoxide, and peroxide.[15] Although these
hurdles can be overcome by using transition-metal complexes
to activate both O2 and C H bond, catalytic activity, stability,
and selectivity are important issues in practical processes.[15] In

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Personal Account
most cases the phenol yield is low because of the unsatisfied
selectivity toward phenol due to the over-oxidation of phenol
to CO2 and liquid byproducts.[16] Rapid deactivation of solid
catalysts by coke deposition during the gas-phase reaction at
high temperatures is also a major issue.[17] Recently, Sarma
Shankha Shubhra Acharyya earned his Ph.
D. degree from Academy of Scientific &
Innovative Research [AcSIR], India in
2015. After his doctoral works, he joined
Innovation Research Center for Fuel Cells,
The University of Electro-Communica-
tions (UEC), and he was awarded as JSPS
postdoctoral research fellow. Currently he
is working as a Project Assistant Professor
at UEC. His research interests lie in
selective catalytic oxidation, zeolite cataly-
sis, mechanisms of catalytic reactions in-
volving C-H activation and inorganic
functional materials.
Shilpi Ghosh received her Ph.D. degree
from Academy of Scientific & Innovative
Research [AcSIR] India in 2015. Subse-
quently, she joined Prof. Iwasawa’s lab at
The University of Electro-Communica-
tions (UEC), Tokyo in 2015. She was
awarded as JSPS postdoctoral fellow in
2016, and now she is a Project Assistant
Professor at UEC. Her present research
includes synthesis of confined single site
materials for catalytic applications.
Yusuke Yoshida received his Ph.D. degree
in 2016 from Chiba University, Japan. He
was a Research Fellow for Young Scien-
tists, JSPS in 2013–2016. He became a
Project Assistant Professor at Innovation
Research Center for Fuel Cells, The
University of Electro-Communications,
Tokyo in 2016. His research interests are
photocatalysis, catalytic nanomaterials syn-
thesis, and XAFS.
Takuma Kaneko was born in 1980 in
Tokyo. He received his Bachelor’s, Mas-
ter’s and Doctor’s degrees from Chiba
University in 2003, 2005, and 2011,
respectively. He worked as a researcher at
Chiba University in 2011–2013. He
became a Project Assistant Professor at
Innovation Research Center for Fuel Cells,
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THE CHEMICAL RECORD
et al. reported 10 % benzene conversion and 97 % selectivity
towards phenol using the H5PV2Mo10O40 polyoxometalate in
> 50 % aqueous H2SO4 as solvent.[18] However, use of H2SO4
makes the process environmentally unbenign, similar to one of
the three steps in the cumene process due to decomposition of
the University of Electro-Communications
in 2013. His current research interests are
in-situ/operando XAFS, theoretical simu-
lation, etc.
Takehiko Sasaki is Associate Professor at
Department of Complexity Science and
Engineering, Graduate School of Frontier
Sciences, the University of Tokyo (UT).
He graduated from UT and received his
Ph.D. degree at Department of Chemistry,
UT in 1992. His research interests are
Surface Physical Chemistry on solid surfa-
ces, Catalytic Chemistry using ionic
liquid-derived materials and nanomateri-
als, and catalyst design and reaction
mechanism study based on computational
methods such as Density Functional
Theory.
Yasuhiro Iwasawa received his Ph.D. de-
gree from The University of Tokyo (UT)
in 1973. He became Professor at Depart-
ment of Chemistry, UT in 1986. He was
Dean of School of Science in UT in
2005–2007. He moved to the University
of Electro-Communications (UEC) in
Tokyo due to retirement at UT in 2009.
He is Director of Innovation Research
Center for Fuel Cells at UEC. He was
President of the Chemical Society of Japan
in 2010–2012. He also served as Head of
Science and Technology Section of Science
Council of Japan, Cabinet Office in
2008–2011. He is President of Japan
Union of Chemical Science and Technol-
ogy (JUCST) composed of 14 Chemical
Societies in 2018–present. His honors
include National Medal with Purple Rib-
bon (2003) and many others. His current
research interests are in in-situ/operando
characterization and chemical design of
catalysts and surfaces on the molecular
level involving fuel cells.
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cumene hydroperoxide intermediate with H2SO4. Acharyya
et al. reported a benzene conversion of 36 % with a phenol
selectivity of 78 % over ultrasmall Cu(II) oxide nanoparticles
supported on CuCr2O4 spinel nanoparticle catalyst,[19] but the
use of high pressure, production of several liquid by-products
and toxic chromium metals inhibits the process from its
industrialization.
According to the conventional concept of catalysis,
selective oxidation reactions do not proceed significantly on
acid base catalysts, such as zeolites, Brønsted and Lewis acidic/
basic metal oxides, etc., but they proceed on redox catalysts,
such as precious and transition metals, reducible metal oxides,
etc.[18] Typically, the gas-phase selective oxidation of benzene
to phenol with O2, N2O and H2/O2 has been observed with
metal and metal oxide catalysts of V, Fe, Cu, Mo, Pd, W, Re,
etc.[8,11–13,17–25] These catalysts possess moderate redox poten-
tials and sufficient M O bond strengths to provide active
lattice oxygen and reactive oxygen intermediates.
Recently, we reported the unprecedented catalysis of large
alkali and alkaline-earth metal ions as active sites incorporated
in zeolite pores for selective oxidation of benzene to phenol.[18]
The results defy the conventional wisdom on catalytic
processes. Alkali and alkaline-earth metal ions cannot activate
benzene and O2, resulting in no reaction between them.
However, in the presence of NH3 the direct phenol synthesis
from benzene with O2 proceeded selectively in a single-path
gas-phase flow reaction. The reactions displayed good con-
version and selectivity in particular for Cs/β-zeolite (typically
85.1 % selectivity at 6.3 % single-path conversion on 0.6 g cat.
at 603 K), which was characterized to possess single Cs + cation
as active site in β pore using HR-TEM/STEM-EDS, XPS,
XAFS, XRF, TPD, XRD, and DFT calculations.[26] Further,
no liquid by-products were detected by GC (FID) and gaseous
CO2 was only a by-product, which brings about an advantage
of no energy-consumed special devises for separation of phenol
product from the others in the reaction system. There are few
reports on solid catalysts with higher than 70 % phenol
selectivity at higher than 5 % benzene conversion, simulta-
neously in a single-path gas-phase flow reaction at atmospheric
pressure, which is regarded as a critical performance for a more
advantageous practical industrial process as compared to the
cumene process. In the benzene-O2-NH3 system consumption/
decomposition of NH3 during the catalytic phenol synthesis is
also demanded to be minimzed as much as possible for
development of a new industrial process. The phenol synthesis
process by the NH3-driven benzene C H activation will be
more promising industrially by decreasing NH3 price. It is
notable that the Cs + /β was also active for the selective
oxidation of benzene to phenol with N2O (99.9 % selectivity
at 25.5 % single-path conversion on 0.4 gcat at 573 K).[26]
The performances of various M ions/β catalysts (M=Pt, Pd,
Ir, Ag, Rh, Ru, V, Mn, Fe, Co, Ni, Cu, etc.) for the synthesis of
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THE CHEMICAL RECORD
phenol from benzene with O2 in the presence of NH3 were also
examined. The phenol synthesis reactions on these catalysts did
not significantly proceed whether NH3 coexisted or not. Among
their negligible performances Ni2 + /β and Pt2 + (partially Pt0)/β
showed relatively good yields as listed in Table S1 though the
performance levels are very low. It was found that their
performances increased by treatments at elevated temperatures.
We discovered Pt6 metallic cluster/β and Ni4O4 oxide cluster/β
catalysts that promote the gas-phase phenol synthesis from
benzene and O2 with high selectivity in the presence of NH3.[11b,
c]
In the corresponding bi-component benzene O2 system
without NH3, benzene underwent deep oxidation to CO2 on
those catalysts. However, in the three-component
benzene O2 NH3 system, benzene was selectively hydroxylated
to phenol (up to 93.6 % selectivity) and the benzene
combustion was remarkably suppressed. Note that the switch-
over of reaction pathways from the complete oxidation to the
selective hydroxylation occured by NH3. The Ni4O4/β catalyst
showed TOFs (turnover frequencies) of 0.62–1.0 h 1 (0.55–
1.3 % single-path conversion with 0.2 g cat. at 593 K) and
selectivities of 87.6–88.0 %, which were comparable to 1.1–
1.6 h 1 (1.7–2.5 % single-path conversion with 0.2 g cat. at
553 K) and 78.3–85.9 %, respectively for Pt6/β catalysts.[11b,c]
The undesirable NH3 consumption to N2 during the catalytic
phenol synthesis proceeded on the above transition and precious
metal ion catalysts, but on Cs + /β, Pt6/β and Ni4O4/β catalysts
the consumed NH3 amount could be suppressed to the lower
levels than 2.0 against the amount of produced phenol, which is
demanded economically to put the new process into practice
industrially.
The reaction pathways for the phenol synthesis involving
transition states and reaction intermediates on the Cs + single
site, Pt6 metallic cluster and Ni4O4 oxide cluster in β pores
were simulated by DFT calculations. We found the inter-
ligand bond rearrangement mechanism among coadsorbed
benzene, O2 and NH3 molecules as a common aspect for the
three Cs + /β, Pt6/β and Ni4O4/β catalysts. In this account
article we summarize the unprecedented catalysis and unique
catalytic property of the Cs + /β, Pt6/β and Ni4O4/β generated
by NH3 and discuss on the inter-ligand concerted mechanism
for the NH3-driven selective benzene C H activation toward
phenol synthesis on the confined single Cs + site platform in
the β pore.[11b,c,26]
2. Experimental Section
Chemicals. High Purity helium (> 99.999 vol %, Taiyo
Nippon Sanso), oxygen (> 99.999 vol %, Taiyo Nippon
Sanso), and ammonia (> 99.999 vol %, Showa Denko) in high
pressure cylinders were available commercially and used with-
out further purification. Benzene, metal precursors, β zeolite
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and other zeolites were purchased from Wako chemicals,
Kanto Chemical Co., and Zeolyst or JGCC &C, respectively.
Catalyst preparation. Pt6 cluster/β, Ni4O4 cluster/β, single
Cs + ion/β, alkali and alkaline-earth metal ions/zeolites (β,
ZSM-5, Y, mordenite) and transition and precious metal ions/
β were prepared as reported previously.[11b,c,26] Briefly, for the
preparation of Pt6 cluster/β 0.938 g (NH3)4Pt(NO3)2
(STREM) was dissolved in 144 mL deionized water in a three-
neck flask (300 mL), to which solution 18 g NH4-β (SiO2/
Al2O3 = 25; Zeolyst) was added under stirring.[11b] To exchange
NH4 ions with Pt ions, the solution was heated from room
temperature to 353 K at a heating rate of 8 K min 1, and kept
at 353 K for 12 h under stirring, followed by filtration and
washing with deionized water (500 mL) three times, and then
drying at 353 K for 6 h. The Pt2 + ion-exchanged sample was
further calcined at 773 K for 30 min in an O2 flow, and cooled
down rapidly to reaction temperature in a He flow to obtain
Pt6 cluster (2.1 wt %)/β.[11b] For the preparation of Ni4O4
cluster/β 0.194 g of [Ni(NH3)6](NO3)2 (Mitsuwa Chemicals
Co.) was dissolved in 10 mL deionized water in a 50 mL
Erlenmeyer flask, to which solution 1.96 g NH4-β (SiO2/
Al2O3 = 25; Zeolyst) was added under stirring.[11c] The Ni2 +
ion-exchanged sample was further calcined at 773 K for
30 min in an O2 flow of 5 mL min 1, and cooled down rapidly
to reaction temperature in a He flow to obtain Ni4O4 cluster
(2.0 wt %)/β.[11c] For the preparation of Cs + /β 0.062 g of
CsNO3 (Kanto Chemical Co.) was dissolved in 10 mL
deionized water in a 50 mL Erlenmeyer flask, to which
solution 1.96 g NH4-β (SiO2/Al2O3 = 25; Zeolyst or
JGCC&C) was added under stirring.[26] Ion-exchanges of NH4
ions with Ni or Cs ions were carried out in the similar way to
that for Pt ions, and then the samples were dried at 353 K for
6 h to obtain Ni (2.0 wt %)/β and Cs (2.1 wt %)/β.[11c,26] Na-
type β (SiO2/Al2O3 = 25) was also used for comparison. The
obtained M/β catalysts were characterized by XAFS, STEM/
EDS, XRD, XRF, XPS, BET, and DFT calculations. STEM
images (× 1,200,000) of the catalysts were measured by JEOL
JEM-2100F (200 kV) with a CCD camera (2048 × 2048
pixels).
Catalytic reaction set-up and GC product analysis.
Catalytic reactions were carried out on catalyst particles, sieved
into 500–850 μm, packed between quartz wools in a fixed-bed
down-flow reactor (quartz tube O.D. 6 mm) at atmospheric
pressure. All gas lines were heated at 423 K to avoid
condensation of the products. The catalysts were pre-treated at
673 K for 0.5 h in a flow of Bz/O2/NH3/He = 0.5/0.5/1.8/
4.0 mL min 1 and cooled rapidly to a given reaction temper-
ature. Benzene was introduced in the reactor by means of a
digital micro syringe pump (AS ONE Corporation, Japan).
The outlet stream was sampled with six-way sampling valves
heated at 423 K every 30 min using on-line Shimadzu GC-
2014 with a FID using a ZB-WAX plus capillary column
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(30 m, Phenomenex CA USA) for NH3, benzene and phenol,
and Shimadzu GC-2014 with a TCD using a WG-100
column (GL Science Japan) for O2, N2, CO, CO2, N2O, NH3
and H2O. The column temperature for TCD was typically
313 K. The column temperature for FID was held at 351 K
for 5 min, and then increased to 453 K at a heating rate of
28 K min 1. The conversion and selectivity in the Bz + O2 +
NH3 system were calculated by using NH3 as an internal
standard taking into account the calibration factors for NH3 in
the FID and TCD GCs.[15,16,26] The elemental carbon and
nitrogen mass balances in the benzene + O2 + NH3 systems
based on the inlet flows of benzene and NH3 were examined
to be the values between 97 % and 100 % in most of the
experimental runs.
XAFS characterization.[27] XAFS spectra at Cs L3-edge for
Cs/β and Ni K-edge for Ni/β were measured at 15 K in a
fluorescence mode and a transmission mode, respectively at
BL36XU in SPring-8. XAFS spectra at Pt L3-edge for Pt/β
were measured at 20 K at BL01B1 in SPring-8. The samples
under treated conditions were kept in sealed states without
exposing to external air until XAFS measurements. XANES
and EXAFS spectra were analyzed using the Larch code
containing the IFEFFIT Package ver.2 (Athena and Artemis),
the background subtraction in the EXAFS analysis using
Autobk and the Victoreen function, and the spline smoothing
method with Cook and Sayers criteria as the μ0 method.[28]
The extracted k2-weighted EXAFS oscillations were Fourier-
transformed to R-space, then curve fitted. The fitting
parameters for each shell were coordination number (CN),
interatomic distance (R), Debye-Waller factor (σ2), and
correction-of-edge energy (~E0). The phase shifts and
amplitude functions for M O and M M (M: Pt, Ni and Cs)
were obtained from FEFF (Ver 8.4).[29–31] Error ranges of the
curve-fitting analysis of EXAFS Fourier transforms were based
on the definition of the Feffit code in the Artemis program.[28]
DFT calculations. All calculations were conducted with
Dmol3 ver 3.0 (Accelrys, USA), using the numerical basis set
with polarization function (DNP), of which quality is
comparable to 6-31G*.[32] All electrons were explicitly
included, and all possible multiplicities of electronic states
were compared in the calculations and optimized multiplicity
was determined in each system. Perdew-Wang 91 functional
(PW91)[33] was used in all the calculations. Transition states
were searched by Dmol3 with the complete QST/LST option,
where the Linear Synchronous Transit (LST) maximization
was performed for the coordinates interpolated between a
reactant and a product, followed by repeated conjugated
gradient minimizations and the Quadratic Synchronous
Transit (QST) maximizations until a transition state has been
located.[34] In order to include the effect of zeolite framework,
a cluster containing 10 Si and O atoms with neighboring 5-
membered ring-4-membered ring-5 membered ring structure
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was taken from the crystal structure of β-zeolite with hydrogen
atom-termination. One Si atom was replaced by Al atom with
adding H atom on the neighboring oxygen atom. Positions of
Al atom, the added H atom and neighboring oxygen atoms
were relaxed by the structural optimization. Then the H atom
was replaced by Cs atom and the structure was relaxed.
Adsorption of benzene, O2 and NH3 and subsequent
intermediate states and transition states were calculated.[26] For
Pt6 cluster/β Pt 6-atom octahedron model was optimized, and
the size of the cluster was compatible with the pore channel of
β zeolite. Hence, octahedral Pt6 model was used for the
calculations.[11b] In the Benzene-O2-NH3 reaction on Pt6
cluster/β, zeolite protons are converted to NH4 + ions and Pt
clusters should interact with NH4 +, NH3, O2 and benzene. At
first the interaction between the Pt6 cluster and NH3/NH4 +
was examined. The Pt6 cluster was more stabilized with the
adsorption of NH3 and NH4 + as compared to two NH3
adsorption. Therefore, adsorption of NH3, NH4 +, O2 and
benzene on the Pt6 cluster and the subsequent reaction
processes were examined by DFT calculations, and the
transition states were also calculated. For Ni4O4 cluster/β
Ni4O4 cubic model was optimized, and the size of the cluster
was readily accommodated in the pore channel of β zeolite.
Similar to the case of the Pt6 cluster/β, the adsorption of NH3,
NH4 +, O2 and benzene on the Ni4O4 cluster and the
subsequent reaction processes involving the transition states
were examined by DFT calculations.[11c] The interaction
between NH3 and Ni4O4 cluster is hydrogen bonding between
the O atom and the NH3 hydrogen atom, which is contrasted
to the case of the Pt6 cluster/β, where NH3 adsorbs on the Pt
metallic cluster via nitrogen lone pair.[11b]
3. NH3-driven Selective Oxidation of Benzene to
Phenol with O2 on Single Cs + /β
The alkali metal ions (Na +, K +, Rb + and Cs +) and alkaline-
earth metal ions (Mg2 +, Ca2 +, Sr2 + and Ba2 +) incorporated into
β zeolite pores promoted neither benzene C H bond activation
nor O2 dissociation, and hence no reactions of benzene with O2
proceeded as typically seen in the case of Cs + /β (Table 1; 10th
entry). Recently, we reported that Pt6 metallic cluster/β and
Ni4O4 oxide cluster/β possessed intrinsic catalytic property of
benzene combustion to CO2 with O2 (Table 2; 1st & 4th
entries), whereas selective hydroxylation of benzene to phenol
with O2 proceeded when NH3 coexisted in gas phase, where the
reaction pathway was switched over from the deep oxidation to
the selective oxidation by NH3 (Table 2).[11b,c] Very recently,
similar NH3 effect, but more remarkable effect of NH3, on
selective oxidation catalysis of the alkali and alkaline-earth metal
ions/β samples was found; Despite the inactive oxidation
capability of the alkali and alkaline-earth metal ions incorpo-
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Table 1. Performances (conversion and selectivity) of various alkali
and alkaline-earth metal ions/β zeolite catalysts and Cs/SiO2-Al2O3
for the selective oxidation of benzene to phenol with O2 under
existing NH3 at 593 K.[26]
[a] The catalysts were pretreated with benzene/O2/NH3/He
(1.0 : 0.5 : 1.8 : 4.0 mL/min) 673 K for 0.5 h. Cat. = 0.2 g; Perfor-
mance values: averaged during 30–180 min time-on-stream; Reac-
tions: benzene/O2/NH3/He = 1.0 : 0.5 : 1.8 : 4.0 mL/min. Zeolite β
was purchased from Nikki Co. [b] Benzene/O2/He = 1.0/0.4/
5.8 mL min 1. [c] The catalysts were pretreated with benzene/O2/
NH3/He = 0.5/0.5/1.8/4.0 mL min 1 at 673 K for 0.5 h. Cat.
= 0.6 g; Performance values: averaged during 30–180 min time-on-
stream; Reactions: benzene/O2/NH3/He = 0.5/0.5/1.8/
4.0 mL min 1. [NH3]reacted/[Phenol]produced: reacted NH3 amount/
produced phenol amount. [d] identical condition to [c] except reac.
temp. 603 K. [e] identical condition to [c] except reac. temp. 623 K.
[f] The number in parenthesis is coordination number around metal
ion from database by Atomic Simulation Group in Materials
Department of Imperial College.
rated into β pores, the benzene C H activation toward phenol
synthesis proceeded under coexisting NH3 with a high selectivity
of 96.0 % at 1.3 % single-path conversion on 0.2 g of Cs
(2.0 wt %)/β and Rb(2.0 wt %)/β at 593 K (Table 1).[26] The
other alkali and alkaline-earth metal ions/β also showed good
selectivities (78–95 %), but the activities (conversions) were
lower than that of the Cs/β (Table 1). It is to be noted that
undesirable NH3 consumption on the Cs/β was low as
[NH3]consumed/[phenol]produced = 0.2. In contrast to the case of the
switchover of reaction pathways with NH3 on the Pt6/β and
Ni4O4/β (Table 2), NH3 opens a new reaction pathway for the
direct phenol synthesis from benzene with O2 on the single site
Cs/β and Rb/β catalysts. It is notable that Cs/amorphous
SiO2 Al2O3 with the similar SiO2/Al2O3 ratio of 25 to that of β
zeolite showed a neglijible performance (0.01 conv.%) and
caused lots of undesirable NH3 decomposition (Table 1; 11th
entry), which indicate a significant confinement effect of the β
zeolite pore architecture on the catalytic benzene C H
functionalization.[26]
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Table 2. Performances (conversion, turnover frequency (TOF) and
selectivity) of Pt6 metallic cluster/β (Pt: 2.1 wt %) and Ni4O4 oxide
cluster/β (Ni: 2.0 wt %) catalysts for phenol synthesis from
benzene/O2 regulated by NH3 and for benzene/O2 and benzene/
N2O reactions.[11b,c]
Cat. = 0.2 g; Pt: 2.1 wt %; Ni: 2.0 wt %; Zeolite β: SiO2/
Al2O3 = 25. Catalysts were calcined at 773 K for 0.5 h before use as
catalysts. Performance values: averaged at 50–210 min time-on-
stream. TOFs are defined as reacted benzene/total metal/h for
convenience. [a] benzene/O2/He = 0.5/1.6/8.0 mL min 1. [b] ben-
zene/N2O/He = 0.5/1.6/8.0 mL min 1. [c] benzene/O2/NH3 = 0.5/
1.6/8.0 mL min 1. [d] benzene/O2/He = 1.0/0.5/5.8 mL min 1. [e]
benzene/O2/NH3 = 1.0/0.5/1.8 mL min 1. [f] benzene/O2/
NH3 = 2.5/1.25/4.5 mL min 1. [g] benzene/O2/NH3/He = 1.0/0.5/
1.8/4.0 mL min 1. cat = 0.8 g.
One might suggest that NH3 is converted to N2O with O2
and the in situ formed N2O is the active species for the
benzene hydroxylation. However, NH3 was converted to N2
with O2 and neither N2O, NO nor NO2 were detected during
the catalytic reaction. Further, even if a small amount of N2O
was added to a mixture of benzene and NH3 instead of O2, the
benzene hydroxylation to phenol was negligible, thus indicat-
ing that the possible benzene oxidation with N2O is inhibited
by the coexisting NH3 on Cs/β. These results demonstrate that
the selective phenol synthesis in the benzene-O2-NH3 reaction
system is ascribed to contribution of O2 molecules. Next, we
attempted optimizing catalyst fabrication and reaction con-
ditions to achieve good performances to exceed 5 % conversion
and 70 % selectivity simultaneously because these values are
regarded as a critical performance economically for the
application to practical process. The ratio of the amounts of
consumed NH3 and produced phenol should also be less than
2 for practical industrial process.[11]
The catalytic performance largely depended on the kind of
Cs precursors (CsNO3, Cs2CO3, CsCl and CsOH) and the
source of β zeolites (Zeolyst, JGC C&C, and Tosoh) as shown
in Table S2. CsNO3 was the best precursor, while CsCl was
worst. The difference may be due to the difference in the ionic
or covalent character among the precursors. CsCl has a higher
degree of covalency, while CsNO3 is highly ionic and Cs ions
can be effectively ion-exchanged and located in the zeolite
pores near the surface layers. Among the zeolite sources, highly
crystalline β zeolite from JGC C&C showed the best perform-
ance as a support for Cs (Table S2). Using 0.6 g of Cs
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THE CHEMICAL RECORD
(2.0 wt %)/β (JGC C&C) at 593 K, we achieved 5.9 % single-
path benzene conversion and 83.4 % phenol selectivity
(Table 1).[26] The conversion and selectivity increased to 6.3 %
and 85.1 %, respectively at 603 K. To the best of our
knowledge, these are the highest yields for the direct phenol
synthesis from benzene with O2 in single-step gas-phase flow
reactions. There is no report on benzene C H activation
toward phenol synthesis by alkali-metal based catalysts. No
other liquid products were detected, and only an observed by-
product was gaseous CO2, which actually eliminates the
problem of separating the phenol product from the reaction
system. In the catalysis on 0.6 g of Cs (2.0 wt %)/β
undesirable NH3 consumption was so low as [NH3]consumed/
[phenol]produced = 1.1 and 1.9 at 593 K and 603 K, respectively.
Moreover, 2 wt %-Cs/β showed the best activity, and the
increment in Cs loading (> 3 wt %) reduced the phenol yield.
The basicity of catalysts increased with an increment in the
alkali loading and the effective charges of O atoms coordinated
to alkali ions increased.[35] Hence, the release of produced
phenol from the catalyst surface becomes hampered, and this
may be a plausible reason for the decrement of the efficiency
of the catalyst with higher Cs loading than 3 wt % (Table S2).
4. Characterization of Alkali Metal Sites/β
The alkali metal (Cs) sites incorporated into the β pores active
for the benzene C H functionalization to phenol synthesis
have been characterized by XPS, XAFS, STEM-EDS, XRD,
and DFT calculations.[26] The ex-situ XPS spectra at the 3d5/2
level for Cs/β samples as-synthesized and after the catalytic
reaction in Figure 1 (a) revealed the binding energies of 724.8
and 724.6 eV, respectively, which resemble 724.8 eV for
Cs2CO3 on Ag and 724.5 eV for CsOH, suggesting that Cs
atoms are situated in a monovalent Cs + level in β pores.[36] Cs
L3-XANES spectrum for the as-synthesized Cs/β catalyst is
shown in Figure 1 (b). The XANES spectrum did not change
with the pretreatment at 673 K before its application as a
catalyst and also remained unchanged after the catalytic phenol
synthesis reaction (Figure 1 (b)). The edge energies for the as-
synthesized, pretreated and spent Cs/β catalysts were all
5012.0 eV, which is the same as the energy for Cs2CO3 with
Cs + valence. However, the white line peak intensity of the Cs/
β catalysts greatly exceeded that of Cs2CO3 as shown in
Figure 1 (b), which is inconsistent with the XPS results in
Figure 1 (a). Simulation of the XANES white line peak
intensity at the Cs L3-edge by FEFF8.4 based on DFT
calculations with Dmol3 ver 3.0 (Accelrys)[32–35] revealed that
the white line peak intensity at Cs L3-edge strongly depends
on the local coordination structure around the Cs ion. The
simulation results confirmed considerably larger peak intensity
for the Cs/β than that for Cs2CO3. The XPS and XANES
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Figure 1. XPS and XAFS characterizations of Cs/β catalyst. (a) Ex situ XPS
spectra at Cs 3d5/2 for fresh (as-synthesized) and spent Cs (2 wt %)/β
catalysts. The binding energies for CsClO4, CsOH and Cs2CO3 on Ag as
references are also shown. (b) Cs L3-edge XANES spectra for the fresh,
pretreated and spent Cs/β catalysts and XANES spectrum for Cs2CO3 as
reference. (c) EXAFS oscillation (black: obs.; red: fitting) of the as-
synthesized Cs/β. (d) EXAFS Fourier transform (black: obs.; red: fitting;
gray: imaginary part; orange: fitting). (e) Structural parameters for the as-
synthesized and pretreated Cs/β catalysts determined by EXAFS curve-fitting
(R-space) analysis.[26]
spectra for the the Cs/β catalyst indicate unique coordination
structure and electronic state of Cs derived from the β pore
architecture, much different from those of Cs + 2CO3. The
EXAFS analysis at Cs L3-edge for the pretreated Cs/β sample
before its use as a catalyst revealed only Cs O bonds at
0.320 nm (� 0.017 nm) with coordination number of 3.7 �
2.1, and no Cs Cs bonds were detected as shown in Figure 1
(c–e).[26] This observation suggests that a single Cs + site
coordinated by three to four O atoms of the β pore wall acted
as the active platform for the selective phenol synthesis from
benzene with O2 in the presence of NH3. STEM images reveal
no feature except for the β zeolite lattice. The edge energies of
XANES spectra for the as-synthesized and spent Rb/β catalysts
were similar to that for Rb + NO3 aq., and Rb K-edge EXAFS
analysis revealed no Rb Rb bonds and only Rb O bonds at
0.299–0.328 nm (� 0.016 nm) were observed. The results also
indicate single Rb + ion site. The single Cs + and Rb + sites
were stable and not aggregated to their oxides under the
catalysis conditions even upon increasing the Cs and Rb
loadings to 8 wt % as suggested from no XRD patterns.[26]
Temperature programmed desorption (TPD) of CO2 and
acetonitrile (CH3CN) on Cs + /β at 300–923 K was conducted
to estimate basic and acidic strengths of the Cs + /β catalyst,
respectively (Figure S1). Most of the adsorbed CO2 desorbed
below 313 K, and the desorbed amount was negligible (< 1% of
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THE CHEMICAL RECORD
Cs), thus indicating very weak or negligible basicity of Cs + /β.
The by-product of the catalytic reaction was solely CO2. The
XAFS analysis revealed no changes in the coordination number
for Cs O, white line peak intensity and edge energy throughout
in the reaction stream, indicating the stable coordination
structure around the single Cs + site and no diffusion of the Cs +
species, which may exclude possibility of Cs2CO3 formation
under the present reaction conditions and in the time-on-
stream. Further, in CO2 TPD on Cs + /β most of the adsorbed
CO2 desorbed below 313 K and CO2 desorption was completed
around 348 K as shown in Figure S1, which is much lower than
the reaction temperatures 593–623 K. These results exclude the
significant formation of stable Cs2CO3. The TPD peak for
CH3CN on Cs + /β was observed around 365 K, and the
desorbed CH3CN amount per Cs after subtracting the desorbed
amount from β was 57 % of the Cs quantity. The results
indicate the weak acidity of single Cs + ions in β pores.
Therefore, the single Cs + sites possess the characteristic of a
weak Lewis acid.
Figure 2. Relation between catalytic performances and ionic radii of metal
cations; Plots of the phenol selectivities (%) and phenol yields (%) versus the
ionic radii of alkali and alkaline-earth metal ions, and for comparison, plots
of the phenol yields (%) vs the ionic radii of transition and precious metal
ions (ionic radii, conv.% and selec.% are shown in Table S1). Reac. temp. =
593 K; Cat. = 0.6 g; Performance values: averaged during 30–180 min time-
on-stream; Benzene/O2/NH3/He = 0.5/0.5/1.8/4.0 mL min 1.
Figure 2 shows the plots of the phenol selectivity (%) and
phenol yield (%) in the single-path gas-phase flow reaction
against the ionic radii of alkali metal ions (Na +, K +, Rb +, and
Cs +) and alkaline-earth metal ions (Mg2 +, Ca2 +, Sr2 + and
Ba2 +) (Table 1) and for comparison, the plots of the phenol
yield (%) vs. the ionic radii of transition and precious metal
ions (V4 +, Cr3 +, Mn2 +, Fe3 +, Co3 +, Ni2 +, Cu2 +, Ag +, and
Ir3 +) (Table S1). These transition and precious metal ions/β
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Figure 3. A computational reaction profile for the concerted inter-ligand reaction mechanism involving coadsorption states and transition states for the selective
oxidation of benzene to phenol with O2 regulated by NH3 on the Cs + /β cluster by DFT calculations. Cs: dark purple, O: red, C: gray, H: white, N: blue, Si:
yellow, Al: pink.[26]

samples with ion diameters smaller than 0.200 nm did not
show significant yields for phenol synthesis as compared to the
yields of the alkali and alkaline-earth metal ions/β samples,
particularly Cs + /β, with the the largest ion diameter
(0.334 nm). The Cs + /β catalyst among the examined alkali
and alkaline-earth metal ions/β catalysts also showed the
advantage of the lowest undesirable NH3 consumption
(Table 1).
5. Reaction Profiles for NH3-driven Benzene C-H
Activation Toward Phenole Synthesis
The benzene C H functionalization (hydroxylation) with O2
toward phenol synthesis is a chemical event involving
oxidation-reduction processes of reactants, but the single Cs +
site incorporated into the β pore possesses a weak Lewis acidic
character and shows almost no change in the oxidation state as
demonstrated from the XANES white line peak intensity and
EXAFS local coordination structure) before and after the
catalytic benzene hydroxylation under coexisting NH3. Partic-
ularly, the single Cs + /β is intrinsically inactive for benzene
oxidation with O2, whereas in the presence of NH3 benzene is
transformed to phenol selectively on the Cs + /β. To understand
the origin of the unique property of the single Cs + site
catalysis, the reaction mechanism and the role of NH3 in the
synthesis of phenol on the single Cs + /β catalyst has been
simulated by DFT.[26] We performed periodic, self-consistent
DFT calculations for the selective oxidation reaction pathway
on the Cs + /β. A detailed computational reaction profile for
the reaction mechanism involving associative coadsorption
states and transition states for the selective oxidation of
benzene to phenol with O2 regulated by NH3 on the Cs + /β
cluster by DFT calculations is shown in Figure 3. A simulated
coordination arrangement for the molecular coadsorption of
benzene, O2 and NH3 on a single Cs + ion at the cross channel
in the β zeolite pore is also shown in Figure 3; this arrange-
ment conforms to the pore channel space of β zeolite.[26] At
the molecular coadsorption state, the adsorbed O2 is activated
with the coadsorbed NH3 to dissociate O2 and form an O C
(benzene) bond in a concerted mechanism via a transition state
(TS1). In this step no free O atom is formed. The inter-

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Figure 4. A computational reaction profile for the inter-ligand reaction mechanism involving coadsorption states and transition states of the four components
(benzene + O2 + NH3 + NH4 +) for the selective oxidation of benzene to phenol with O2 regulated by NH3 on the Pt6 cluster/β by DFT calculations. Pt6 cluster:
blue, O: red, C: gray, H: white, N: bright blue.[11b]
coadsorbate reaction (three-molecular concerted mechanism)
on a single Cs + site is a plausible explanation for the high
phenol selectivity. In the subsequent step, the H atom on the
O C (benzene) carbon atom migrates to the oxygen atom
(proton transfer) to form phenol via the second transition state
(TS2). In summary, DFT calculations indicate that the
catalytic activity arises from the single Cs + cations in β pores
and that the activation barriers are sufficiently moderate for
the reactions to proceed at low temperatures in agreement with
the experimental results. This reaction pathway proceeds on a
single Cs + site; in other words, a large reaction platform is
necessary to enable the accommodation of the three adsorbed
molecules and subsequent bond rearrangements on the single
Cs + site in the β pore (Figure 3). The ion diameters of Cs +
(0.334 nm) and Rb + (0.304 nm) are significantly larger than
the diameters of other alkali and alkaline-earth metal ions.
Therefore, this process can proceed on the single Cs + and Rb +
sites.[26]
The switchover of the reaction pathways from the deep
oxidation to selective oxidation of benzene by NH3 has been
reported on the Pt6 metallic cluster/β and Ni4O4 oxide cluster/
β catalysts in our previous work,[11b,c] which involves a different
mechanistic aspect from the case of the single Cs + site/β
catalyst.[26] For the Pt6/β catalyst EXAFS, STEM/EDS and
DFT calculations demonstrated that an octahedral Pt6 cluster
in β pore is stable and active for the benzene oxidation to
phenol in the presence of NH3.[11b] The reaction path for the
phenol synthesis was simulated by DFT, which involves the
Pt6 intermediates with Pt-O C(Bz) bonding and phenol
product (Figure 4). In the steady-state benzene-O2-NH3
reaction, zeolite protons are converted to NH4 + ions and Pt
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THE CHEMICAL RECORD
clusters may also interact with NH4 + besides NH3, O2 and
benzene. The Pt6 cluster was more stabilized with the
additional adsorption of NH4 + (DFT calculation). O2 adsorbs
molecularly and readily dissociates to two O atoms, followed
by the inter-ligand bond rearrangement (NH3-O Bz) to make
a Pt-O C(Bz) bond with a carbon atom of π-coordinated
benzene via the transition state TS1. Then, H atom bound to
the carbon atom migrates to the oxygen atom to produce the
adsorbed phenol on the Pt6 cluster with the much larger
energy barrier than that for the Cs + /β catalyst (Figures 3 and
4).
The Ni (2.0 wt %)/β catalyst showed a similar XANES
white line peak energy to those for Ni(acac)2, Ni(NO3)2, and
NiO, indicating the Ni2 + oxidation state.[11c] The Ni O and
Ni Ni bond distances at 0.207 nm (CN(Ni O): 5.9) and
0.296 nm (CN(Ni Ni): 2.8), respectively determined by
EXAFS resembled those for NiO bulk (0.2084 nm and
0.2948 nm, respectively), whereas the CN(Ni Ni) (2.8) was
much smaller than 11.5 for the NiO bulk, which suggests a
cubic Ni4O4 cluster structure (CN(Ni Ni): 3.0). However, the
observed CN(Ni O) was larger than 3.0. Hence, Ni atoms in
the Ni4O4 clusters may be coordinated with O atoms of the β
pore walls and/or minor Ni2 + species with octahedral Ni O
coordination may also exist without clusterization in the β
pores upon the pretreatment at 773 K. The octahedral NiO6
species do not work as an active structure for the phenol
synthesis because benzene and O2 cannot adsorb on it as
proved by DFT calculations.[11c] STEM images demonstrated
that the [NiO]x clusters were located in the β pores though the
[NiO]x image contrast was weak and fragile under the STEM
electron irradiation.[11c]
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Figure 5. A computational reaction profile for the phenol synthesis reaction via the reaction intermediates and transition states in the benzene + O2 + NH3 +
NH4 + system on the Ni4O4 cluster/β. Ni: blueish gray, O: red, C: gray, H: white, N: blue.[11c]
DFT calculations demonstrate that the Ni4O4 cubic cluster
in the β pore is stable and active for the selective benzene
oxidation to form phenol in the presence of NH3 (Figure 5).
Oxygen atoms of the Ni4O4 cluster were inactive for the
benzene oxidation at 593 K. Thus, the reaction path for the
phenol synthesis from benzene and O2 in the presence of NH3
was simulated by DFT as shown in Figure 5, where a NH4 +
cation was also involved in the coordination sphere similar to
the case of the Pt6/β.
The interaction between NH3 and Ni4O4 cluster is hydrogen
bonding between the O atom and the NH3 hydrogen atom
(Figure 5), which is contrasted to the cases of the Pt6 cluster/β
and single Cs + /β, where NH3 adsorbs on the Pt6 metallic cluster
and singel Cs + ion via nitrogen lone pair.[11b,c,26] The adsorbed O2
readily dissociates to two O atoms bonded to Ni atoms. One of
the two O atoms interacts with NH3 by hydrogen bonding and
another O atom interacts with NH4 +. Then, the inter-ligand
bond rearrangement (NH3 O Bz) proceeds to make a Ni O C
(Bz) bond through the transition state TS2. In the Ni4O4
intermediate with Ni O C(Bz) bond another O atom abstracts
proton from NH4 + to form Ni OH + ….NH3 moiety, which
indicates that no free O atoms remain on the cluster. Thereby
further deep oxidation is suppressed. In the final step the H atom
migrates as H + to the oxygen atom to produce an adsorbed
phenol via the transition state TS3 with the higher activation
barrier than that for the Cs + /β and the lower barrier than that
for the Pt6/β (Figure 5).[11c]
Chem. Rec. 2019, 19, 1 – 14 © 2019 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
THE CHEMICAL RECORD
The switchover of the reaction pathways from the CO2
formation to phenol synthesis on the Pt6 and Ni4O4 clusters/β
catalysts (Table 2) proceeds by the inter-ligand bond rearrange-
ment mechanism between Bz O NH3 (Figures 4 and 5). By
contrast, the genesis of the selective oxidation activity of the
single Cs + /β catalyst is brought about by the concerted inter-
ligand bond rearrangement between Bz O2 NH3 (Figure 3),
where no benzene oxidation occurs without NH3 (Table 1).[26]
6. Summary
The benzene C H activation toward selective phenol synthesis
in a gas-phase single-path flow reaction process on a
heterogeneous catalyst is still a great challenge. We have found
the unprecedented catalysis of alkali and alkaline-earth metal
cations incorporated into β zeolite pores, particularly single
Cs + ion/β and single Rb + ion/β catalylsts with metal ion
diameters greater than 0.300 nm, which selectively promotes
direct phenol synthesis from benzene and O2 in the presence
of NH3. The amount of undesirable NH3 consumption was
suppressed to be [NH3]consumed/[phenol]produced < 2.0, which
may be a critical value for a practial process. The lower the
NH3 price, the more the NH3-driven benzene hydroxylation
with O2 will be promising industrially. The single Cs + and
Rb + sites without significant Lewis acidic basic property nor
redox property cannot activate benzene, O2, and NH3 when
they get adsorbed independently. However, when they
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coadsorbed together, the reaction of the inter-coadsorbates on
the single alkali-metal ion site proceeds concertedly (the inter-
ligand concerted mechanism), causing benzene C H activation
toward phenol synthesis. We have also compared to the
switchover of the reaction pathways from the deep oxidation
of benzene to CO2 to the selective oxidation of benzene to
phenol by NH3 on Pt6 metallic cluster/β and Ni4O4 oxide
cluster/β. The NH3-driven selective oxidation mechanism
observed with the Cs + /β and Rb + /β differs from the tradi-
tional redox catalysis (Mars-van Krevelen) mechanism, simple
Langmuir-Hinshelwood mechanism, and acid base catalysis
mechanism involving clearly defined interaction modes. The
single Cs + and Rb + sites with the large ion diameters provide
the pivotal confined single metal ion site platform with a
sufficiently large coordination sphere for the selective inter-
ligand concerted reaction pathway. These findings present a
new approach for designing of highly efficient selective C H
activation catalysis under mild conditions.
Acknowledgements
The study was supported by Grant-in-Aid for Scientific
Research (16F16078 and 16F16383). S. S. A. and S. G. thank
JSPS Postdoctoral Fellowship for foreign researchers. The
XAFS measurements were performed with the approval of
SPring-8 subject number 2016 A7840, 2016B7840,
2017 A7840, 2017B7840, 2018 A7840, and 2018B7840.
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Manuscript received: April 3, 2019
Revised manuscript received: June 1, 2019
Version of record online: ■■ ■■, ■■■■

Chem. Rec. 2019, 19, 1 – 14 © 2019 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Wiley Online Library 13
PERSONAL ACCOUNT
We have found the unprecedented NH3- Dr. S. S. Acharyya, Dr. S. Ghosh, Dr. Y.
driven benzene C H activation toward Yoshida, Dr. T. Kaneko, Dr. T. Sasaki*,
selective phenol synthesis on single Cs + Prof. Dr. Y. Iwasawa*
and Rb + /β catalysts with metal ion
1 – 14
diameters greater than 0.300 nm. The
inter-ligand concerted mechanism NH3-Driven Benzene C H Activation
observed with the Cs + /β and Rb + /β with O2 that Opens a New Way for
differs from the traditional redox Selective Phenol Synthesis
catalysis mechanism and acid base
catalysis mechanism. These findings
present a new approach for designing of
highly efficient selective C H activation
catalysis under mild conditions.