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I O N I C M AT E R I A L S

Large, soft, and polarizable hydride ions

sneak around in an oxyhydride
A perovskite containing highly electropositive cations conducts hydride anions

onic conductivity in solids, a eld initiated by Faraday (1), has led to materials
that help chemists spatially separate the
oxidation and reduction steps of reactions, enabling technologies such as fuel
cells. Many solid oxides are good oxygen
ion (O2) conductors, but getting hydrogen
ions, either protons (H+) or hydride anions
(H), to conduct through oxides has been a
major challenge. A proton-conducting oxide
reported in 1981 (2) marked the beginning of
oxide protonics, a materials science based
on solid solutions of oxides and hydroxides.
On page 1314 of this issue, Kobayashi et al.
(3) report a material with pure H conductivity (and yet an electronic insulator) in an
oxyhydride system, which has been a last
frontier in solid state ionics.
Except in the ionosphere, H is exceedingly rare on Earth because of its extremely large pKa (acidity constant) for
the deprotonation reaction of hydrogen.
Eforts to discover H conductors have
primarily followed two strategies, one on
oxide protonicsexploring oxyhydride maDepartment of Materials Engineering, The University of Tokyo,
Tokyo, Japan. E-mail: yamaguchi@material.t.u-tokyo.ac.jp

terials (4) and the other exploring metal

hydride systems with strong ionic bonding
characters, such as alkali-earth hydrides
(5) and their analogs (6). Because metal
hydrides have high electronic conductivity,
it had been assumed that H conductivity
was negligible. Thus, the discovery of hydride ion conductivity in undoped BaH2
was surprising, and was only revealed by
the coincidence of the measured electromotive force (emf ) for a hydrogen concentration cell with the theoretical one
predicted by the Nernst equation for a
pure H conductor (7).
For oxyhydride systems, although H
was incorporated into perovskite oxides in
a metastable condition that preserved the
crystal framework (8, 9), no clear evidence
of H conductivity could be obtained, except for a subtle trace, because of interference from the electron-predominant
conductivity (4, 10). The presence of H in
mayenite (12CaO7Al2O3 or C12A7) (11, 12)
shed light on the importance of chemical
stability of C12A7 during heat treatment
under an extremely reducing condition, in
order to increase electron energy to stabilize H.
Several lines of experimental evidence
support the report of Kobayashi et al. (3)

of H conductivity in La2-x-ySrx+yLiH1-x+yO3-y.
Detailed crystallographic analyses with
neutron difraction suggest an ordered arrangement of H and oxide ion (O2) ions
in the anion sublattice. The authors also
performed electrochemical measurements
of the conductivity and electrochemical
polarization in the concentration cell with
a protocol nearly identical to the so-called
Tubandt method. The polarity, the magnitude of the cell emf, and consistent hydrogen transport all provide evidence for the
transport of H during direct-current (dc)
polarization under blocking conditions for
O2 transport.
What are the origins of H conductivity
in this material? First, all of the component
cationsLa3+, Sr2+, and Li+are extremely
electropositive. They form very stable oxides and hydrides, and would produce
donor states for electron (e) conductivity
with great difculty, even under extremely
reducing conditions. Further, these oxides and halides form stable intermediate
oxyhydride compounds with extended solid
solubilities.
To obtain a pure H conductor, electronic
conductivity must be suppressed. Carrier
mobility is typically more than 1000 times
greater for electrons than for much larger

Large and soft O2

Small and hard H+

Hard and electropositive

cation

Stealthy hydride ions. The two images contrast how (A) protons localize in an oxide, but (B) hydrides delocalize and conduct through an oxide with very electropositive cations.
sciencemag.org SCIENCE

18 MARCH 2016 VOL 351 ISSUE 6279

Published by AAAS

ILLUSTRATION: P. HUEY/SCIENCE

Large and soft H

Hard cation

1262

Downloaded from on April 9, 2016

By Shu Yamaguchi

ions. The partial H conductivity can be easily hindered even by a small amount of electrons formed by the reaction

where
and
, expressed in Krger-Vink
notation, are the H ion on a regular H sublattice and its vacancy, respectively.
The origin of fast ion conduction in ionic
solids is still unclear. Apparently, such materials should have defects that increase
the chance of hoppingthat is, the number of mobile ions and stable regular sites
should not be equal. An easier way to introduce ionic defects is the introduction
of anion vacancy by chemical doping of an
acceptor, to avoid the electron formation
discussed above. For example, electrons
can be trapped by acceptors like O2, which
suggests an important role for oxide ions.
The faster H migration is likely favored in
the mobility competition between anions
because H has a lower charge density than
O2 with a lower nominal valence and a similar ionic radius (1.46 for H and 1.4 for
O2). This explanation, however, needs further verication. The low charge density of
H may lead to a large polarizability, which
provides an inspiration for the sneaking
H migration (see the gure). This feature
contrasts with the extremely high charge
density of protons.
The result of Kobayashi et al. is just
the beginning of a new materials science
of H conductivity in oxyhydride systems
that will require further elaboration of the
underlying mechanisms, as well as potential applications of the extremely reducing
H ion in chemical synthesis. A drawback
of the current material is its chemical reactivity in oxidizing atmospheres, but this
disadvantage may be overcome by various
techniques, like surface protection coatings.
These explorations of H conductors now
leave the question of what will be the next
last frontier for solid state ionics.

PHOTO: SPL/SCIENCE SOURCE

REFERENCES

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7. M. C. Verbraeken, C. Cheung, E. Suard, J. T. S. Irvine, Nat.
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8. M. A. Hayward et al., Science 295, 1882 (2002).
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(2006).
11. K. Hayashi, S. Matsuishi, T. Kamiya, M. Hirano, H. Hosono,
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10.1126/science.aaf3361

Web of defense. In this false-color scanning electron micrograph, a Klebsiella pneumoniae bacterium is caught in
a web of extruded chromatin in a mouse lung. The web contains antimicrobial components that kill the bacterium.
K. pneumoniae and other Enterobacteriaceae are increasingly becoming resistant to antibiotics, including last-resort
compounds such as colistin.

A N T I M I C R O B I A L R E S I STA N C E

New mechanisms, new worries

The increasing spread of colistin resistance is
resulting in untreatable infections
By Marc Sprenger and Keiji Fukuda

rowing levels of resistance to available

antimicrobial medicines are causing tens of thousands of deaths each
year across the world (1). By 2050,
the overall costs associated with antimicrobial resistance (AMR) could reduce global gross domestic product (GDP) by
2 to 3.5% (2). One concern is the development
of resistance to the carbapenem antibiotics
among Gram-negative bacteria, in particular,
the carbapenemase-producing Enterobacteriaceae (CPE) (see the image). Enterobacteriaceae are the source of community- and
hospital-acquired infections and commonly
cause opportunistic infections, including
pneumonia, and sometimes death (3). CPE
are resistant to nearly all available antibiotics, with the exception of colistin. Emerging
resistance to colistin therefore has troubling
implications for patient care.
Carbapenemase enzymes confer resistance to most -lactam antibiotics, including carbapenem, making them particularly
dangerous because they can inactivate a
wide range of diferent antibiotics (4). Accurate detection of carbapenemase producers
is therefore essential for infection control
Antimicrobial Resistance Secretariat, World Health
Organization, 1211 Geneva 27, Switzerland. E-mail:
sprengerm@who.int; fukudak@who.int

SCIENCE sciencemag.org

and management of antibiotic therapy (5).

Carbapenemases are divided into three main
classes, which difer in their mechanism of
action. Class A includes the most common
carbapenemase, Klebsiella pneumoniae carbapenemase. Class B carbapenemases are
metallo-lactamases. An important member of this class is New Delhi metallo-betalactamase (NDM), which has spread widely

E. coli and K. pneumoniae

are already increasingly
resistant to all other
available antibiotics; the
transfer of colistin resistance
to such bacteria can thus
result in untreatable
infections.
since it was rst described in 2009. Class D
includes carbapenem-hydrolyzing oxacillinase-48 (OXA-48) (6), which is being reported
with increasing frequency in outbreaks and
case reports across the world (7). OXA-48 is
particularly difcult to detect (8).
Over the past 2 years, Enterobacteriaceae
that produce OXA-48 and NDM have rapidly
18 MARCH 2016 VOL 351 ISSUE 6279

Published by AAAS

1263

Large, soft, and polarizable hydride ions sneak around in an

oxyhydride
Shu Yamaguchi
Science 351, 1262 (2016);
DOI: 10.1126/science.aaf3361

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