Stereoselective Transfer Semi-Hydrogenation of Alkynes to E-Olefins with N-Heterocyclic Silylene–Manganese Catalysts

Article abstract of DOI:10.1002/chem.201705745

The synthesis and structures of the first Si^II-donor supported manganese(II) complexes [L1]MnCl₂, [L2]MnCl₂, and [L3]₂MnCl₂ are reported, bearing a pincer-type bis(NHSi)-pyridine ligand L1, bidentate bis(NHSi)-ferrocene ligand L2, and two monodentate NHSi ligands L3 (NHSi = N-heterocyclic silylene), respectively. They act as unprecedented very active and stereoselective Mn-based precatalysts (1 mol % loading) in transfer semi-hydrogenations of alkynes to give the corresponding E-olefins using ammonia–borane as a convenient hydrogen source under mild reaction conditions. Complex [L1]MnCl₂ shows the best catalytic performance with quantitative conversion rates and excellent E-stereoselectivities (up to 98 %) for different alkyne substrates. Different types of functional groups can be tolerated, except CN, NH₂, NO₂, and OH groups at the phenyl group of 1-phenyl substituted alkynes.

Full text of DOI:10.1002/chem.201705745

A Journal of
Accepted Article
Title: Stereoselective Transfer Semi-Hydrogenation of Alkynes to (E)-
Olefins with N-Heterocyclic Silylene-Manganese Catalysts
Authors: Matthias Driess, Yupeng Zhou, Zhenbo Mo, and Marcel Philip
Lücke
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201705745
Link to VoR: http://dx.doi.org/10.1002/chem.201705745
Supported by

10.1002/chem.201705745
Chemistry - A European Journal
COMMUNICATION
A Molecular Approach to Manganese Nitride Acting as a High
Performance Electrocatalyst in the Oxygen Evolution Reaction
Carsten Walter,[a]+ Prashanth W. Menezes,[a]+ Steven Orthmann,[b] Jona Schuch,[c] Paula Connor,[c]
Bernhard Kaiser,[c] Martin Lerch,[b] and Matthias Driess[a]*
Abstract: The scalable synthesis of phase-pure crystalline
manganese nitride (Mn3N2) from a molecular precursor is reported; it
acts as a superiorly active and durable electrocatalyst in the oxygen
evolution reaction (OER) from water under alkaline conditions. While
electrophoretically deposited Mn3N2 on fluorine tin oxide (FTO)
requires an overpotential of 390 mV, the latter is substantially
decreased to merely 270 mV on nickel foam at a current density of
10 mAcm-2 with a durability of weeks. The high performance of this
material is due to the rapid transformation of manganese sites at the
surface of Mn3N2 into an amorphous active MnOx overlayer under
operation conditions intimately connected with metallic Mn3N2 which
increases the charge transfer from the active catalyst surface to the
electrode substrates and thus outperforms the electrocatalytic
activity in comparison to solely MnOx-based OER catalysts.
active sites and their dynamics by means of various microscopic
and spectroscopic methods.[9] One of the decisive factors to
boost the catalytic OER activity is the ability of polynuclear MnOx
moieties in different coordination environments to undergo
reversible redox transitions with mixed-valent states and to
facilitate the formation of Mn3+ during O–O bond formation.
Since all known MnOx systems are electrical insulators, they
need to be immobilized on conducting supports to enable
efficient electron transport from the catalyst surface to the
electrode in the electrocatalytic OER. This ‘thwarted’
performance of MnOx in electrocatalytic OER prompted us to
investigate whether or not its performance can be substantially
increased if produced in situ on the surface of metallic
manganese nitride. It has been shown lately, that nitrides of iron,
cobalt and nickel can act as highly efficient pre-catalysts for
OER and HER.[10] In spite of the fact that only a few manganese
nitrides exist in the binary phase diagram of Mn−N, the
applications of them are rather limited, primarily due to a lack of
effective synthetic methods.[11,12] The commonly used solid state
techniques require high temperature and favor the formation of
multi-phase products.[12,13] Manganese nitrides are typically
synthesized by annealing Mn powder in ammonia (NH3)
atmosphere at relatively high temperature.[13,14,15] Other
procedures include a solvothermal route via a high-temperature
and high-pressure method using autoclaves.[15,16] Attaining
manganese nitrides from molecular precursors is highly
compelling due to the rational access and shape selectivity
determined on the molecular level. Up to now only a few
protocols on manganese nitrides have been reported using a
molecular approach but they gave merely air-sensitive
materials.[17,18]
The electrochemical overall water-splitting has emerged as an
alternative approach for the large-scale production of hydrogen
through the cathodic hydrogen evolution reaction (HER) along
with the anodic oxygen evolution reaction (OER).[1,2] Although
numerous inexpensive and active non-noble HER catalytic
systems have been well established, the development of
effective OER catalysts for the oxidative half-reaction of water is
still challenging.[1] Presently, most of the best catalysts for OER
are based on precious metals (i.e., MOx (M = Ir, Ru)), however,
the high cost and scarcity greatly limit their practical large scale
application.[2] Thus, considerable research efforts have been
undertaken to the betterment of non-precious metal-based OER
electrocatalysts employing earth-abundant metals.[3–7]
In this regard, Mn-based materials have drawn much
attention as potential OER catalysts inspired by the Mn-
containing oxygen evolving complex (OEC) in the natural
photosystem II (PSII). Accordingly, various crystalline and
amorphous MnOx materials have been synthesized and tested in
the OER in the last few years.[8] The investigations led to the
Here we present the novel molecular route to air-stable,
reliably scalable and phase pure crystalline manganese nitride
(Mn3N2) which displayed an excellent performance as pre-
catalyst in OER with outstanding durability in alkaline media.
Mn3N2 was successfully prepared in a straightforward route
disposal of functional materials where
a structure-activity
relationship could be uncovered through the identification of the
through ammonolysis of manganocene [(C5H5)2Mn] as
a
molecular precursor at 700 °C for 12 h using a tube furnace
(Scheme 1; see Supporting Information). Reproducibility, easy
handling, fast production and facile up-scaling are the major
advantages in comparison to other synthetic protocols reported
for metal nitrides as yet. The as-prepared material was
characterized by powder X-ray diffraction (PXRD) and Rietveld
refinement; the reflections could be unambiguously assigned to
the pure η-Mn3N2 phase (Figure S1 in Supporting Information).
The morphology of η-Mn3N2 was analyzed by scanning electron
microscopy (SEM) which showed agglomeration of large,
irregular shaped particles (Figures 1a and S4). The transmission
electron microscopy (TEM) revealed that the η-Mn3N2 particles
were highly crystalline; the resulting selected area diffraction
[a]
C. Walter, Dr. P. W. Menezes, Prof. Dr. M. Driess
Department of Chemistry, Metalorganics and Inorganic Materials
Technische Universität Berlin
Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin (Germany)
E-mail: matthias.driess@tu-berlin.de
[b]
[c]
[+]
S. Orthmann, Prof. Dr. M. Lerch
Department of Chemistry, Solid State Chemistry
Technische Universität Berlin
Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin (Germany)
J. Schuch, P. Connor, PD. Dr. B. Kaiser
Institute of Material Science
Technische Universität Darmstadt
Jovanka-Bontschits-Straße 2, 64287 Darmstadt (Germany)
pattern (SAED), extracted from
a
high-resolution TEM
These authors contributed equally to this work.
micrograph, revealed the spacing of 0.243 nm and 0.127 nm
corresponding to (013) and (123) planes, respectively (Figures
1b and S5). The energy dispersive X-ray analysis (EDX)
Supporting information for this article is given via a link at the end
of the document.
This article is protected by copyright. All rights reserved.

10.1002/chem.201705745
Chemistry - A European Journal
COMMUNICATION
mapping of Mn3N2 confirmed the homogenous distribution of Mn
and N in the particles and the phase composition in accordance
with the molar ratio derived from the chemical formula (Figures
1c-1d, S3 and Table S1).
Mn3N2 whereas an overpotential of 470 mV was needed for
Mn2O3 to reach the same current density. The Tafel slope
(Figure S13) of Mn3N2 was found to be 97 mVdec-1 which was
lower compared to the Mn2O3 (108 mVdec-1).
Scheme 1. Synthesis and crystal structure of Mn3N2 which was
electrodeposited (EPD) on the electrode substrate for the OER (green
spheres: two-coordinated Mn; chartreuse spheres: five-coordinate Mn; blue
spheres: six-coordinated N).
Mn3N2 crystallizes in the tetragonal Al3Os2-type structure in
the space group I4/mmm.[19] Two types of crystallographically
non-equivalent Mn positions exist in the structure, the first Mn
has two neighboring nitrogen atoms with shorter Mn-N bonds
while the second Mn is penta-coordinated to nitrogen atoms,
leaving vacant octahedral voids within the structure (detailed
descriptions are given in Figure S2 in Supporting Information).[19]
The comprehensive surface composition of the as-synthesized
Mn3N2 was gathered from X-ray photoelectron spectroscopy
(XPS). The corresponding photoemission lines of Mn2p, Mn3p
and Mn3s are shown in Figures 2 and S6. The Mn2p core level
spectrum features two main spin–orbit peaks of 2p3/2 at 641.1 eV
and 2p1/2 at 652.7 eV with a distance of 10.8 eV to the 2p1/2
satellite corresponding to a mixture of Mn2+/Mn3+ oxidation
states.[20,21] This is also supported by the Mn3s photoemission
line with a multiplet splitting distance of 5.3 eV as well as by
Mn3p at binding energy of 48.1 eV.[20,21] The presence of Mn3+ is
corroborated to surface passivation of Mn3N2 due to an ex-situ
transport in air (see Figure S6).
Interestingly, it has been found that the presence of Mn3+
in the structure of manganese oxide is decisive for influencing
catalytic activity and in this regard, Mn2O3 materials have been
widely studied and proven to enhance catalytic OER activity
significantly.[22] For comparison, the Cp2Mn precursor was also
oxidized in dry synthetic air to give the highly crystalline
manganese (Mn2O3) oxide with the cubic bixbyite-type structure.
(Figures S7-S11 in Supporting Information). Four-probe
resistivity measurements were carried out which confirmed
significantly higher charge mobility of Mn3N2 compared to Mn2O3
(Table S2).
Figure 1. (a) SEM micrographs of Mn3N2 particles revealing large particles, (b),
TEM image of a particle indicating the crystalline character as shown by SAED
in the inset, (c) and (d) depicts the EDX mapping of homogenously distributed
Mn (green) and N (blue) in the Mn3N2 particles.
While cycling between 1.12 V to 1.53 V vs RHE, a pair of
reversible redox peaks were attained (prior to the OER) for both
Mn3N2 as well as for Mn2O3 (Figure S12). This is attributed to the
oxidation of Mn2+/Mn3+ to higher oxidation states and is well
known for Mn-based materials.[23–26] The chronopotentiometric
(CP) responses of both Mn3N2 and Mn2O3 were measured in
alkaline OER conditions maintaining a constant current of
1 mAcm-2 and 10 mAcm-2. Remarkably, Mn3N2 was found to be
very stable over 3 hours with a constant overpotential of 330 mV
(at 1 mAcm-2) and 530 mV (10 mAcm-2). However, Mn2O3
required overpotential of 430 mV to maintain 1 mAcm-2 and
showed a constant rise in overpotential within 3 h while
maintaining a current of 10 mAcm-2 (Figure S12). The catalytic
activity of Mn3N2 vs Mn2O3 were additionally compared to the
commercial benchmark RuO2 and IrO2 catalyst on FTO, and Pt-
wire under exactly the same conditions (Figure S12). Apart from
RuO2, all other catalysts exhibited decreasing trends in
overpotentials compare to Mn3N2 making it to one of the best
catalysts in the series of Mn-based OER catalysts (see Table
S3).
The electrocatalytic OER performance was examined
using
a
standard three-electrode cell (see Supporting
Information) where the Mn3N2 deposited on fluorine doped tin
oxide (FTO) via the electrophoretic deposition (EPD) that directly
served as working electrodes in aqueous 1 M KOH solution.
Figure S12 displays the cyclic voltammogram (CV) of similarly
prepared Mn3N2 and Mn2O3. Interestingly, Mn3N2 exhibited
strikingly higher catalytic activity in terms of both overpotential
and current density compared to Mn2O3. An overpotential as low
as 390 mV was achieved at a current density of 10 mAcm−2 for
Figure 2. High-resolution (a) Mn2p and (b) Mn3s XPS spectra of Mn3N2 (see
text for details)
This article is protected by copyright. All rights reserved.

10.1002/chem.201705745
Chemistry - A European Journal
COMMUNICATION
As the Mn3N2 manifested as efficient OER catalyst on FTO,
we embarked further its catalytic activity on nickel foam (NF)
which is currently an attractive choice among electrode
substrates. The uniform, three-dimensionally interconnected
network structure of the NF has been described as highly
macroporous with a high specific surface area and increased
electrical conductivity.[27] Consequently, Mn3N2 and Mn2O3 were
electrophoretically deposited on NF and investigated for alkaline
OER in aqueous 1 M KOH solutions. Figure S14 presents the
recorded CV curves of Mn3N2 that displays much higher current
density and extremely low overpotential compare to the
respective Mn2O3 electrode. Remarkably, the overpotential
exhibited at 10 mAcm-2 was merely 270 mV and at 100 mAcm-2,
the overpotential was just 390 mV (Figure S14) while the derived
Tafel slope was 101 mVdec-1 (Figure S15). The acquired
overpotentials here are not only one of the lowest reported for
Mn-based catalysts to date but also lower than most of the high
performance first-row transition metal based catalysts.
Additionally, the mass activity of catalysts were also compared
with literature known catalysts (Tables S3, S4 and S5).[28]
Furthermore, the commercially available precious metal-based
RuOx and IrOx were deposited on NF and measured under
similar conditions along with a Pt-wire. Notably, the activity of
the Mn3N2 pre-catalyst was outstanding and exceeded those of
RuOx, IrOx, and Pt wire (Figure 3a). Again, while cycling
between 1.12 V to 1.53 V vs RHE, both Mn3N2 and Mn2O3
displayed a pair of redox peaks prior to oxygen evolution (Figure
S14). The peaks appeared in the same potential region as that
of FTO and could therefore be well attributed to the oxidation of
Mn2+/Mn3+ to higher valencies excluding the possible influence of
NF in OER catalysis.[23–26,29] Subsequntly, the long-term stability
of Mn3N2 was tested in strongly alkaline OER conditions
maintinaing a current of 10 mAcm-2. Unexpectedly, the stability
The XPS of as-prepared Mn3N2 was further compared with
the post electrochemical CV (OER CV) to perceive immediate
transformation on the surface and after long stability run (OER
CP). The Mn2p photoemission lines (Figure 4b) of both post
treated samples (OER CV and OER CP) displayed a shift to
higher binding energies at ~ 642 eV and ~ 654 eV for Mn2p3/2
and Mn2p1/2, respectively. The distance of the Mn2p1/2 signal to
the corresponding satellite changed from the as-synthesized
10.8 eV to 11.4 eV for the OER CV and increased to 11.8 eV for
the OER CP. The values obtained here are consistent with the
literature values reported for Mn2+/Mn3+ to Mn3+/ Mn4+.[20,21] The
Mn3s multiplet splitting and Mn3p also followed a similar trend
(Figure S21).[20,21]
Figure 3. a) Current-potential curves of similarly prepared Mn3N2 and Mn2O3
with commercial noble based catalysts electrophoretically deposited on NF
with a scan rate of 5 mV/s in aqueous 1 M KOH. b) The chronoamperometric
durability test of Mn3N2 in aqueous 1 M KOH.
The N1s spectrum exhibited a peak at 396.3 eV for all
catalysts (as-prepared, after CV and CP) that can be assigned
to elemental nitrogen (Figure S21).[17] The O1s XPS spectra of
OER CV and OER CP displayed two peaks, one at ~ 529.7 eV
corresponding to formation of metal-oxygen bonds (MnOx) on
the surface due to corrosion whereas the second peak at
531.1 eV is largely related to oxyhydroxide/hydroxides (Figure
S21).[30] Incidentally, similar modifications can also be observed
for Mn2O3 with the formation of amorphous MnOx layers on the
surface and no drastic increase in the oxidation state of Mn2O3
occurred after electrochemical OER in comparison to the as-
prepared material. All related SEM, TEM, SAED, XPS and FT-IR
results are presented in the Supporting Information (Figures
S22-S25).
exceeded
a
week (180 h) with exceptionally sustained
overpotentials (~ 290 mV) which makes it the best durable
system known among Mn-based OER catalysts (Figure 3b).
After CP, a CV was measured again to provide a comparison
with the initial CV (Figure S16). Negligible difference in
overpotentials and current density was attained at 10 mAcm-2
and at 100 mAcm-2 with only a slight change in the current.
To gain insights into the near-surface structure
transformations as well as the morphological alteration to arrive
at the actual responsible active centers during the OER catalysis,
microscopic, spectroscopic and analytical investigations were
performed on both Mn3N2 and Mn2O3 post electrochemical (OER
CP) materials (see Supporting Information). The respective TEM
and HR-TEM images show the formation of an amorphous shell
on the surface of the particles evidencing the structural
reorganization at the near-surface structure after OER catalysis
(Figures 4a and S19). Interestingly, the corrosion was limited
only to the surface; the core of the Mn3N2 particles remained
unchanged as shown by the lattice planes underneath of the
amorphous shell. The reflections in the SAED pattern also
confirmed that the core of the particles was intact (Figure S19).
In addition, the Fourier transform infrared spectra (FT-IR)
exhibited broad bands that are typical for hydroxylation in
comparison to the as-prepared Mn3N2 material, where the
respective bands were absent (Figure S2).
Figure 4. a) HR-TEM image of Mn3N2 particle after OER CP forming a thick
layer of amorphous MnOx. b) Comparison of Mn2p XPS spectra of as-
prepared, after OER CA and OER CP of Mn3N2 depicting Mn oxidization.
This article is protected by copyright. All rights reserved.

10.1002/chem.201705745
Chemistry - A European Journal
COMMUNICATION
[9]
a) D. Shevchenko, M. F. Anderlund, S. Styring, H. Dau, I. Zaharieva, A.
Thapper, Phys. Chem. Chem. Phys. 2014, 16, 11965; b) H. Dau, I.
Zaharieva, Acc. Chem. Res. 2009, 42, 1861; c) M. Huynh, C. Shi,
Billinge, Simon J. L., D. G. Nocera, J. Am. Chem. Soc. 2015, 137,
14887; d) K. Rajiv, J. Rajni, Spectrochim. Acta Mol. Biomol. Spectrosc.
2011, 79, 1042; e) A. Bergmann, I. Zaharieva, H. Dau, P. Strasser,
Energy Environ. Sci. 2013, 6, 2745; f) M. M. Najafpour, A. N.
Moghaddam, H. Dau, I. Zaharieva, J. Am. Chem. Soc. 2014, 136, 7245;
g) F. Zhou, A. Izgorodin, R. K. Hocking, L. Spiccia, D. R. MacFarlane,
Adv. Energy Mater. 2012, 2, 1013; h) C. E. Frey, F. Kwok, D. Gonzáles-
Flores, J. Ohms, K. A. Cooley, H. Dau, I. Zaharieva, T. N. Walter, H.
Simchi, S. E. Mohney, P Kurz, Sustainable Energy Fuels 2017, 1, 1162;
i) M. Mahdi Najafpour, D. Jafarian Sedigh, S. Maedeh Hosseini, I.
Zaharieva, Inorg. Chem. 2016, 55, 8827.
Based on the aforementioned results, the exceptional OER
activity and remarkable stability of Mn3N2 can be dedicated to
the following aspects. Foremost, the distinct crystal structure of
Mn3N2 with two and five coordinatively unsaturated Mn undergo
rigorous corrosion at the surface of the particles evidencing
major structural rearrangement under strongly alkaline media of
electrochemical OER.[19] Further, this corrosion leads into an
active amorphous MnOx layer at the surface of Mn3N2 particles
by oxidizing Mn2+/Mn3+ to Mn3+/Mn4+. Such Mn3+ (in t2g3eg
1
configuration) assisted by Mn4+ are known to provide Jahn–
Teller distorted Mn–O bonds for binding O–O with appropriate
strength to felicitates OER and often documented as the real
active sites in the literature.[3–7] Moreover, the metallic character
of Mn3N2 also functions as a highly conductive layer between the
surface of the catalyst and electrode substrate providing faster
charge transfer capability by controlling the OER activity, which
is rather a notable drawback in the case of merely MnOx-based
systems.[31]
[10] a) K. Xu, P. Chen, X. Li, Y. Tong, H. Ding, X. Wu, W. Chu, Z. Peng, C.
Wu, Y. Xie, J. Am. Chem. Soc. 2015, 137, 4119; b) M. Shalom, D.
Ressnig, X. Yang, G. Clavel, T. P. Fellinger, M. Antonietti, J. Mater.
Chem. A 2015, 3, 8171; c) Y. Zhang, B. Ouyang, J. Xu, G. Jia, S. Chen,
R. S. Rawat, H. J. Fan, Angew. Chem. Int. Ed. 2016, 55, 8670; d) F. Yu,
H. Zhou, Z. Zhu, J. Sun, R. He, J. Bao, S. Chen, Z. Ren, ACS Catal.
2017, 7, 2052.
[11] a) R. Niewa, F.J. DiSalvo, D.-K. Yang, D.B. Zax, H. Luo, W.B. Yelon, J.
Alloys Compd. 1998, 266, 32; b) X. Song, Z. Sun, Q. Huang, M.
Rettenmayr, X. Liu, M. Seyring, G. Li, G. Rao, F. Yin, Adv. Mater. 2011,
23, 4690; c) J. B. Gosk, M. Drygaś, J. F. Janik, M. Palczewska, R. T.
Paine, A. Twardowski, J. Phys. D: Appl. Phys. 2006, 39, 3717.
[12] N. A. Gokcen, Bull. Alloy Phase Diagr. 1990, 11, 33.
[13] M. D. Lyutaya, A. B. Goncharuk, Soviet Powder Metall. Met. Ceram.
1977, 16, 208.
[14] a) A. D. Mah, J. Am. Chem. Soc. 1958, 80, 2954; b) W. J. Feng, N. K.
Sun, J. Du, Q. Zhang, X. G. Liu, Y. F. Deng, Z. D. Zhang, Solid State
Commun. 2008, 148, 199; c) J.-W. Huang, J. Li, H. Peng, Powder Metall.
2013, 50, 137.
[15] G. Kreiner, H. Jacobs, J. Alloys Compd. 1992, 183, 345.
[16] a) J. Choi, E. G. Gillan, Inorg. Chem. 2009, 48, 4470; b) S. I. U. Shah, A.
L. Hector, X. Li, J. R. Owen, J. Mater. Chem. A 2015, 3, 3612.
[17] T. S. Spicer, C. W. Spicer, A. N. Cloud, L. M. Davis, G. S. Girolami, J. R.
Abelson, J. Vac. Sci. Technol. 2013, 31, 30604.
Acknowledgements
The authors gratefully acknowledge the financial support by the
Bundesministerium für Bildung und Forschung (BMBF cluster
project MANGAN). The authors are also indebted to Mr.
Christoph Fahrensohn for SEM measurements and Mr. Sören
Selve for TEM measurements.
[18] M. Drygaś, M. M. Bućko, M. Musiał, J. F. Janik, J. Mater. Sci. 2016, 51,
8177.
[19] H. Jacobs, C. Stüve, J. Less Common Metals 1984, 96, 323.
[20] A. A. Audi, P. M. A. Sherwood, Surf. Interface Anal. 2002, 33, 274.
[21] M. Oku, K. Hirokawa, S. Ikeda, J. Electron. Spectrosc. Relat. Phenom.
1975, 7, 465.
Keywords: metal nitrides • conductive materials • corrosion •
energy storage • overpotentials •
[22] U. Maitra, B. S. Naidu, A. Govindaraj, C. N. R. Rao, Proc. Natl. Acad.
Sci. U.S.A. 2013, 110, 11704.
[23] I. Zaharieva, P. Chernev, M. Risch, K. Klingan, M. Kohlhoff, A. Fischer,
H. Dau, Energy Environ. Sci. 2012, 5, 7081.
[24] M. M. Najafpour, F. Rahimi, M. Fathollahzadeh, B. Haghighi, M.
Holynska, T. Tomo, S. I. Allakhverdiev, Dalton Trans. 2014, 43, 10866.
[25] M. Kölbach, S. Fiechter, R. van de Krol, P. Bogdanoff, Catal. Today
2017, 290, 2.
References
[1]
[2]
H. B. Gray, Nat. Chem. 2009, 1, 7.
P. W. Menezes, A. Indra, A. Bergmann, P. Chernev, C. Walter, H. Dau,
P. Strasser, M. Driess, J. Mater. Chem. A 2016, 4, 10014.
A. Indra, P. W. Menezes, I. Zaharieva, E. Baktash, J. Pfrommer, M.
Schwarze, H. Dau, M. Driess, Angew. Chem. Int. Ed. 2013, 52, 13206.
P. W. Menezes, A. Indra, P. Littlewood, M. Schwarze, C. Göbel, R.
Schomäcker, M. Driess, ChemSusChem 2014, 7, 2202.
P. W. Menezes, A. Indra, N. R. Sahraie, A. Bergmann, P. Strasser, M.
Driess, ChemSusChem 2015, 8, 164.
[3]
[4]
[5]
[6]
[7]
[8]
[26] M. M. Najafpour, S. Salimi, R. Safdari, Int. J. Hydrogen Energy 2017, 42,
255.
[27] X. Lu, C. Zhao, Nature Commun. 2015, 6, 6616.
[28] a) L. Trotochaud, J. K. Ranney, K. N. Williams, S. W. Boettcher, J. Am.
Chem. Soc. 2012, 134, 17253; b) M. B. Stevens, L. J. Enman, A. S.
Batchellor, M. R. Cosby, A. E. Vise, C. D. M. Trang, S. W. Boettcher,
Chem. Mater. 2017, 29, 120.
[29] M. M. Najafpour, B. Haghighi, M. Z. Ghobadi, D. J. Sedigh, Chem.
Commun. 2013, 49, 8824.
[30] V. M. Jiménez, A. Fernández, J. P. Espinós, A. R. González-Elipe, J.
Electron. Spectrosc. Relat. Phenom. 1995, 71, 61.
P. W. Menezes, A. Indra, P. Littlewood, C. Göbel, R. Schomäcker, M.
Driess, ChemPlusChem 2016, 81, 370.
A. Indra, P. W. Menezes, C. Das, D. Schmeißer, M. Driess, Chem.
Commun. 2017, 53, 8641.
a) D. M. Robinson, Y. B. Go, M. Mui, G. Gardner, Z. Zhang, D.
Mastrogiovanni, E. Garfunkel, J. Li, M. Greenblatt, G. C. Dismukes, J.
Am. Chem. Soc. 2013, 135, 3494; b) C. C. L. McCrory, S. Jung, J. C.
Peters, T. F. Jaramillo, J. Am. Chem. Soc. 2013, 135, 16977; c) J. Masa,
W. Xia, I. Sinev, A. Zhao, Z. Sun, S. Grutzke, P. Weide, M. Muhler, W.
Schuhmann, Angew. Chem. Int. Ed. 2014, 53, 8508; d) P. W. Menezes,
A. Indra, V. Gutkin, M. Driess, Chem. Commun. 2017, 53, 8018.
[31] a) R. N. de Guzman, A. Awaluddin, Y.-F. Shen, Z. R. Tian, S. L. Suib, S.
Ching, C.-L. O'Young, Chem. Mater. 1995, 7, 1286; b) R. Yu, X. Chong,
Y. Jiang, R. Zhou, W. Yuan, J. Feng, RSC Adv. 2015, 5, 1620.
This article is protected by copyright. All rights reserved.

10.1002/chem.201705745
Chemistry - A European Journal
COMMUNICATION
COMMUNICATION
Better late than never: A versatile
molecular route has been achieved
to produce manganese nitride as a
suitable high-performance material
for the electrocatalytic oxygen
evolution reaction (OER) in alkaline
Carsten Walter, Prashanth W. Menezes, Steven
Orthmann, Jona Schuch, Paula Connor,
Bernhard Kaiser, Martin Lerch, and Matthias
Driess*
Page No. – Page No.
media.
The
coordinatively
unsaturated nature of manganese,
the active amorphous surface layer
as well as the metallic character in
manganese nitride pre-catalyst are
identified as key factors for the
outstanding catalytic performance
with high durability.
A Molecular Approach to Manganese
Nitride Acting as a High Performance
Electrocatalyst in the Oxygen Evolution
Reaction
This article is protected by copyright. All rights reserved.