Tuning the Adsorption Energy of Methanol Molecules Along Ni-N-Doped Carbon Phase Boundaries by the Mott–Schottky Effect for Gas-Phase Methanol Dehydrogenation

Article abstract of DOI:10.1002/anie.201713429

Engineering the adsorption of molecules on active sites is an integral and challenging part for the design of highly efficient transition-metal-based catalysts for methanol dehydrogenation. A Mott–Schottky catalyst composed of Ni nanoparticles and tailorable nitrogen-doped carbon-foam (Ni/NCF) and thus tunable adsorption energy is presented for highly efficient and selective dehydrogenation of gas-phase methanol to hydrogen and CO even under relatively high weight hourly space velocities (WHSV). Both theoretical and experimental results reveal the key role of the rectifying contact at the Ni/NCF boundaries in tailoring the electron density of Ni species and enhancing the absorption energies of methanol molecules, which leads to a remarkably high turnover frequency (TOF) value (356 mol methanol mol^?1 Ni h^?1 at 350 °C), outpacing previously reported bench-marked transition-metal catalysts 10-fold.

Full text of DOI:10.1002/anie.201713429

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Accepted Article
Title: Tuning the adsorption energy of methanol molecules along Ni-N-
doped carbon phase boundaries via the Mott-Schottky effect for
highly efficient dehydrogenation of gas-phase methanol
Authors: Zhong-Hua Xue, Jing-Tan Han, Wei-Jie Feng, Qiu-Ying Yu,
Xin-Hao Li, Markus Antonietti, and Jie-Sheng Chen
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201713429
Angew. Chem. 10.1002/ange.201713429
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10.1002/anie.201713429
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Tuning the adsorption energy of methanol molecules along Ni–N-
doped carbon phase boundaries via the Mott-Schottky effect for
highly efficient dehydrogenation of gas-phase methanol
Zhong-Hua Xue, Jing-Tan Han, Wei-Jie Feng, Qiu-Ying Yu, Xin-Hao Li,* Markus Antonietti, and Jie-
Sheng Chen*
Abstract: Engineering the adsorption of molecules on active sites is
an integral and challenging part for the design of highly efficient
transition-metal-based catalysts for methanol dehydrogenation. Here
we report a Mott-Schottky catalyst composed of Ni nanoparticles and
tailorable nitrogen-doped carbon-foam (Ni/NCF) and thus tunable
adsorption energy for highly efficient and selective dehydrogenation
of gas-phase methanol to hydrogen and CO even under relatively high
weight hourly space velocities (WHSV). Both theoretical and
experimental results reveal the key role of the rectifying contact at the
Ni/NCF boundaries in tailoring the electron density of Ni species and
enhancing the absorption energies of methanol molecules, which
leads to a remarkably high turnover frequency (TOF) value (356 mol
methanol mol−1 Ni h−1 at 350 °C), 10-fold outpacing the bench-marked
transition-metal catalysts in the literature.
activation energy and also mass transfer barriers over specific
metal centers for methanol dehydrogenation. It is thus reasonable
for the more weakly binding transition metal species to enhance
the adsorption of methanol molecules and intermediate species
[2a,7]
with lone-pair electrons
onto their surface, a question which
however is less touched at the moment as people are mostly not
aware that this energy can be adjusted.
Herein, we described a direct way to modulate the adsorption
of gas-phase methanol molecules on N-doped carbon-foam-
embedded
Ni
nanoparticles
(Ni/NCF)
for
selective
dehydrogenation into H2 and CO via the Schottky effect with N-
doped carbon. We recently developed the concept and some
series of Mott–Schottky catalysts composed of metallic
nanocatalyst and semiconductive support with significantly
promoted redox power due to the Mott-Schottky effect-induced
band bending of the semiconductor part for specific reactions in
the liquid phase.[8] The Schottky barrier at the interface of metal
and semiconductor can also be principally applied to modify the
electron density of the Ni nanoparticle and thus the adsorption
energy of methanol molecules on their surface. Indeed, textural
and theoretical analysis in this work demonstrates the first
example, as far as we know, of an on-demand tuning the
absorption energy over a Mott-Schottky-type binary catalyst for
high-throughput dehydrogenation of gas-phase methanol,
resulting in a state-of-the-art turnover frequency among all
reported Ni based catalysts in the literature.
The detailed synthetic process for the large-scale fabrication
of the Ni/NCF catalyst is illustrated in Figure 1a and described in
the experimental section, Table S1 and Figure S2-9 of the
supporting information. The high-resolution TEM (HRTEM) image
(Figure 1c and d) indicates a highly integrated nanostructure of a
layered carbon-coated Ni nanoparticle (~21 nm, Figure S7-9).
Further high-angle annular dark-field (HAADF) and the
corresponding energy dispersive X-ray spectroscopy (EDX)
investigations (Figure 1e and f) directly confirm the homogenous
distribution of the Ni nanoparticles inside the carbon-nitrogen
matrix. X-ray diffraction (XRD) patterns (Figure S10) corroborate
the coexistence of graphitic carbon and nickel as the main
components of the Ni/NxCF samples.[9] X-ray photoelectron
spectrum (XPS) results (Figure S11 and S12) and the Raman
spectrum (Figure S13) further reveal the presence of pyridinic and
graphitic N,[8b,10] and the gradually increased nitrogen contents in
the Ni/NxCF samples (x refers to the molar ratio of N and C) from
Ni/N0.03CF via Ni/N0.06CF to Ni/N0.09CF. The Ni K-edge of X-ray
absorption near-edge structure (XANES) of the Ni/N0.09CF sample
(Figure S14) demonstrates the metallic nature of the embedded
Ni species. The corresponding Fourier transform (FT) extended
X-ray absorption fine structure (EXAFS) of Ni K-edge in R-space
(Figure S14) strikingly exclude the formation of Ni-O, Ni-C and Ni-
N bonds in the Ni/N0.09CF sample, given as an example. The Ni
Activation of small molecules, such as methane, carbon
dioxides and methanol, are important targets in modern catalysis
science.[1] Selective dehydrogenation of methanol to H2 and CO
by heterogenous catalysts is of great interests for both
fundamental studies and practical applications.[2] The noble-
metal-based catalysts exhibit a high activity but suffer from a high
price and a low tolerance to CO.[3] The transition-metal-based
catalysts promise great potentials as cheap and stable candidates
for methanol dehydrogenation, although currently the relatively
insufficient activity still restricts real-life applications.[4] Despite
great efforts,[5] developing effective methods to significantly
elevate the conversion and selectivity of the cheap transition
metal based nanocatalysts for methanol dehydrogenation still
remains a great challenge.
Considering the requirement of gas-solid heterogeneous
systems when running high throughput gas reactions, we also
paid our attention to the design of efficient nanostructured
catalysts for the fast absorption of methanol molecules at high
flow rates. Indeed, the adsorption energy for methanol molecules
or the decomposed pathway intermediates on the surface of a
metal catalyst has a volcano-shaped relationship with the final
catalytic rate.[6] As a result, an appropriately high adsorption
energy of methanol is thus equally important to the lowered
[*] Z. H. Xue, J. T. Han, W. J. Feng, Q. Y. Yu, Prof. X. H. Li, Prof. J. S.
Chen
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong
University, Shanghai 200240 (P. R. China)
E-mail: xinhaoli@sjtu.edu.cn
chemcj@sjtu.edu.cn
Prof. M. Antonietti
Department of Colloid Chemistry, Max Planck Institute of Colloids and
Interfaces, Wissenschaftspark Golm, Potsdam 14424 (Germany)
Supporting information for this article is given via a link at the end of the
document.
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10.1002/anie.201713429
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loadings remained to be ca. 19 wt% for all samples as
demonstrated by inductively coupled plasma atomic emission
spectroscopy (ICP-AES) analysis results (Figure S15), which can
be lowered by reducing the weight of the nickel sheet at fixed
amount of DCDA (Table S1 and Figure S16).
and mesoscale structures (Figure 1 and S7-9), the Ni/NxCF
catalysts enable gradually increasing conversions of methanol
(Figure 2a) along with the elevated concentrations of N dopants
in the supports, whilst the selectivity to CO was not disturbed too
much (> 90%, Figure 2b). A notable effect of surface area on the
final catalytic activity can be excluded along with the fact that the
Ni/N0.09CF with a lowest specific surface area (37.1 m2 g−1)
exhibits the best catalytic performance amongst the Ni/NxCF
samples (Figure S19). The highest conversion rate and also the
lowest slope of Arrhenius plot (210−250 °C, Figure 2c) supplied
by the Ni/N0.09CF sample suggests that Mott-Schottky-type
catalyst with higher nitrogen content provide a preferred activity
for methanol dehydrogenation.
Figure 1. Fabrication and structure. (a) Solid-state synthesis of Ni/NCF from
nickel sheet and dicyandiamide (DCDA). (b) Transmission electron microscopy
(TEM), HRTEM (c, d), HAADF images and the corresponding EDX mapping
results (e, f) of typical Ni/N0.09CF sample.
Figure 2. Study of reaction conditions. Temperature-dependent methanol
conversions (a) and selectivity (b) of Ni/NxCF samples with a WHSV of 15 h−1
and corresponding Arrhenius plots (c). Catalytic stability test of Ni/N0.09CF
sample including the evolution in both conversions (d) and selectivity (e). (f)
Temperature-dependent methanol conversions by the Ni/N0.09CF catalysts with
varied WHSV.
We initially tested the catalytic performance of all catalysts
used in this work in typical fixed-bed reactor under a medium and
widely used WHSV value of 15 h−1. Blank reactions without a
catalyst or by using metal-free nitrogen-doped carbon catalyst
could not give detectable conversions of methanol (Figure 2a and
S17). The workable light-off temperature in the conversion curve
was ~200 °C with 100% selectivity to CO (Figure 2 and S18) with
the addition of Ni/NCF catalysts. Methane and dimethyl ether
were the only two detectable carbonaceous byproducts at even
higher temperatures. The Ni loading is with 19 wt% optimal to
offer the highest conversion for methanol dehydrogenation
(Figure S16 and S18) and was thus used as the best-in-class Ni
loading for further characterizations and applications.
The Mott–Schottky barrier formation also significantly
improves the stability of the Ni based nanocatalysts, which is of
pivotal importance for industrial applications. The long-term
durability of Ni/N0.09CF catalyst for methanol dehydrogenation for
over 3 days (Figure 2d) was excellent, keeping the high
conversions and a constant selectivity to CO (Figure 2e). More
than 90% of activity was maintained for more than 24 h at 350 °C.
Both structure and chemical composition of the used Ni/N0.09CF
catalysts were found to be structurally stable after the long-term
durability test (Figure S20-23).
The temperature dependency of methanol conversion over
the Ni/NxCF catalysts (Figure 2a) directly quantifies the support
effect on catalytic activity. With the same Ni loading (Figure S15)
High throughput conversions of gas molecules in gas-solid
heterogeneous systems is the key challenge for the extended
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application of potential catalysts in industry. The Ni/NxCF based
Mott-Schottky catalyst with modified electron affinity may
principally enhance the pre-adsorption of methanol molecules
even at high flow rate. Indeed, the best-in-class Ni/N0.09CF
catalyst can provide excellent to good conversions of methanol
and high selectivity to CO and H2 even at significantly elevated
WHSV (Figure 2f and S24), rendering a considerable reaction rate
of more than 424 mmol methanol g−1 catalyst h−1 at 300 °C and
area of the carbon support were also enlarged in the nitrogen-rich
sample Ni/N0.09CF as marked with the blue and red arrows
respectively in the charge density difference (CDD) stereograms
(Figure 3b and S27), demonstrating the formation of a rectifying
Mott-Schottky heterojunction.[8a]
Indeed, the electron-deficient Ni nanoparticles in Ni/NxCF
catalyst exhibit strong interaction with methanol molecule, which
is believed to be the descriptive factor to enhance the possibility
of the O−H bond scission on the surface of Ni nanoparticles and
thus accelerate the methanol dehydrogenation reaction.[2a,6b,7] As
illustrated in the CDD stereograms (Figure 3c and S28), the
methyl group is totally embedded in the electron-rich region. The
increasing surface electron density (Figure 3c left) of the carbon
support as nitrogen concentration increases, significantly
attracted the −CH3 group to the surface.The equilibrium distance
between the carbon surface and the adjacent hydrogen of the
methanol over the Ni/N0.09CF catalyst is only 2.7 Å, further
suggesting the even stronger interaction between the electron
deficient methyl group and the electron rich region of carbon
surface, which can be also expresses as a partial bonding of the
hydride to be eliminated from the methyl group. Due to this
secondary binding, the calculated adsorption energy of methanol
on the surface of Ni/N0.09CF is the most negtive value among all
the models, with the C-H bond thereby weakened by at least 0.3
eV.
WHSV of 45 h−1. Such
a reaction rate for methanol
dehydrogenation at a relatively low temperature is close to or
even higher than those of classical noble-metal nanocatalysts
(Table S2).
Figure 3. DFT calculation of a model unit of a Ni/NxCF Mott-Schottky catalyst.
(a) The calculated band structures of NxCF supports along Г-M-K-Г. The models
were built on the basis of experimental results. The energies are measured with
respect to the Fermi level. (b) CDD stereograms (side view) of Ni/NxCF after the
introduction of metallic Ni clusters. Blue and red represent electron depletion
and accumulation, respectively; color arrows are draw to guide the eye. (c) CDD
stereograms after the adsorption of a CH3OH molecule onto the Ni/NxCF models.
(d) The calculated adsorption energy of CH3OH molecules adsorbed on the
Ni/NxCF catalysts. Insets of d: corresponding structures of the CH3OH and the
active centers.
Density functional theory (DFT) calculations were applied to
quantify the Mott-Schottky effect in promoting the methanol
dehydrogenation reaction, confirming the support effect to tune
the adsorption energy of gas-phase methanol molecules on the
surface of the catalysts. The band gap (Figure 3a and S25-26) of
the carbon support is gradually enlarged by increasing the
concentrations of nitrogen dopant,[10d] especially the pyridinic
nitrogen, resulting in a valence band edge close to the Fermi level
and thus a p-type semiconductive structure.[11] The electron
deficient area of the loaded Ni nanoparticles and electron rich
Figure 4. Schematic of Mott-Schottky contact (a). The measured work functions
(Φ) via UPS analysis (b) and Ni 2p XPS spectra (c) of Ni/NxCF catalysts. (d) The
CO2-TPD results of Ni/NxCF samples and the acid-etched sample Ni/N0.09CF-
H+. The activation energies (e) and TOF values (f) for the methanol
dehydrogenation over Ni/NxCF catalysts.
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All the DFT calculation (Figure 3a-b and S29) and XPS results
indicate that more electrons of metallic Ni nanoparticles were
transferred to the nitrogen-doped carbon support (Figure 4a) of
the Ni/N0.09CF, which has a higher work function (Figure 4b and
S30) and an even lower valance band position (Figure S31-S33)
in the carbon support as demonstrated by the ultroviolet
photoelectron spectroscopy (UPS) results.[12] Typical XPS peaks
of nickel gradually shift to a higher binding energy with the
increase of nitrogen dopants (Figure 4c), whilst N 1s XPS peaks
(Figure S34) shift to a lower binding energy values. The gradually
enhanced electron enrichment of the carbon support, as directly
reflected by their Lewis basicity, of the Ni/NxCF samples with
more nitrogen dopants could be also experimentally confirmed by
the temperature-programmed desorption (TPD) analysis results
(Figure 4d). A mild acid treatment of the Ni/N0.09CF sample could
not obviously change the nitrogen content (Figure S35) but
significantly temporarily knocks-out its Lewis base sites (Figure
4d), rather supporting our picture of the source of the catalytic
activity.
Keywords: heterogeneous catalysis • Mott-Schottky effect •
nanostructures • adsorption energy • gas-solid reactions
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This work was supported by National Natural Science Foundation
of China (21720102002, 21722103 and 21673140), Shanghai
Basic Research Program (16JC1401600), SJTU-MPI partner
group, SJTU-Chuntsung Program (2017603), Shanghai Eastern
Scholar Program and Shanghai Rising-Star Program
(16QA1402100). The authors thank Shanghai Synchrotron
Radiation Facility for providing beam time (BL14W1).
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Zhong-Hua Xue, Jing-Tan Han, Wei-Jie
Feng, Qiu-Ying Yu, Xin-Hao Li,* Markus
Antonietti, and Jie-Sheng Chen*
Page No. – Page No.
Title: Tuning the adsorption energy of
methanol molecules along Ni–N-
doped carbon phase boundaries via
the Mott-Schottky effect for highly
efficient dehydrogenation of gas-
phase methanol
Active boundaries: the ability of the Mott-Schottky-type nanocatalysts to change the
adsorption energy of methanol molecules for highly efficient and selective
dehydrogenation of gas-phase methanol was achieved by constructing Ni
nanoparticle/N-doped carbon-foam catalyst. The electron redistribution along the Ni–
N-doped carbon phase boundaries via the Mott-Schottky effect significantly and
generally promotes the adsorption and further activation of methanol molecules, thus
efficiently boosting the methanol dehydrogenation reaction.
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