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Research Articles
Gold Clusters
Controllable Conversion of CO2 on Non-Metallic Gold Clusters
Dan Yang+, Wei Pei+, Si Zhou,* Jijun Zhao, Weiping Ding, and Yan Zhu*
Dedicated to the 100th anniversary of the School of Chemistry and Chemical Engineering, Nanjing University
Abstract: Gold nanoparticles in metallic or plasmonic state
have been widely used to catalyze homogeneous and hetero-
geneous reactions. However, the catalytic behavior of gold
catalysts in non-metallic or excitonic state remain elusive.
Atomically precise Aun clusters (n = number of gold atoms)
bridge the gap between non-metallic and metallic catalysts and
offer new opportunities for unveiling the hidden properties of
gold catalysts in the metallic, transition regime, and non-
metallic states. Here, we report the controllable conversion of
CO2 over three non-metallic Aun clusters, including Au9, Au11,
and Au36, towards different target products: methane produced
on Au9, ethanol on Au11, and formic acid on Au36. Structural
information encoded in the non-metallic clusters permits
a precise correlation of atomic structure with catalytic proper-
ties and hence, provides molecular-level insight into distinct
reaction channels of CO2 hydrogenation over the three non-
metallic Au catalysts.
Introduction
Atomically precise metal clusters, ideally composed of an
exact number of metal atoms, recently have attracted
significant interests due to the breakthrough in determination
of total structures (surface plus core) and distinctive elec-
tronic structures.[1–6] Different from metallic catalysts with
collective excitation behavior, the atomically precise metal
clusters can be classified into three distinct states: metallic,
transition regime, and non-metallic.[7] Non-metallic or mo-
lecular-like clusters possess discrete electron energy levels.[8]
With the evolution of electronic structures from metallic to
non-metallic state, these clusters can reveal a hidden mystery
in the catalytic field: the non-metallic cluster-catalysts may
have similar or even superior catalytic abilities compared to
the metallic ones. More than that, they are opening up a new
era for catalytic science. For example, these clusters provide
exciting opportunities to map out the explicit structure-
[*] D. Yang,[+] Prof. W. Ding, Prof. Y. Zhu
Key Lab of Mesoscopic Chemistry, School of Chemistry and Chemical
Engineering, Nanjing University
Nanjing 210093 (China)
E-mail: zhuyan@nju.edu.cn
W. Pei,[+] Dr. S. Zhou, Prof. J. Zhao
Key Laboratory of Materials Modification by Laser, Ion and Electron
Beams, Dalian University of Technology
Dalian 116024 (China)
E-mail: sizhou@dlut.edu.cn
[+] These authors contributed equally to this work.
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201913635.
Angew. Chem. Int. Ed. 2020, 59, 1919 – 1924 T 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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International Edition: DOI: 10.1002/anie.201913635
German Edition: DOI: 10.1002/ange.201913635
property relationship and allow for identification of active
sites with atomic precision.[9–15] Specifically, they can be used
to explore how the catalytic performance can be tailored by
only one atom alteration.[16, 17] They can also circumvent the
sluggish kinetics of electron transfer for non-photosynthetic
bacteria to enable photosynthesis of acetic acid from CO2.[18]
Such studies are typically impossible for traditional metallic
catalysts.
In this work, the catalytic hydrogenation of CO2 is
selected as a target reaction. The effective conversion of
CO2 into liquid fuels and chemicals is of paramount impor-
tance for mitigating the global warming and energy supply
problems.[19–27] Recent successes in the transformation of CO2
into C2 products has added additional spotlights on this area.
C2 compounds, relative to C1 species, are really high-value-
added products and can be used as entry platform chemicals
for existing high-value products.[28] The controllable reduction
of CO2 with renewable hydrogen into C1 or C2 products is thus
highly desirable, which may become feasible by modulating
the competition of C@C bond formation with C@H and C@O
bond formation. Several reports have shown that CO2 can be
converted into C2 products by both, homogeneous and
heterogeneous catalysis.[29–34] However, it remains challenging
to control the rate-determining route or intermediates from
CO2 conversion that determine different pathways purpose-
fully towards C1 or C2 products.
Herein, we utilize non-metallic gold clusters such as
[Au9(PPh3)8](NO3)3 (denoted as Au9), [Au11(PPh3)8Cl2]Cl
(denoted as Au11), and Au36(TBBT)24 (denoted as Au36 ;
TBBT = 4-tert-butylbenzenethiol) as catalysts for the hydro-
genation reaction of CO2. The investigation of how the
atomicity of gold clusters dictates the reaction channels of
CO2 hydrogenation selectively towards C1 or C2 products
shows totally different performance compared to plasmonic/
metallic gold nanoparticle catalysts.
Results and Discussion
Electrospray ionization mass spectra (ESI-MS) showed
true mono-dispersity of the three clusters, confirming the
exact formulas: [Au9(PPh3)8]3+, [Au11(PPh3)8Cl2]+, and Au36-
(TBBT)24. As shown in Figure 1 a, peaks at 3208.12, 3470.44
and 3732.71 Da were assigned to [Au9(PPh3)53+ + 2 NO3@]+,
[Au9(PPh3)63+ + 2 NO3@]+, and [Au9(PPh3)73+ + 2 NO3@]+, re-
spectively. In Figure 1 b, only one sharp peak at 4336.3 Da was
observed, verifying the formula of [Au11(PPh3)8Cl2]+. The m/
z 5528.77 peak was 2 + charged (Figure 1 c), as revealed by
the isotope peak spacing, which corresponded to [Au36-
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Figure 1. ESI-MS profiles of a) [Au9(PPh3)8]3+, b) [Au11(PPh3)8Cl2]+, and
c) Au36(TBBT)24. Atomic structures of d) [Au9(PPh3)8]3+, e) [Au11-
(PPh3)8Cl2]+, and f) Au36(TBBT)24. Color codes: green = Au, pink = P,
yellow = S; orange = Cl.
(TBBT)24@2 e]2+. A small peak at 5446.16 Da arose from
a fragment of [Au36(TBBT)23@2 e]2+.
The three gold clusters have individually precise atom-
packing structures. The total structure of [Au9(PPh3)8]3+
resembles a butterfly with eight gold atoms surrounding the
central gold atom. The peripheral gold atoms are bonded to
PPh3 (Figure 1 d).[35] [Au11(PPh3)8Cl2]+ can be viewed as an
incomplete icosahedron with an approximate C3v symmetry.
The ten surface gold atoms are linked to eight PPh3 and two
halogen atoms (Figure 1 e).[36] Au36(TBBT)24 has a 28-gold-
atom kernel with a truncated fcc (face-centered cubic)
tetrahedron exposing 4 of {111} facets and 12 of {100} facets.
Each {111} facet is protected by one dimeric staple, and each
{100} square is capped by one bridging thiolate (Figure 1 f).[37]
The non-metallic properties of the three gold clusters are
indeed reflected by discrete electron energy levels and
multiple absorption bands in optical spectra. The UV-vis
absorption spectrum of the [Au9(PPh3)8]3+ cluster showed two
prominent peaks at 313 and 442 nm and two weak peaks at
348 and 378 nm (Figure 2 a). The [Au11(PPh3)8Cl2]+ cluster
showed optical absorption bands centered at 312, 375 and
Figure 2. UV-vis spectra of a) [Au9(PPh3)8]3+, b) [Au11(PPh3)8Cl2]+ and
c) Au36(TBBT)24. Kohn–Sham orbitals of d) Au9(PPh3)8, e) Au11-
(PPh3)8Cl2 and f) Au36(SCH3)24 from DFT calculations and the corre-
sponding HOMO and LUMO charge density distributions. H, C, O, S
and Au atoms are shown in white, gray, red, brown and yellow,
respectively.
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415 nm (Figure 2 b). The Au36(TBBT)24 cluster exhibited two
obvious absorption bands at 374 and 580 nm and one broad
band at 426 nm (Figure 2 c). From DFT (density functional
theory) calculations, the Kohn–Sham (KS) molecular orbital
(MO) energy levels and atomic orbital components in each
KS MO of the three clusters indicate that the absorption
peaks in the three clusters mainly involve Au(sp) ! Au(sp)
transitions (Figure 2 d–f). Optical energy gaps were deter-
mined to be 1.49, 1.73 and 1.84 eV between the highest
occupied molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) by our DFT calculations.
X-ray absorption near edge structure (XANES) experi-
ments were carried out to monitor the charge states of the
gold clusters. As shown in Figure 3 a, the white line intensities
Figure 3. a) XANES profiles and b) EXAFS data with fits of [Au9-
(PPh3)8]3+, [Au11(PPh3)8Cl2]+, Au36(TBBT)24 and Au foil.
of the Au9, Au11, and Au36 clusters were higher than for Au
foil, which were generally caused by interactions of the
ligands with surface Au atoms.[38] The Au L3-edge white line
results from electronic transitions from occupied 2p to
unoccupied 5d states, where the higher 5d electronic density
is due to more metal-ligand charge transfer.[39] By the aids of
liner combination fits, the charge states of the three gold
clusters were positive: the average charge state of Au9 was the
highest, that of Au36 was the lowest, and that of Au11 was in
between. Furthermore, local coordination environments in
the three clusters were probed by the extended X-ray
absorption fine structure (EXAFS) studies. The Au-X (Au-
P for Au9, Au-P/Cl for Au11, and Au-S for Au36) bonds and the
Au-Au bonds for each gold cluster are given in Figure 3 b and
Table S1 (Supporting Information), indicating that the inten-
sities of Au-Au bonds in the three clusters were shown in the
descending order: Au36 > Au11 > Au9.
We next turned our attention to the catalytic properties of
the non-metallic gold clusters. The three gold clusters were
exploited as heterogeneous catalysts to explore if the non-
metallic gold can be indeed operative in determining the
reaction pathways for the hydrogenation of CO2. A similar
trend was found when different oxides were used as supports
(Figure S1 and Table S2; the supplemental discussion of the
effect of supports on the catalytic conversion of CO2 can be
found in Supporting Information). The Au9 catalysts gave rise
to the selectivity of methane with & 90 % and other products
like methanol, ethanol and formic acid etc. as minor products.
The Au36 catalysts can give the high selectivity (> 80 %) for
formic acid with a small amount of methanol, methane and
ethanol etc. Interestingly, the Au11 catalysts can improve C@C
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coupling to form ethanol as C2 chemical with > 80 %
selectivity. Furthermore, the temperature effect on the
catalytic performances of the three cluster catalysts for CO2
hydrogenation was investigated (Figure 4 a). The activities in
Figure 4. Catalytic CO2 hydrogenation performance on Au9, Au11 and
Au36 supported on ZrO2 under different conditions: a) reaction temper-
ature, b) reaction pressure, and c) reaction time. d) Catalytic results of
CO2 hydrogenation on the three gold clusters pretreated to remove all
ligands. Reaction conditions: catalyst (100 mg, & 1 % Au), H2O
(15 mL), 3 MPa (CO2 + 3 H2), 120 8C. Note that beside the four
products other products formed in small amounts were not further
studied. Stars denote as TOF or TON. Error bars correspond to the
deviations from three independent experiments.
terms of TOF (turnover frequency) of the three catalysts were
increased with increasing temperature (note that the atomic
structures of the clusters can be destroyed at higher temper-
atures). The results in Figure 4 b revealed that the increase of
reaction pressure was also beneficial to the conversion of
CO2, but the reaction pressure did not influence the
selectivity of products. The catalytic behavior of the three
clusters was further studied by exploring the activity and
product selectivity as a function of the reaction time. The
conversion of CO2 (where TON is turnover number) in-
creased with the reaction time, and the selectivity of products
almost remained unchanged with the reaction time (Fig-
ure 4 c). Moreover, the distinct selectivity towards C1 or C2
products was also embodied in the recyclability of the three
catalysts (Figure S2). The typical UV-vis spectra of the spent
catalysts showed that a certain quantity of the clusters was still
intact after reactions (Figure S3). Notably, supports had no
activity (Table S3, entries 1–3).
Considering the clusters themselves containing carbon
sources (ligands), additional experiments were performed:
either CO2 or H2 was introduced and no product was detected
(Table S3, entries 4–9), which ruled out the possibility of the
products originating from ligands. A question that naturally
occurs is whether the ligands can have an influence on the
catalytic activity and selectivity. To address this, clusters
protected by different ligands (Figure S4) were synthesized to
catalyze the hydrogenation of CO2. As shown in Figure S5,
methane was still the major product over Au9 protected by
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diphenyl-methylphosphine (MePPh2); formic acid was the
major product over Au36 protected by p-isopropyl benzene-
thiol (TPBT); ethanol was the major product over Au11
capped by 2-diphenylphosphino pyridine (PyPPh2). These
findings support that the catalytic selectivity is mainly
determined by the gold sites rather than the surface ligands.
When the ligands were completely removed by thermal
treatment (Figure S6), the clusters became gold nanoparticles
with metallic state (namely nanocrystals, Figure S7). The
metallic Au nanoparticles with 5–10 nm size had very low
activity with methane as major product (Figure 4 d), implying
that the underlying reaction path has been altered.
Considering that the three clusters were protected by
organic ligands, the active site-blocking impact of ligands
might lead to gold sites not available for adsorption and
conversion of reagents. How can the three clusters catalyze
the conversion of CO2 ? To approach this question, the
changes of ligands in the three clusters under reaction
conditions were detected by in situ diffuse reflectance infra-
red Fourier transform spectroscopy (DRIFTS). In compar-
ison with the FT-IR features of TBBT and PPh3 ligands
(Figure S8), the IR features marked with purple rectangular
frames in Figure S9 and S10 were assigned to PPh3, the
characteristic IR bands in Figure S11 were assigned to TBBT.
Clearly, these bands gradually decreased in intensity with
treatment time, and finally held steady. This indicates that the
ligands could be partially removed under reaction conditions
and the exposed gold sites of the clusters can activate
reagents.
The three gold clusters are capable of driving reaction
pathways of CO2 conversion towards different products,
which implies different reaction mechanisms for the three
catalysts. Therefore, the reaction intermediates formed in the
three catalytic cycles were monitored by time-resolved in situ
FT-IR spectroscopy. As shown in Figure 5 a, a series of bands
was observed: the band at 1457 cm@1 assigned to
OCO*;[31, 39, 40] the bands at 1630, 1868 and 2072 cm@1 assigned
to HCO*, OH* and CO* species, respectively.[41, 42] Based on
these results, the reaction mechanism of CO2 hydrogenation
on the Au9 catalyst was proposed: methane was produced
through a H-assisted pathway, possibly via formyl (HCO*)
and formaldehyde (H2CO*, 2921 cm@1) species to form
surface CHx. For the Au11 reaction system (Figure 5 b), two
bands at 1457 and 1396 cm@1 were assigned to adsorbed
OCO* species[31, 39, 40] and the band at 2060 cm@1 was assigned
to CO* species adsorbed on gold.[43–45] IR bands at 2977 and
2892 cm@1 were also observed, which were assigned to
u(CH).[29–31, 39] The band at 1687 cm@1 was assigned to
CH2O*.[39] It was speculated that C2H5OH on the Au11
catalyst was likely to be formed via CO* insertion in CH2*
species. In addition, the band at 1747 cm@1 emerged, corre-
sponding to u(C=O) in the adsorbed HCOOH species,[46]
indicating that HCOOH was also formed on the Au11 catalyst.
For the Au36 catalyst system (Figure 5 c), bands at 2877, 1627
and 1385 cm@1 assigned to u(CH) and d(CH) modes in
HCOO* species were found.[47, 48] The bands at 2955 and
1747 cm@1 corresponding to u(CH) and u(C=O) in the
adsorbed HCOOH were also observed.[46, 48] This means the
formation of HCOOH on the Au36 catalyst occurs via
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Figure 5. Time-resolved in situ IR spectra of the reaction intermediates
formed on a) Au9, b) Au11 and c) Au36 supported on ZrO2 for the
hydrogenation of CO2 at 120 8C and 0.8 MPa (CO2 + 3 H2).
adsorbed formate intermediates. IR spectra of standard
samples are shown in Figure S12 and S13 for clear compar-
ison. Overall, the above observations confirm that COOH*,
CO*, and CHx* species are formed on the Au9 and Au11
catalysts during CO2 hydrogenation, which are regarded as
important intermediates for the formation of methane and
ethanol. The HCOO* species is an essential intermediate for
formic acid formation on the Au36 catalyst.
To understand the distinct selectivity of the three non-
metallic gold clusters, we performed DFT calculations to
further explore the CO2 hydrogenation processes on each of
the clusters. The phenyl group in PPh3 and TBBT ligands were
replaced by methane (@CH3) and methane thiolates
(@SCH3) to simplify our models and reduce the computa-
tional cost.[49] According to in situ FTIR measurements
(Figure S9–S11), the ligands were partially shed from the
gold clusters. Therefore, we considered Au9(P(CH3)3)4, Au11-
(P(CH3)3)6 and Au36(SCH3)14 as model structures (displayed
by Figure S14), in which some of the Au atoms are exposed
and can serve as active sites. According to our test calcu-
lations, the energy required for removing ligands has little
dependence on the coverage of ligands on the clusters
(Figure 6 a). The gold clusters fully protected by ligands show
no activity for chemisorption of molecules and reaction
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Figure 6. a) Energies required for removing ligands from the Au9(P-
(CH3)3)8, Au11(P(CH3)3)8Cl2 and Au36(SCH3)24 clusters determined by
DFT calculations. b) Binding energies of the COOH* intermediate on
the three clusters as a function of number of removed ligands.
c) Binding energies of key reaction intermediates and d) kinetic
barriers of the rate-limiting steps toward various products on Au9(P-
(CH3)3)4, Au11(P(CH3)3)6 and Au36(SCH3)14 clusters.
intermediates involved in CO2 hydrogenation. With increas-
ing number of shedding ligands, the binding strength of
reaction intermediates on the exposed Au atoms enhances
and quickly achieves convergence with about half of the
ligands being removed (Figure 6 b).
The three gold clusters exhibit noticeable distinct chem-
ical reactivities. The kinetic barriers for dissociation of H2
molecules on Au9(P(CH3)3)4, Au11(P(CH3)3)6 and Au36-
(SCH3)14 are 0.31, 0.55 and 0.75 eV, respectively, leading to
the formation of two H* adatoms on the Au sites. The binding
capabilities of the clusters reduce as the atomicity increases
(Figure 6 c). The adsorption energies of CO* (a critical
intermediate toward various products) relative to the free
CO molecule are @1.24, @1.15 and @0.73 eV for Au9(P-
(CH3)3)4, Au11(P(CH3)3)6 and Au36(SCH3)14, respectively. For
Au36(SCH3)14 with weak binding strength, HCOOH mole-
cules can desorb easily from the cluster and thus may be the
main products of CO2 hydrogenation. Au9(P(CH3)3)4 and
Au11(P(CH3)3)6 having strong binding with CO* and other
intermediates would allow further hydrogenation of CO* or
C@C coupling, such that C1 products beyond CO and
HCOOH and even C2 products are possible. The binding
capabilities of gold clusters are correlated to the d-orbital
center of Au atoms, as demonstrated by their electronic
structures in Figure S15. The smaller-size cluster has a higher
d-orbital center relative to HOMO, which results in less
occupancy of the antibonding states formed with reaction
intermediates, and thus provides stronger binding strength
with reaction intermediates, consistent with the d band
theory.[50]
To further evaluate the activity and selectivity of the three
gold clusters, we explored the full reaction pathways and
energy diagrams of CO2 hydrogenation, as presented by
Figure 7. On all these gold clusters, CO2 molecules can only
be physisorbed, and have thus to be activated by direct
reaction with a H* adatom to form either formate (HCOO*)
Angew. Chem. Int. Ed. 2020, 59, 1919 – 1924

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Figure 7. Energy diagrams of CO2 hydrogenation on Au9(P(CH3)3)4,
Au11(P(CH3)3)6 and Au36(SCH3)14 clusters by DFT calculations. Kinetic
barriers for each elementary step are presented, and the limiting
barriers for various products are highlighted. The insets show the
atomic structures of reaction intermediates during the formation of
CH4, C2H5OH and HCOOH for Au9(P(CH3)3)4, Au11(P(CH3)3)6 and
Au36(SCH3)14, respectively. The H, C, O, P, S and Au atoms are shown
in white, grey, red, green, magenta and yellow, respectively.
or carboxyl (COOH*) species. HCOOH molecule and CO*
intermediate are then produced by hydrogenation of HCOO*
and COOH*, respectively. Further hydrogenation of CO*
and C@C coupling can yield C1 and C2 products, such as
CH3OH, CH4 and C2H5OH. As expected, Au36(SCH3)14 with
weak binding capability favors the HCOO* pathway and
produces HCOOH easily with the maximum barrier of
0.51 eV. The COOH* pathway toward the other products
involves a large barrier of 0.93 eV during the formation of
COOH*, and is thus kinetically hindered. For Au9(P(CH3)3)4
and Au11(P(CH3)3)6, the COOH* pathway is kinetically more
favorable than the HCOO* one with barriers of 0.49 and
0.18 eV, respectively. Formation of HCOOH requires a large
barrier of about 0.88 eV due to the strong adsorption of
HCOO* and unfavorable desorption of HCOOH. In partic-
ular, Au9(P(CH3)3)4 catalyzes CO* hydrogenation by going
through HCO*, H2CO* and H2COH*, to form CHx and
finally produce CH4 with a maximum barrier of 0.49 eV. In
comparison, hydrogenation of H2CO* to CH3OH or C@C
coupling toward C2 products involves larger barriers of 0.60
and 0.93 eV, respectively. For Au11(P(CH3)3)6, C@C coupling
by chemical bonding between CO* and CH2* is much easier
than that on Au9(P(CH3)3)4, involving a small barrier of
0.24 eV mainly due to the steric effect. Further hydrogenation
of CH2*-CO* toward C2H5OH is kinetically favorable, and
the rate-limiting step is the CH2OH* formation with a barrier
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of 0.60 eV. CH3OH and CH4 products require larger barriers
of 1.26 and 0.78 eV, respectively, and thus, have lower yield.
The DFT calculations demonstrate that the three gold
clusters possess different binding capabilities with intermedi-
ate species governed by their electronic structures, which in
turn determine the reaction pathway and product selectivity
of CO2 hydrogenation. As illustrated in Figure 6 d, Au9(P-
(CH3)3)4, Au11(P(CH3)3)6 and Au36(SCH3)14 exhibit high
selectivity for CH4, C2H5OH and HCOOH with limiting
kinetic barriers of 0.49, 0.60 and 0.51 eV, respectively. Product
selectivity and intermediates formed during the reaction
agree well with our experimental results.
Conclusion
Our results explicitly indicate that the non-metallic gold
clusters, Au9, Au11 and Au36, exhibit atomicity-dependent
catalytic performances in the hydrogenation processes of
CO2, where they can selectively determine the reaction
pathways towards C1 or C2 products. Au11 can give > 80 %
selectivity for ethanol as high-value chemical and Au36 can
achieve > 80 % selectivity for formic acid. In contrast, the
activity of the non-metallic gold clusters is 10–70 times higher
than that of metallic nanoparticles. DFT calculations reveal
the molecular-level mechanisms of CO2 reaction with H2 on
the three clusters, which are governed by their distinct binding
capabilities and electronic structures. The exceptional proper-
ties of the non-metallic gold clusters highlight the importance
of pursuing non-metallic metal clusters for catalytic applica-
tions and will open an avenue for a new type of metal catalysts
with high efficiency for a series of challenging chemical
reactions.
Acknowledgements
We acknowledge financial supports from National Natural
Science Foundation of China (21773109, 91845104).
Conflict of interest
The authors declare no conflict of interest.
Keywords: cluster · CO2 · gold · non-metallic properties ·
selectivity
How to cite: Angew. Chem. Int. Ed. 2020, 59, 1919 – 1924
Angew. Chem. 2020, 132, 1935 – 1940
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Manuscript received: October 25, 2019
Accepted manuscript online: November 19, 2019
Version of record online: December 17, 2019
Angew. Chem. Int. Ed. 2020, 59, 1919 – 1924