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Controlling Cubic versus Octahedral Morphology in Plasmonic

Aluminum Nanoparticle Synthesis with Titanocene Catalysts: A
Systematic Study
Jaekwan Kim, Christian R. Jacobson, Naomi J. Halas, and Ian A. Tonks*
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ABSTRACT: Ti precatalysts containing the titanocene moiety

(Cp2Ti−, Cp = cyclopentadienyl) can, under certain conditions,
selectively produce cubic Al nanocrystals through the dehydrocou-
pling of alane amine adducts such as AlH3·NMe2Et. A systematic
study of reaction conditions reveals that cubic Al nanoparticle
formation occurs at a higher temperature (e.g., 65 °C) and/or higher
catalyst-concentration conditions (e.g., 0.5 mol % [Ti]). Kinetic
studies reveal that under these conditions nanoparticle formation and
alane consumption are much faster, and cubic nanoparticle formation
takes place under kinetically controlled conditions. On the other
hand, employing a wide suite of TiX4 (X = anionic ligand)-type
precatalysts yielded only octahedral-shaped aluminum nanoparticles
regardless of conditions. Finally, we report the synthesis of a hydride-bridged Ti−Al heterobimetallic compound from the reaction of
Cp2TiCl2 with AlH3·NMe2Et and characterized it to show that it is a reaction intermediate in the Ti-catalyzed aluminum
nanoparticle synthesis.
KEYWORDS: Aluminum nanoparticles, Titanium catalysts, Titanocene, Shape control, Dehydrogenation, Bimetallic complex

■ INTRODUCTION
Metal nanoparticles (NPs) have been widely used in many
include (i) the formation of Ti/Al heterometallic intermedi-
ates, (ii) the dehydrogenation of alane (AlH3, the precursor of
applications such as catalysis and sensing owing to their unique Al NPs), and (iii) the subsequent formation of Al−Al bonds.
optical properties, in particular, localized surface plasmon Comprehensive evidence for each of these steps and the overall
resonance (LSPR).1,2 The size, shape, and the surrounding mechanism remains elusive. It has also been reported that
environment of the nanoparticles influence LSPR, which has different ligands of the Ti complexes can control the growth
prompted extensive research into the controlled synthesis of and subsequent morphology of the AlNPs.13,16 Notably, Ti
nanoparticles with specific size and shape characteristics.3,4 catalysts containing the titanocene moiety (Cp2Ti−, Cp =
Considerable progress has been achieved in the study of noble- cyclopentadienyl) have demonstrated the ability to produce
metal-based nanoparticles, such as gold (Au) and platinum cubic AlNPs. However, further investigations are required to
(Pt) NPs, by tuning their size and shape and elucidating their unravel the factors of the catalyst structure and reaction
formation mechanism.5−9 However, the demand for cost- conditions that influence the shape of AlNPs and enable
effective material has been increasing, and aluminum (Al) is an precise modification.
attractive candidate among metals because Al is the most Overall, the mechanisms and controlling factors of Ti-
abundant metal in Earth’s crust and can achieve LSPR across catalyzed alane dehydrocoupling remain poorly understood
the IR, visible, and UV regions.10 There have been efforts to despite an increased interest in solid aluminum hydride
understand the mechanism(s) of Al nanoparticle (AlNP) dehydrogenation for hydrogen storage.17−19 However, there
formation,11,12 but there remain significant gaps in our have been significant advances in related dehydrocoupling
understanding owing to intrinsic difficulties in handling
reactive AlNP precursors and because�unlike noble metal
NP synthesis�AlNP formation occurs in the presence of Received: October 12, 2024
catalysts, which are typically Ti-based. Revised: November 22, 2024
The Halas group has undertaken extensive investigation to Accepted: November 22, 2024
gain insight into the role of Ti catalysts in the AlNP synthesis
process and to achieve controllable AlNP morphologies.13−16
The fundamental steps in AlNP synthesis are proposed to

© XXXX American Chemical Society https://doi.org/10.1021/acscatal.4c06286

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reactions such as dehydrocoupling of an amine-borane adduct

by titanocene (or zirconacene) catalysts20−30 and AlIII hydride
catalysts.31 In addition, recent studies of dehydrogenation of
aluminum dihydride have highlighted the potential of this
chemistry.32,33 These prior studies indicate that understanding,
and ultimately control of, alane dehydrocoupling should be
possible.
In this study, we present a systematic study of reaction
conditions for the optimization of the controlled synthesis of
AlNPs, shedding light on how each set of reaction conditions
impacts the resulting morphology with a particular focus on
how the kinetics of AlNP formation/alane dehydrocoupling
impact resultant AlNP morphology. Additionally, we isolated
and characterized a bridged Ti−Al heterobimetallic com-
pound, which was demonstrated to be an early reaction
intermediate through further reactivity studies.

■ RESULTS AND DISCUSSION

Prior work from the Halas group on AlNP morphology control
focused on Ti(OiPr)4 and Cp2Ti derivatives. These studies
revealed that Ti(OiPr)4 yields truncated octahedron AlNPs
having both {111} and {100} facets, in alignment with the
Wulff theorem for FCC metals, while Cp2Ti derivatives led to
cubic AlNPs with {100} facets.5 Figure 2. SEM images of shape-controlled AlNP syntheses using
[Cp2TiCl]2 (0.05−0.5 mol %) at 40−65 °C. [AlH3·NMe2Et]: 1 mM
To start our investigation, we sought to examine how Ti in THF.
catalyst structure could impact the morphology of AlNPs with
a wider range of Ti catalysts under a broad range of and catalyst loading was not confined to [Cp2TiCl]2: other
temperatures (40−65 °C) and catalyst loadings (0.1 mol % precatalysts containing the Cp2Ti group, including Cp2TiCl2,
to 1 mol % of [AlH3·NMe2Et]). Simple TiX4-type (X = anionic Tebbe’s reagent (Cp2Ti(μ-CH2)(μ-Cl)Al(CH3)2), and Cp2Ti-
ligand) catalysts (Ti(OiPr)4, TiCl4, Ti(NMe2)4, TiBn4, and (BTMSA) (BTSMA = bis(trimethylsilyl)acetylene) also
TpTiCl3 (Tp = Tris(pyrazolyl)borate)) all produce predom- showed the same effect (Figure 3 and Figures S6 and S7).
inantly truncated octahedra regardless of the ligand with 1 mol
% of catalyst loading at 40 °C (Figure 1, Figures S3 and S4). A

Figure 1. Dehydrocoupling of alane with a simple TiX4 catalyst leads

to truncated octahedral nanocrystals. Right: SEM image of AlNPs
synthesized using 1 mol % of TiCl4 at 40 °C.

deeper examination of Ti(OiPr)4-catalyzed reactions revealed

successful truncated octahedral AlNP formation with catalyst Figure 3. SEM images of cubic AlNPs with other Cp2Ti-type catalysts
(Cp2TiCl2, Cp2Ti(BMTSA), Cp2Ti(μ-CH2)(μ-Cl)Al(CH3)2, condi-
loadings ranging from 0.1 mol % to 1 mol % at 40 °C, although tions: 1 mol % [Ti], 65 °C, [AlH3·NMe2Et]: 1 mM in THF).
at higher temperatures of 50 and 60 °C, the Al NPs became
irregularly shaped or fused.
In contrast to the TiX4-type catalysts, Cp2Ti-bearing These results indicate that the oxidation state of the Ti
catalysts yielded either cubic or octahedral-shaped Al NPs, precatalyst is not correlated to the shape of the AlNPs since the
depending on reaction conditions (Figure 2, Figure S5). formal oxidation states for the preceding complexes range from
[Cp2TiCl]2 selectively catalyzes the formation of cubic AlNPs Ti(II) to Ti(IV). This is perhaps to be expected, as AlH3 is a
under higher temperature (e.g., 65 °C) and higher catalyst strong reductant that should be able to easily reduce Ti(IV).
loading conditions (e.g., 0.5 mol %), while under lower Interestingly, CpTiCl3, a Ti precatalyst containing only 1 Cp
temperature (e.g., 40 °C) and lower catalyst loading (e.g., 0.05 ring, led to octahedral AlNP formation even at 65 °C and
mol %) conditions, AlNPs are predominantly octahedral. under 1 mol % catalyst loading, showing that cubic shape
Under the cubic AlNP reaction conditions, right bipyramid control from the catalyst appears to rigorously require a
shapes were also produced with the Al nanocubes. Both have metallocene fragment (Figure S8).
{100} facets, but the right bipyramids grow from singly Given that AlNP shape control could be modulated with
twinned seeds, while the cubes originate from single crystal titanocene precatalysts under different conditions, we next
seeds (Figure S5).34 The shape control by varying temperature conducted experiments where the reaction conditions were
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varied in situ to study whether (1) shape control was dictated Cp2TiCl2 as the catalyst across different catalyst loadings
at the seeding stage vs crystal growth phase and (2) one shape (Figure 5a) and temperature regimes (Figure 5b). In all cases,
could be interconverted into the other.
First, the shape of AlNPs as they grow over time was
observed by quenching aliquots of a “cube-controlled” reaction
(0.5 mol % of [Cp2TiCl]2 at 60 °C) every 10 min and
monitoring shape by SEM. At early stages (<50 min), the
AlNPs were multifaceted, containing both {100} and {111}
facets (Figure S10). The {100} facet proportion increased as
the NPs grew larger over time, showing clear nanocubes at 70
min of the reaction. At 90 min, most of the NPs were cubic,
with some elongated and fused NPs. The findings indicate that
the clear cubic shape is determined after nanoseed or
nanocluster formation.
Next, an “octahedral-controlled” reaction (0.05 mol % of
[Cp2TiCl]2 at 50 °C) was dosed with additional 0.45 mol %
[Cp2TiCl]2, resulting in total 0.5 mol % Ti, at different time
points to probe if octahedrally shaped seeds could be
converted to cubic AlNPs. Every attempt yielded cubic
AlNPs (Figure 4a, Figure S11), which further demonstrates

Figure 4. SEM images of AlNPs after changing reaction conditions in

situ. (a) Increase in catalyst concentration. (b) Change in temper-
ature. NR3 = NMe2Et.

that shape is determined in the middle or late phase of AlNP

Figure 5. Kinetic trace of AlH3·NMe2Et dehydrogenation in THF-d8
synthesis, consistent with the quenching experiments described (a) with different catalyst loadings of Cp2TiCl2 at 60 °C and (b)
above. The size of Al nanocubes formed when the stock different reaction temperatures with 1 mol % of Cp2TiCl2.
solution was added after 20 min was larger than that of cubes
formed after the stock solution was added after 50 min because
the shorter seeding time likely leads to fewer seeding events, the consumption of AlH3·NMe2Et shares a common shape
and the seeds can then grow larger owing to the relatively characterized by a slower induction period, followed by a faster
larger amount of Al for fewer seeds. decay. These features indicate that AlH3·NMe2Et reacts with
Finally, in situ temperature changes were examined. Raising the Ti complex, likely predominantly forming Ti/Al clusters
the reaction temperature from 40 °C to 65 °C in the middle of during the induction period. Then, after a critical seeding
the reaction (after 1.5 or 3 h) produced more {100} facets period, AlH3·NMe2Et undergoes rapid catalytic dehydrogen-
than reactions held at 40 °C, leading to elongated rodlike ation−reduction and deposition onto growing seeds. SEM
crystals with {100} sides (Figure 4b). Here, the increase in analysis and UV/vis spectroscopy were also used to monitor
temperature likely facilitates faster Al reduction, leading to the the reaction behavior during the induction period and the
formation of a structure with more {100} facets on the pre- faster decay phase (Figures S13 and S14). The results showed
existing Al nanoseeds. On the other hand, decreasing the that a small number of immature AlNPs formed during the
temperature from 65 °C to 40 °C after 50 min yielded induction period, while the majority were rapidly formed after
inhomogeneous shapes, probably because reactive Al nano- the faster decay, consistent with the NMR analysis. At higher
clusters could not grow larger due to an insufficient amount of catalyst concentrations or temperatures, the slope of the
reduced Al, causing them to fuse together. catalytic reaction period is steep, indicating that Al reduction is
The above experiments indicate that the rate of Al reduction rapid and Al nanocubes are selectively formed, suggesting that
and deposition under different reaction conditions (temper- the cubic shape is kinetically controlled.
ature or catalyst concentration) during AlNP growth is a key To test the hypothesis that cubic AlNP formation was
factor in determining their shape. Thus, we next conducted kinetically controlled, we next explored catalytic AlNP
kinetic studies of AlH3·NMe2Et dehydrogenation using formation under a purge of H2 gas. As H2 is a byproduct of
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dehydrogenation, introduction of excess H2 into the headspace previously synthesized through the reaction of AlH3·Et2O with
could perturb the equilibrium of dehydrogenation and result in Cp2TiCl2.35 In addition to 1, several Ti/Al bimetallic or
overall slower AlNP growth. As hypothesized, the reaction of multimetal complexes sharing the same motif, [Ti-μ2H2-Al],
AlH3·NMe2Et with [Cp2TiCl]2 at high concentration and have been reported.36−40 All of these complexes feature a Cp
temperature under a purge of H2 results in truncated (or Cp*) ligand on Ti, suggesting that the Cp ligand provides
octahedral AlNPs (Figure S12). Because the equilibrium of the stability necessary for isolation.
alane dehydrogenation is perturbed by increasing [H2], the From a simple electron-counting analysis, the limiting
rate of Al0 formation and deposition decreases, while the rate electronic structures of 1 could be either TiIII/AlIII or TiIV/
of Al0 diffusion remains constant, since the reaction temper- AlII, indicating a net reduction of the system en route to full
ature is unchanged. Al 0 can then be relocated to reduction of alane. 1 contains two bridging hydrides, with Ti−
thermodynamically more stable sites, yielding octahedra H average bond lengths of 1.797 Å (1.757, 1.821, 1.813, 1.797
under thermodynamic rather than kinetic control. Å of two complexes, respectively, in the unit cell), which are
Of particular interest is how reduced Al clusters initially slightly longer than the average TiIV−H bond length (1.781 Å)
form during the catalytic induction period prior to AlNP but shorter than TiIII−H (1.865 Å).41 Since 1 is paramagnetic,
growth. Here, we are undertaking studies to isolate and it was characterized by EPR spectroscopy to better understand
characterize early reaction intermediates, including Ti−Al the electronic structure (Figure 6c). 1 has a g value of 1.987,
heterobimetallic complexes. Reaction of Cp2TiCl2 with 1 equiv with hyperfine splitting parameters ATi = 15, AAl = 29.5, AH =
of AlH3·NMe2Et in THF for an hour yielded a purple solution 9.7, and ACl = 1.9. The hyperfine couplings of atoms in the [Ti-
containing Ti−Al bimetallic complex 1 (Cp2Ti(μ2-H2)- μ2H2-Al] scaffold indicates that the best description of 1 is a
AlCl2(THF)). Repeated in vacuo drying of the reaction delocalized radical shared between the metal centers rather
mixture followed by redissolution into THF was critical to than a formally TiIII/AlIII or TiIV/AlII complex. Excitingly, 1
remove excess NMe2Et from the reaction, which then enabled acts as a precatalyst for AlH3·NMe2Et dehydrogenation,
the crystallization of 1 from a pentane/p-xylene mixture at −35 yielding AlNPs identical to those formed from Cp2TiCl2
°C. The solid state structure of 1 is reported in Figure 6. A with similar kinetic behavior, indicating that 1 is an early
similar compound coordinated by Et2O instead of THF was intermediate en route to productive catalysis (Figure 7).
Catalysis with 1 still reveals an induction period, indicating
that there are still more key intermediates to be investigated in
the future.

Figure 7. Kinetic trace of AlH3·NMe2Et dehydrogenation catalyzed

by 1. Conditions: 20 mM [Al], 50 °C, and 0.2 mM 1 in THF.

Figure 6. Reaction intermediate 1 isolation and characteristics. (a) Based on the above studies into the kinetics of AlNP
Reaction scheme of the synthesis of 1. (b) Molecular structures of 1.
One complex in the unit cell (Z = 2) is shown. p-Xylene cosolvent
formation under various conditions, we can propose a more
and hydrogen atoms except bridging hydrides are omitted for clarity. detailed reaction mechanism for shape-controlled AlNP
Light gray ellipsoids are disordered Cp. Ellipsoids are drawn at the synthesis (Figure 8). First, Ti precatalysts form a [Ti-μ2H2-
50% probability level. Selected bond distances (Å): Ti1A−H1A 1.757, Al] intermediate with one equivalent of alane, which then
Ti1A−H2A 1.821, Al1A−H1A 1.730, and Al1A−H2A 1.678. (c) likely proceeds to make larger Ti/Al multimetal clusters via
Experimental and simulated EPR spectra of 1. additional dehydrocoupling reactions with alane. The reaction
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aligns with prior in situ studies,15 although reactions catalyzed

by 1 still have an induction period, meaning that further
transformations must take place before rapid Al deposition.

■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.4c06286.
Full experimental section (synthesis, SEM images,
kinetic study, and simple calculation of Cp coverage
on AlNP surface) (PDF)
Crystallographic details (CIF)

■ AUTHOR INFORMATION
Corresponding Author
Ian A. Tonks − Department of Chemistry, University of
Figure 8. Proposed mechanism for AlNP shape control catalyzed by Minnesota−Twin Cities, Minneapolis, Minnesota 55455,
Cp2Ti-derived catalysts. United States; orcid.org/0000-0001-8451-8875;
Email: [email protected]
eventually reduces Al3+ to Al adatoms growing into “nano- Authors
seeds”. With titanocene catalysts, competing kinetic and Jaekwan Kim − Department of Chemistry, University of
thermodynamic regimes dictate the AlNP shape. Prior work Minnesota−Twin Cities, Minneapolis, Minnesota 55455,
from the Halas group indicates that Cp rings can bind to the Al United States
NP surface through π-electron interaction of the arene,13 Christian R. Jacobson − Department of Chemistry and
affecting its shape by modulating surface energy.5 At high Laboratory for Nanophotonics, Rice University, Houston,
catalyst concentration and high temperature, the rate of Texas 77005, United States; orcid.org/0000-0002-9578-
nanoseed formation (dehydrogenation and deposition) is high, 8763
along with significant catalyst-bound surface coverage (see Naomi J. Halas − Department of Chemistry and Laboratory
Supporting Information), resulting in kinetic deposition onto for Nanophotonics, Rice University, Houston, Texas 77005,
the {111} facet, leading to cubic AlNPs. In contrast at low United States; Department of Physics and Astronomy,
catalyst concentration or temperature, dehydrogenation and Department of Electrical and Computer Engineering, Rice
deposition are slower and there are fewer catalyst-bound University, Houston, Texas 77005, United States;
AlNPs under the equilibrium conditions, leading to the orcid.org/0000-0002-8461-8494
formation of thermodynamically controlled octahedral shape.
Thus, counterintuitively, less-stable cubic {100} AlNPs are Complete contact information is available at:
formed at higher temperature, while more stable octahedral https://pubs.acs.org/10.1021/acscatal.4c06286
{111} AlNPs are formed at lower temperature.5 In contrast,
TiX4-type catalysts do not have capping effects through arene− Author Contributions
surface interaction, leading solely to octahedral shapes across N.J.H. and I.A.T. conceived of and directed the research. J.K.
all concentration and temperature regimes. However, simple planned and executed the research and data analysis. C.R.J.
capping effects are not solely responsible for cubic Al NP conducted initial experiments and assisted in data analysis. All
formation: for example, the potentially capping precatalyst authors contributed to the writing and revision of the
CpTiCl3 does not produce cubic Al NPs, even at high manuscript.
precatalyst stoichiometries where there are sufficient Cp Notes
groups to fully cap all Al surfaces (Figure S9). This highlights The authors declare no competing financial interest.
the critical role of the overall catalyst structure in addition to
capping effects. ■ ACKNOWLEDGMENTS

■ CONCLUSION
In conclusion, we have systematically studied how the shape of
Financial support was provided by the National Science
Foundation (2154998) and the University of Minnesota
Department of Chemistry (4th year Excellence Fellowship to
AlNPs is controlled by using Cp2Ti-type precatalysts. At high J.K.). Instrumentation for the University of Minnesota
temperature and catalyst concentration, the cubic shape Chemistry NMR facility was supported from a grant through
predominates, but in low temperature and catalyst concen- the National Institutes of Health (S10OD011952). Funding
tration, a truncated octahedral shape results. These two shapes for NMR instrumentation at the Minnesota NMR Center was
can be described as the kinetic- or thermodynamic-controlled provided by the Office of the Vice President for Research, the
shape, respectively. This work provides further evidence that Medical School, the College of Biological Science, NIH, NSF,
the mechanism for cubic shape control is likely a function of and the Minnesota Medical Foundation. X-ray diffraction
Cp surface binding equilibria,11,15 although the morphology of experiments were performed with a diffractometer purchased
seeds13 remains in question. In addition, the reaction of through a grant from NSF/MRI (1229400) and the University
Cp2TiCl2 and alane yielded the Ti/Al heterobimetallic of Minnesota. Dr. Victor G. Young Jr. is acknowledged for
complex (1), which was characterized by XRD and EPR. helping to solve the crystal structure. Parts of this work were
Complex 1 is an early intermediate in the Al NP synthesis and carried out in the Characterization Facility, University of
18433 https://doi.org/10.1021/acscatal.4c06286
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