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Article
Microwave Enhancement of Autocatalytic Growth of Nanometals
Bridgett Ashley, Parth N. Vakil, Brian Lynch, Christopher M.
Dyer, Joseph B. Tracy, Jeffery Owens, and Geoffrey F. Strouse
ACS Nano, Just Accepted Manuscript • DOI: 10.1021/acsnano.7b04040 • Publication Date (Web): 02 Oct 2017
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Page 1 of 18 ACS Nano

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Microwave Enhancement of Autocatalytic Growth of Nanometals
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6 Bridgett Ashley1,2, Parth N. Vakil1, Brian Lynch3, Christopher M. Dyer1, Joseph B. Tracy3, Jeffery
7 Owens2, Geoffrey F. Strouse1*
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9 1 Department of Chemistry and Biochemistry, Florida State University; Tallahassee, FL 32306-4390
10 2 Air Force Civil Engineer Center, Tyndall AFB, FL 32403
3 Department of Materials Science and Engineering, North Carolina State University; Raleigh, NC 27695
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12 * Corresponding Author strouse@chem.fsu.edu
13
14 Abstract: The desire for designing efficient synthetic methods that lead to industrially important
15 nanomaterials has led a desire to more fully understand the mechanism of growth and how modern
16
synthetic techniques can be employed. Microwave (MW) synthesis is one such technique that has
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18 attracted attention as a green, sustainable method. The reports of enhancement of formation rates
19 and improved quality for MW driven reactions are intriguing, but the lack of understanding of the
20 reaction mechanism and how coupling to the MW field leads to these observations is concerning.
21 In this manuscript, the growth of a metal nanoparticles (NP) in a microwave cavity is
22 spectroscopically analyzed, and compared with the classical autocatalytic method of NP growth to
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elucidate the underpinnings for the observed enhanced growth behavior for metal NPs prepared in
25 a MW field. The study illustrates that microwave synthesis of nickel and gold nanoparticles below
26 saturation conditions follows the Finke–Watzky mechanism of nucleation and growth. The
27 enhancement of the reaction arises from the size dependent increase in MW absorption cross
28 section for the metal NPs. For Ni, the presence of oxides is considered via theoretical computations
29
and compared to dielectric measurements of isolated nickel NPs. The study definitively shows that
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31 MW growth can be modeled by an autocatalytic mechanism that directly leads to the observed
32 enhanced rates and improved quality widely reported in the nanomaterial community when MW
33 irradiation is employed.
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35 Keywords: Microwave, autocatalytic, mechanism, spectroscopy, nanoparticle, nickel, core/shell
36
37
38 The early days of nanoscience were enhancement has not been satisfactorily
39 focused on developing efficient synthetic explained.
40 methods, including hot injection, microwave, In nanometal growth in a MW, the
41 microfluidic, and use of single source reported enhanced reactions are poorly
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43
precursors.1 Since then the nanoscience field understood but clearly must reflect the
44 has matured with a growing focus on absorption of the MW energy to produce heat,
45 understanding the growth mechanisms for which is measurable by dielectric spectroscopy.
46 nanocrystals and how the reaction can be There is no possibility that a single MW photon
47 controlled via heating and precursor addition.2-7 at 2.45 GHz can initiate a reaction; however, the
48 Of the recently developed synthetic tools for absorption of the 2.45 GHz photon can produce
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50 reproducible preparation of nanomaterials, heat via frictional processes.12 In addition, the
51 microwave (MW) heating techniques3-15have formation of nanometal under identical reaction
52 been purported to enhance nucleation and conditions must follow the well-defined
53 growth rates and produce improved material thermodynamic and kinetic models for
54 quality in II–VI,5,6 III–V,7,8 IV9 nanoparticle growth from a monomer. The
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semiconductors, and metals.10,11,23,24 While growth behavior of Ni and Au nanoparticles
57 there is no doubt of the claims, the rationale for grown under mildly reducing conditions in a
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convective reaction has been fully developed studied in the field due to plasmonic properties,
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5 and ascribed to an autocatalytic mechanism.13- Ni NPs was chosen as a classical soft magnetic
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6 The autocatalytic mechanism for metal material that mechanistically has been studied
7 growth, occurs under conditions where a M0 in solvothermal reactions13,22 and is an
8 monomer is formed far below saturation important material for applications in
9 conditions due to a slow kinetic conversion of electromagnetic shielding and catalytic
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the metal coordination complex (precursor) to applications.23 By correlating the MW power
12 an active monomer step. This leads to a absorbed and the temperature of the reaction it
13 condition where the separation of nucleation is demonstrated that the MW-facilitated growth
14 and growth occur due to the rate of growth of metal NP follows the F-W autocatalytic
15 being faster than the rate of nucleation. model.2 The data support a model wherein
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Turkevich, et al.15 originally observed this MW-induced growth enhancement is due to
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18 behavior in AuNPs, which led to Finke, et al. efficient energy coupling to the reactants, and
19 proposing an autocatalytic mechanism sustained growth is due to MW absorption into
20 occurring through a series of steps. 2 More the metal NP as it grows, resulting in uniform
21 recently the autocatalytic theory was expanded nucleation, accelerated NP growth, and thus
22 to account for multiple steps in the reaction to narrower size dispersities. The results of this
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explain the narrow size dispersity of study are consistent with recent work by de la
25 materials.16-18 The Finke–Watzky (F-W) Hoz,24,25 which showed that, for a chemical
26 mechanism for NP growth assumes activation reaction in the MW, both the activation energy
27 of the precursor is kinetically slow while and MW absorption are important factors in
28 growth at a nuclear facet is energetically more determining that a reaction performed in a MW
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favorable than formation of new nuclei. The reactor will or will not improve noticeably
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31 autocatalytic mechanism is unlike the LaMer when compared to a conventional lyothermal
32 classical nucleation theory where super reaction. A theoretical framework comparing
33 saturation is required to initiate burst nucleation size and temperature response of metal NPs
34 and diffusion limited growth. grown in a 2.45-GHz MW field can provide a
35 Since the earliest report of autocatalytic context to understand the growth of nanometals
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37 growth by Turkevich and defined by Finke- in a MW cavity.
38 Watzky, the autocatalytic mechanism has been As part of the study, scaling law
39 validated for several transition metals,19,28-30 behavior for metal NP MW absorption is
40 including Ni,13 and has even been expanded to developed to elucidate the temperature- and
41 describe several natural phenomena, including size- dependent permittivity, permeability, and
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plaque formation in Alzheimer’s disease.20 role of potential oxides at the surface on the
44 Measuring the growth kinetics of a nanometal NiNP during nucleation and growth. The
45 under MW reaction conditions and correlating permittivity and permeability data of the
46 the behavior with the predictive autocatalytic isolated Ni nanocrystals support the rapid
47 models can allow the MW enhancement to be formation of a native oxide layer (3
48 understood and correlated to observation in monolayers, ~1.2 nm) on the surface following
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50 convective reactions. isolation of the Ni from the reaction and not
51 To interrogate the growth mechanism during the reaction. The presence of a stable
52 for metal NPs in mildly reducing solvents in a oxide that rapidly forms after isolation may
53 MW reactor and the influence of the MW field, answer a common question why NiNPs
54 the growth of NiNPs, and as a comparison to embedded in polymers to enhance EMI
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literature reported autocatalytic growth for shielding exhibit reduced shielding until the
57 AuNPs,16,21 is analyzed. While AuNPs are well percolation threshold is exceeded. The
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observation can be explained by the oxide proportional to the complex permittivity of a
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5 contributions, as the experimental size- material, ε* = ε' + iε" and is frequency and
6 dependent dielectric data suggest that the temperature dependent. The complex dielectric
7 presence of as little as a monolayer of oxide includes a term for the ability of a material to
8 results in loss of the dielectric benefits of NiNP store electrical charge—known as the
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inclusion for EMI shielding. 23,26 permittivity and represented by ε'—and a term
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Although NiNP and AuNP are the only for the combined electronic losses (dipole,
12 metal NPs fully explored in this manuscript the ionic, and Maxwell–Wagner) of a material,
13 insights can be extended to materials grown in known as the loss factor, represented by ε".27
14 a MW reactor when the precursor activation For simplicity, MW chemists often use the term
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step is kinetically slow. By carrying out tan δ = ε"/ε' because the absorbed power (Pabs)
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nanometal growth reactions in mildly reducing ∝ tan δ. The rate of growth of the metal NP
18 conditions, control of growth behavior can be from the precursor will depend on Pabs into the
19 achieved through power and concentration even system (MW cavity, vessel, solvents, and
20 at conditions below supersaturation. The precursors). Pabs is related to the complex
21 understanding of the MW growth behavior for
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dielectric and the heat capacity, such that
a nanometal as merely a thermodynamic and
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kinetic problem allows the extension of MW 𝑃𝑃abs = 𝑀𝑀 𝐶𝐶𝑝𝑝
∆𝑇𝑇 1
= 𝜔𝜔𝜀𝜀0 𝜀𝜀ʺeff ∫𝑉𝑉�𝐸𝐸�⃗ ∗ ∙ 𝐸𝐸�⃗ � 𝑑𝑑𝑑𝑑 +
𝑡𝑡 2
25 methods to a much wider range of materials 1
�⃗∗ ∙ 𝐵𝐵
�⃗�
𝜔𝜔𝜇𝜇0 𝜇𝜇ʺeff ∫𝑉𝑉�𝐵𝐵 [1]
without invoking non-thermodynamic effects. 2
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27 M is the mass, Cp is the specific heat capacity,
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Results and Discussion ΔT is the change in temperature, t is time, ω is
30 frequency, ε0 is the permittivity of free space,
Size- and Temperature-Dependent MW
31 ε"eff is the lossy permittivity of the material, µ0
32 Absorption. During the growth of a metal NP
33 from a molecular precursor the impingent MW is the permeability of free space, µ"eff is the
34 energy is converted into heat through molecular lossy permeability of the material, V is volume,
35 motion driven by dipolar polarization of the ���⃗
𝐸𝐸 ∗ is the complex conjugate of the electric
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37 solvent and precursors to initiate critical nuclei field, 𝐸𝐸�⃗ is the electric field, ���⃗
𝐵𝐵 ∗ is the complex
38 formation. As the precursor is consumed and conjugate of the magnetic field, and 𝐵𝐵 �⃗ is the
39 the metal NP grows, the dipolar cross-section of magnetic field.
40 the system will evolve. For a metal, MW The magnitude of coupling of the
41 coupling also includes ohmic losses, charge
42 impinging MW photon on a reaction mixture
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separation, and Maxwell–Wagner heating at the will strongly depend on the electric dipoles of
44 solution– metal interface, which enhances the the reaction constituents. Applying the Beer–
45 MW heating. The contribution from the Lambert assumption in absorption
46 individual components will evolve with the spectroscopy leads to the simple conclusion that
47 size-dependent metallic properties of the
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the MW energy is absorbed by the material with
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growing metal NP. Additionally, solvent and the largest ε" and scattered by the material with
50 vessel contributions, which vary with the largest ε' term in the system.27
51 temperature and dielectric properties, must also Pabs for the solvent decreases with
52 be considered. increasing reaction temperature, while Pabs for
53 The complex dielectric is related to the
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the precursor and NiNP will be time dependent
absorption cross-section or the point at which as the precursor is consumed and the NiNP
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the amplitude of the impinging MW field grows. As the MW cross section of the
57 decreases by 1/e. The rate of decrease is
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precursor is orders of magnitude lower than for in Figure 1A for comparison. Using eqn 1, the
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5 the NiNP, the largest change in MW absorption theoretical Pabs is calculated from dielectric
6 will reflect the size-dependent evolution of the measurements at 2.45 GHz at room temperature
7 NiNP’s complex dielectric. To account for the on neat material using a vector network
8 change in MW absorption a scaling law can be analyzer (VNA). Tan δ for OAm is 0.040, for
9 derived by considering the work of Gor’kov Ni(acac)2 is 0.006, for HAuCl4 is .031, (though
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and Eliashberg40,41 and of Marquardt and this number is complicated by the highly
12 Nimtz,42,43 on the size-dependent dynamic hygroscopic nature of HAuCl4) and the
13 electric susceptibility (xe) of metallic NPs in a predicted values for 4- and 6-nm Ni and Au are
14 MW field. The early studies demonstrated that derived using eqn 2. From the tan δ values, the
15 the value of ε* can be described within a quasi- order of Pabs will be Ni > OAm >Ni(acac)2 for
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DC quantum model when the size difference the neat materials. The same behavior is
18 between the photons and the NPs is 6–8 orders observed for the AuNPs. This leads to the
19 of magnitude. The complex dielectric can be conclusion that in the formation of NiNPs,
20 written as the Gorkov–Eliashberg equation during the reaction, the contribution of
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22 𝑚𝑚∗ 𝑘𝑘F (2𝑟𝑟)2 139 𝜔𝜔𝑚𝑚∗ 𝑘𝑘F (2𝑟𝑟)3
Ni(acac)2 to MW absorption is nominal, as at
𝜀𝜀 ∗ = 1 + + �2 + 𝑖𝑖 � [2]
23 20π2 𝑎𝑎B 1200 π2 𝑎𝑎B 6ℏ this concentration of Ni(acac)2 (0.15 mmol) to
24 OAm (45 mmol), the MW power absorbed by
25 where m* is the effective electron mass, aB is
26 Ni(acac)2 will be four orders of magnitude
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the Bohr radius, r is the radius of the NP, ω is lower than by OAm. As Ni nucleates, it
28 the frequency of EM radiation, kF is the becomes the dominant absorbing species and is
29 magnitude of the Fermi wave vector, and ħ is expected to increase the reaction temperature as
30 Plank’s constant. The temperature dependency the NiNP grows larger at fixed MW power. The
31 of the dielectric constant can thus be written by
32 same trend by analogy will be observed for
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coupling the Debye equation27-30,45 to the AuNP growth within the MW field.
34 Gorkov–Eliashberg equation, such that ε*(T) is As shown in eqn 1–3, the cross section
35 expressible as for MW absorption for the metal NP evolves in
36 time as the NP grows and the precursor is
2� 1�
37 𝑒𝑒 − Δ𝑇𝑇 𝑒𝑒 − Δ𝑇𝑇
38 𝜀𝜀 ∗ (𝑇𝑇) ≅ 𝜀𝜀 ′ 0 �1 + 1� 1� � + 𝑖𝑖𝑖𝑖"0 �1 + 1� 1� � [3] depleted. Therefore, as a reaction progresses to
𝑒𝑒 Δ𝑇𝑇 + 𝑒𝑒 − Δ𝑇𝑇 𝑒𝑒 Δ𝑇𝑇 + 𝑒𝑒 − Δ𝑇𝑇
39 completion, MW absorption is expected to
40 evolve from simple dipolar polarization-driven
41 A detailed derivation of eqn 3 is provided in the motion of precursor and solvent molecules to
42 Supporting Information. The model predicts contributions arising from NP absorption and
43 that as the metal NP’s size and reaction scattering, depending on the material’s
44 temperature increase, the power absorbed also
45 dielectric.
increases, creating a positive feedback loop of The predicted heating-vs.-NiNP size
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continuously increasing power absorption. correlation is graphed in Figure 1B, while the
48 Using eqns 1–3, the evolving dielectric curve for AuNP is plotted in Figure 1C. The
49 environment that leads to MW heating can be solid line represents the predicted reaction
50 evaluated in terms of the size and temperature.
51 trajectory assuming normal diffusion controlled
In Figure 1A, the theoretical Pabs is compared growth in both graphs. Inspection of Figure 1B
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as a function of temperature for single confirms that at the temperature of the reaction
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54 molecules of oleylamine (OAm), Ni(acac)2, (280 °C), absorption by the 20-nm NiNP is an
55 HAuCl4 and single 4- and 6-nm Ni and AuNPs. order of magnitude larger than by the 3-nm
56 The 8 nm AuNP and monomers are also plotted NiNP. For the 8-nm AuNP, the heating curve is
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Evidence of Finke–Watzky Growth. The
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5 growth of AuNPs under mild reducing
6 conditions was originally described within the
7 autocatalytic mechanism by Turkevich, and
8 theoretically described by Finke and reported
9 by others.16 The autocatalytic mechanism was
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extended to explain Ni growth under mildly
12 reducing conditions in organic solvents by
13 Tilley, et al.13 In both cases the autocatalytic
14 growth occurs for reactions performed below
15 supersaturation conditions, wherein burst
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nucleation cannot occur due to the slow
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18 continuous formation of reactive M0 monomers
19 from M(II) ionic precursors.31-33 The
20 autocatalytic mechanistic behavior for the
21 growth of metal nanoparticles thus reflects the
22 kinetic barrier for formation of M0 monomers
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effectively suppressing nuclei formation.33,34
25 The autocatalytic growth mechanism is
26 described effectively as a two-step mechanism
27 with nucleation in step 1, M0monomoer  Mcrit
28 with a rate of k1 (Mcrit is the critical nuclei),
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followed by the addition of additional monomer
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31 to generate a larger nuclei, where nM0monomoer +
32 Mcrit  M* with a rate of k2. The growth to
33 the final NP size occurs by repeating step 2 so
34 that M* represents a continuously evolving
35 Figure 1. A) Theoretical Pabs vs. temperature plot for larger nuclei. In effect, the final M NP size is
36 oleylamine (OAm), Ni(acac)2, HAuCl4, 4-nm, and 6-nm
37 NiNP and AuNP based on experimental room temperature
achieved by continuous growth from the
38 dielectric measurements on neat materials. B) Plot of Pabs evolving nuclei once the monomer is depleted,
39 vs. size and reaction temperature for Ni nanoparticles such that nM0monomoer + M*  M NP. It is worth
40 based on the size- and temperature-dependent change in
permittivity (eqns 2 and 3). C) Plot of Pabs vs size and
noting that the autocatalytic mechanism
41 reaction temperature for Au nanoparticles based on the equations are often misinterpreted as formation
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size- and temperature-dependent change in permittivity of two-nuclei due to the nomenclature being
(eqns 2 and 3). In (B) and (C) the solid line is a guide to
44 eye for the reaction trajectory.
erroneously interpreted as new nuclei rather
45 than increasing nuclei size.17,33, 35
46 steeper than for Ni reflecting the increased ε" In the autocatalytic mechanism the rate
47 contribution to heating as Au increases in size of nucleation (k1) therefore is slow relative to
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49
(larger ε" or Au vs. Ni). In addition, the AuNP the rate of growth (k2) due to the surface energy.
50 reaction is held at 150 °C and is not allowed Since k1 << k2, growth from the initially formed
51 reach the boiling point of the solvent. Based on nuclei is energetically favored over formation
52 the theoretical heat plots in Figures 1B and C, of new nuclei The kinetic slow step is the amine
53 the increased dielectric absorption leading to reduction of the metal complex to produce M0
54 higher reaction temperatures as the metal NP monomers prior to nucleation of a critical sized
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56 grows may explain the MW enhanced rates and cluster.14,33
57 control observed in MW-based reactions.
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In the nomenclature of the autocatalytic the nucleation rate will remain constant at
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5 mechanism the ratio of growth to nucleation constant temperature or follow an Arrhenius
6 rates, i.e. k2[MSA] /k1, is defined as the RFW- behavior as the reaction temperature increases.
7 value, where MSA is the number of surface It is worth noting that the influence of MW
8 atoms on the growing nuclei. High RFW values absorption of energy on the kinetic rates would
9 indicate a high level of kinetic control, and at theoretically continue to enhance the reaction
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high R-values the reaction produces smaller behavior until either all the precursor in the
12 nanoparticles with a tighter size dispersity, and initial solution is consumed or until a steady
13 vice-versa for a low RFW-value. A correlation state is reached at which heat being emitted by
14 between k1 and k2 can easily be derived from the NPs back into the solution is equivalent to
15 the rate expression expressed at constant the heat being generated by the NP’s power
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temperature with respect to the growing M* (M absorption.
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18 is Au or Ni)36 To test this hypothesis, the growth
19 The rate of formation of d[M NP]/dt can mechanism for Ni and Au in a MW cavity is
20 thus be expressed as equation 4 evaluated using absorption spectroscopy to
21 follow the increase in the localized surface
22 𝑑𝑑
[M NP] = −𝑘𝑘1 [M salt]+𝑘𝑘2 [M salt][M ∗] [4] plasmon intensity for Ni and Au during MW
23 𝑑𝑑𝑑𝑑

24
irradiation. The Ni absorption was followed in
25 while the depletion of monomer (M0monomer/dt) real time, while the AuNP results were analyzed
26 can be expressed as at selected time-points. The NiNP reaction is
27 carried out at 1500, 1600, and 1700 W (2.45
28 𝑑𝑑 GHz) in a single pass cavity. The Au reactions
− [M 0 ] = 𝑘𝑘1 [M salt]+𝑘𝑘2 [M salt][M ∗] [5]
29 𝑑𝑑𝑑𝑑
were carried out at 150 W in a single mode
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31 In the reaction, it is assumed that the M* cavity.
32 concentration is invariant in time (d[M*]/dt Inspection of the absorption properties
33
~0), and will be equal to the concentration of of Ni(acac)2 and NiNPs in solution reveals that
34 Ni(acac)2 does not absorb at 488 nm, while for
35 critical nuclei formed at the nucleation. [M*]
36 during the reaction can be evaluated, the NiNP a strong extinction feature attributable
37 to the localized surface plasmon is observed at
38 [M salt]0 +[Mcrit]0 488 nm (Figure 2A). The non-overlapping
[M ∗ ]𝑡𝑡 = [M salt]0 −([Msalt] +[M [6]
39 1+ [M 𝑒𝑒 0 crit]0 )𝑘𝑘𝑘𝑘
crit]0 absorption simplifies monitoring of Ni growth,
40
allowing the rate of growth of Ni* (d[Ni]/dt) to
41 Where [M salt] is the concentration of the
42 be directly monitored by plotting the change in
precursor (Ni(acac)2 or HAuCl4), and [Mcrit]0 is the Ni absorption at 488 nm as a function of
43
44 the critical concentration of nuclei to trigger NP time, as absorption intensity will scale linearly
45 growth. Solving eqn 6 produces a sigmoidal with [Ni] following from the Beer–Lambert
46 growth curve at large R-values. law.
47
In Figure 2A, growth of Ni was
48 By coupling the predictions of eqns 4
49 monitored by measuring the absorption
and 6 to the MW cross section for a growing
50 spectrum with a UV–visible spectrometer at
metal NP (Figure 1), a large value of RFW
51 defined time points (0, 120 s, 240 s, and t∞,
52 should arise leading to a narrow dispersity.
From the dielectric arguments, the growth rate where t∞ is the time point at which all precursor
53
has converted into NiNPs). Each line is the
54 will increase as the NP volume increases (V∝r3)
55 and herefore as Pabs, which is proportional to
56 the MW power and MW cross section, while
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Figure 2: Time dependent change in optical absorption of 0.01M Ni(acac)2 irradiated in OAm at 2.45 GHz. A) absorption
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50 spectrum at t = 0 s, 120 s, 240 s, and 300 s for 1700-W irradiation, and B) a plot of A488 vs time at 1500, 1600, and 1700 W,
with a sigmoidal fit and C) a plot of time and temperature at 1500, 1600, and 1700 W. Figures 2A-2C have an n=3, though
51 error bars are left out for clarity of the figure. Time dependent change in optical absorption of 0.01 M HAuCl4 irradiated in
52 OAm at 2.45 GHz, D) absorption spectrum at t = 0 s, 81 s, 101 s, 110 s, 126 s, 139 s, and 141 s, n=3 E) a plot of A530 vs time
53 at 150 W, with a sigmoidal fit, n=1 and F) a plot of time and temperature for AuNP synthesis, n=1.
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55 average of 3 runs in the UV-Vis. In Figure 2B continuous irradiation with absorption data
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growth was monitored at 488 nm (A488) during collected every 2.5 s from 0 to t∞. Each line is
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the average of three runs in the Gerling,
4
5 smoothed with boxcar averaging (window of
6 3). The value of t∞ varies from 300 to 450 s
7 depending on the power applied. As can be seen
8 in Figure 2C, the thermal ramp stabilizes
9 beyond ~120 s. The temperature at each time
10
11
point at a given power only varied 2-4 °C.
12 In an effort to baseline the studies to a
13 well-known autocatalytic reaction, the same
14 approach was applied to monitor AuNP growth
15 in a MW cavity. In Figure 2D, the localized
16
surface plasmon for a gold nanoparticle was
17
18 followed in order to monitor the growth rate of
19 8 nm AuNP carried out at a maximum
20 temperature of 150 °C at 150 W. The reaction
21 was monitored at fixed time points (0 s, 81 s,
22 101 s, 110 s, 126 s, 139 s, 141 s) during the
23
24
growth and the change in the absorption value
25 plotted in Figure 2E. The reaction asymptotes
26 after 120 s at a temperature of 140 °C. Unlike
27 the Ni reaction, a single power was carried out
28 (150 W) and the maximum temperature was set
29
at 150 °C thus in Figure 2F only the linear
30
31 region for heating oleylamine is plotted.
32 To evaluate the correlation of the
33 absorption changes for Ni and AuNPs with
34 d[M*]/dt, it should be remembered the
extinction coefficient (ϵ) will follow a simple
35
36
37 size-dependent scaling function (ϵ ∝ r3) if the
38 NPs remain spherical. The assumption of near
39
40
sphericity is confirmed by the TEM data,
41 wherein Ni spheres of ~25 nm (Figure 3) and Figure 3: TEM of Ni NPs formed at A) 1700 W, B) 1600
Au spheres of 12 nm (Figure 4) are formed from W and C) 1500 W with distribution curves of >300 NPs.
42
D) Shows a plot of the average NP diameter formed at
43 thermal decomposition at 2.45 GHz. The size- each power, with error bars of the FWHM showing that
44 dependent scaling for the absorption behavior the higher the power, the smaller the NP size and the
45 for can thus be estimated by considering the tighter the distribution
46
47 Drude model, which predicts that the dielectric
dispersion will scale with the number of metal By using the size-dependent extinction
48
49 atoms. For Au, the localized surface plasmon value for Ni, the experimental UV–visible data
50 can be effectively followed to monitor the (Figures 2A, SI2, SI3) can be fit to the
51 number of AuNPs in solution37, 38; however, for autocatalytic expression (eqn 4), yielding a k1
52 value of 2.43×10-5 ± 2.66×10-5 s-1 and a k2 value
53
Ni which does not exhibit a well-defined
54 plasmon modes, the Ni absorption manifold of 1.20x10-2 ± 0.006 M·s-1. The reported k1 =
55 will show only intensity and not spectral 1.5 × 10-5 s-1 and k2 = 1.1 x 10-2 M·s-1for Ni
56 changes. grown in the presence of trioctylphosphine at
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exhibit a size distribution much narrower than
4
5 observed for isolated NiNPs grown via hot-
6 injection synthetic methods.1,7,41,42
7 The power dependent enhancement in
8 dispersity for NPs grown in a MW is readily
9 explained within the F-W autocatalytic
10
11
mechanism without invoking MW special
12 effects. In a MW, higher power will not affect
Figure 4: TEM of Au NPs formed at 150 W with
13 distribution curves of >300 NPs. the rates but rather the number of nuclei
14 produced at the initiation of the reaction. In
15 0.06M Ni(acac)2 in OAm.13 The value of k1 is addition, within a MW cavity nucleation will be
16 slightly enhanced while k2 is unchanged, albeit uniform since heating is volumetric and does
17
the reaction conditions are different. The not possess thermal gradients typical of
18
19 experimental UV Vis data for the AuNP (Figure convections reactions.40,43 Thus, the larger RFW
20 2E) fit to eqn 4 yields values for k1 = 1.21×10-5 values will lead to better-controlled growth and
21 ±1.53×10-6 s-1 and k2 =0.102 ×10-2 ± 1.53×10-4 tighter size distributions.
22 M·s-1. While no values were reported for The assumption that the power
23
AuNPs for k1and k2, extraction of the values dependent narrowing of size dispersity is
24
25 form Liu’s results yield rates of k1 ~ 1 x 10-8 s-1 related to MW absorption can be demonstrated
26 and k2 ~ 1 x 10-4 M·s-1.39 The enhancement in by calculating the power-dependent RFW value.
27 k1 is notable but requires further investigation Finky-Watzke assumed the value of RFW can be
28 to conclusively correlate the rate to the MW approximated from the number of nanoparticles
29
effects. in solution at the end of the reaction since the
30
31 As expected for an autocatalytic number of nuclei are invariant during the
32 reaction, k1 (10-5 s-1) << k2 (10-2 M·s-1) for the reaction allowing RFW ~ k1[MNP]/k2.2 A more
33 observed metal NP growth. The agreement in rigorous calculation would require the number
34 the measured and reported kinetic rates for of surface atoms (MSA) to be explicitly known
35 as the NP grows, which is experimentally
36
metal NP growth in a convective reaction and
37 in a MW, supports the conclusion that reactions intractable.
38 follow the same thermodynamic paths and the Using the formalism of F-W, for the
39 observed MW effects arises from the efficiency growth of metal NPs, it is assumed the number
40 of coupling MW energy to the reaction of nuclei at the start of the reaction (M*) are
41 equal to the number of nanoparticles at the
components to reach reaction temperature,
42
43 rather than invoking special MW processes, as completion of the reaction (MNP).2 The nuclei
44 suggested in earlier literature.40 concentration can therefore be calculated from
45 the solution absorption spectrum using the size
46 RFW values. A notable effect in the MW is the dependent Mie scattering absorption cross-
47 power dependence of the size dispersion of the section of a single nanoparticle.37,44,45 The
48 calculation of the number of nuclei follows
49 Ni (Figure 3). The power-dependent Ni sizes at
50 the completion of the reaction are 27.5 ± 9.12 from the methods employed in CdSe QDs and
51 nm at 1500 W, 26.7 ± 5.84 nm at 1600 W, and AuNPs. A more through derivation is in the
52 21.4 ± 2.33 nm at 1700 W. The TEM Supplemental Information. It is worth noting
53 distributions observed for the power dependent the F-W reactions are carried out below
54 saturation (LaMer limit) making the estimation
55
Ni reactions do not show the typical tailing to
56 smaller sizes observed in Ostwald ripening and of nuclei easier. For the NiNP power dependent
57 study, the calculation yields concentrations of
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3.42×10-5 M (1500 W); 4.58×10-5 M (1600 W); dependence of permeability and the presence of
4
5 and 1.47×10-5 M (1700 W). a surface oxide forming a core@shell motif
6 The validity of the assumption from F- should be considered theoretically.
7 W that the number of nuclei in the reaction are In analogy to the effect of size
8 equivalent to the final NP concentration can be dependent permittivity on MW reactions (eqns
9 tested by analyzing the number of nuclei at the 1-3), the size dependent complex permeability
10
11
initiation of the reaction. TEM images of NiNPs (µ*) can be calculated, although in this study
12 2 min into the reaction (1500W) are 3 nm in size the contribution will be small in the
13 (SI5) and as shown in Figure 3 reach 27.6 nm. temperature-dependent growth as the magnetic
14 Using the Mie scattering extinction value for a field strength is 1/377 the electric field
15 3nm Ni, yields a value of 3.2 x 10-5 M for the strength,46 and the reaction temperatures are
16
number of NPs in solution. The value is within well above the blocking temperature for the
17
18 experimental agreement with the number of NiNPs (15 nm super paramagnet limit) in this
19 NPs at the completion of the reaction. Such study.47,48
20 agreement supports the F-W assumption, as this The frequency- and size-dependent
21 would not be expected in a classical LaMer permeability can be described by the Landau–
22 model where small NPs dissolve to form larger Lifshitz–Gilbert expression.49,50
23
24
NPs. 35
From the calculated k1, k2, and number (4𝜋𝜋𝑀𝑀s )2
25 𝜇𝜇 ∗ = 1 + 𝜔𝜔 2 𝜔𝜔
[7]
26 of NPs, the power- dependent RFW values for 2𝐾𝐾−�
2𝜋𝜋𝜋𝜋
� +𝑖𝑖𝑖𝑖(4𝜋𝜋𝑀𝑀s )�
2𝜋𝜋𝜋𝜋
�
27 the Ni reactions are 1.02×1019 (1500 W),
28 1.36×1019 (1600 W), and 2.04×1019 (1700 W).
29 where γ is the gyromagnetic ratio, α is the
Similarly, the gold nanoparticles grown at 150 dampening factor, K is the crystalline
30
31 W have a concentration of 1.36×10-4 M, and anisotropy and Ms is the saturation
32 yield an RFW value of 6.93×1018. The narrowing magnetization. Both K and Ms are size- and
33 of size dispersity observed for the NiNPs with shape-dependent, with the size dependency of
34 increasing power correlates with the change in
35 K written as51
NP concentration, and thus the RFW values. In 6
36 𝐾𝐾 = 𝐾𝐾v + 𝑥𝑥 𝐾𝐾s [8]
37 effect, increased power increases the number of
38 nuclei in the reaction due to the more efficient
39 absorption of energy within a MW cavity where in which Kv is the crystalline anisotropy, Ks is
40 volumetric heating occurs. the surface anisotropy and x is the diameter of
41 the NP. The size dependency of Ms is52
42
43
Role of magnetic moment (permeability) and
2𝑑𝑑 𝑆𝑆vib
44 surface oxides on MW heating. From the above 𝑀𝑀s(nano) ≈ 𝑀𝑀s(bulk) �1 − �1 + �� [9]
𝑥𝑥 3𝑅𝑅
45 results it is clear the growth of Ni and Au in a
46 MW follow the expected autocatalytic growth where Ms(bulk) is the bulk magnetic saturation
47 behavior. The improvement of metal NP
48 moment, d is average distance between atomic
formation in the MW, as reflected by the centers, x is the diameter of the NP, Svib is the
49
50 dispersity with increasing power, reflects the vibrational melting entropy, and R is the ideal
51 more efficient conversion of MW energy gas constant.
52 leading to more uniform nuclei formation with The presence of an oxide forming a
53 a power dependent RFW value and not changes
54 core@shell structure will have impact the
to the reaction mechanism. For completeness of permeability and the permittivity. In the case
55
56
understanding the special effects that might of a core@shell NP the change to the
57 arise for MW grown materials, the size
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9
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19
20
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22
23
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25
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27
28
29
30
31
32
33
34
35
36 Figure 5: A and B) Complex permittivity and permeability of Ni@NiO nanoparticles embedded in wax theoretical compared
37 to measured. n=3. C-F) Theoretical complex permittivity and permeability of Ni vs Ni@NiO nanoparticles showing the NiO
38 layer suppresses the dielectric and the permeability.
39
40 permeability effects is proportional to the value temperature, NP size, and magnetic moment of
41 of Ms(nano). When the shell is antiferromagnetic the metal cores.
42
43 (AFM), as is the case of NiO, the saturation The effect on permittivity will be more
44 moment for the core can be redefined as a significant though, as an oxide has a much
45 core@shell moment (M's(nano)) lower dielectric value, and thus a lower Pabs.
46 The effect of a surface oxide is easily seen by
47 2𝐾𝐾 𝐽𝐽
48 𝑀𝑀′ s(nano) = 4𝜋𝜋𝐻𝐻 + 𝑥𝑥 [10] considering the size-dependent permittivity for
ex 𝑐𝑐 𝐻𝐻ex Ni by derivation of the size-dependent complex
49
50 dielectric (ε*) in eqn. 2. The effective ε* value
where Hex is the exchange bias coercivity, J is
51 for a Ni@NiO core@shell NP can be calculated
52
the exchange bias constant, K is the core
using the Maxwell Garnett effective medium
53 anisotropy, and xc is the diameter of the core.
theory, which determines the effective
54 The effect on the MW reaction for Ni and Au is
polarizability (αk), and the Claussius–Mossoti
55 insignificant reflecting the reaction
56 equation, which relates αk to ε*eff, such that
57
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For a MW reaction, the measurements
4 𝛼𝛼𝑘𝑘
5 𝜀𝜀 ∗eff = 1 + 𝛼𝛼 [11] allow speculation of the impact on a reaction for
1− 𝑘𝑘�3
6 NiNP growth if an oxide layer is present during
7
and the growth step. From TEM images (Figure
8 SI7), the thickness of the oxide is 1.2 nm,
9 consistent with the reported values. The 1.2 nm
(𝜀𝜀∗ −1)(𝜀𝜀∗ +2𝜀𝜀∗ )+𝑔𝑔(2𝜀𝜀∗ +1)(𝜀𝜀∗ −𝜀𝜀∗ )
10 𝛼𝛼𝑘𝑘 = 3 (𝜀𝜀∗s +2)(𝜀𝜀∗c +2𝜀𝜀∗s )+2𝑔𝑔(𝜀𝜀∗s −1)(𝜀𝜀∗c −𝜀𝜀∗s ) [12] oxide layer would lead to a large suppression in
11 s c s s c s

12 ε* and µ* accompanied by an order of

13 where ε*s is the dielectric of the shell, ε*c is the magnitude suppression of Pabs. While it would
14 dielectric of the core and g is the radius of the be exciting to measure the MW dielectric
15 core squared divided by the radius of the NP spectrum of the NiNPs during growth, the
16
squared. experiment is impractical as in situ MW
17
18 From eqns 11-12, the impact of a native absorption experiments are difficult due to the
19 1.2 nm oxide on a 20-nm NiNP vs a pure NiNP difference of 5–6 orders of magnitude between
20 results in an order of magnitude higher Pabs for the power needed to induce a MW-assisted
21 Ni vs. Ni@NiO (Figure SI6). Based on the chemical reaction (kW) and the power needed
22 theoretical predictions, the presence of NiO to measure small dielectric perturbations (mW)
23
24
formed during the reaction would effectively caused by a sample in a field.
25 slow the heating rate. The effect of oxides on
26 AuNPs is assumed to be minor due to surface Conclusions: Microwave chemistry has come
27 passivation, and thus while the equations can be a long way since the mid twentieth century.
28 applied to AuNP, it is not considered further in Given its potential for green chemistry
29
this manuscript to conserve space. applications and rapid prototyping of novel
30
31 The size dependent behavior for materials, a deeper understanding of the exact
32 isolated NiNPs embedded in wax can be used to nature of the evolution of a chemical reaction is
33 test the predictions in eqns 7-12 (Figure 5A–B). desirable. By combining theoretical work with
34 As one can see, the wax and NiO layers flatten static and dynamic measurements of metal NP
35 the difference between sizes, but there is a synthesis, the enhanced dipersity and growth
36
37 slight rise with size in the dielectric and, from behavior of metal NPs in a MW cavity can be
38 15 to 25 nm, in the permeability. Figure 5C–F understood purely from mechanistic arguments
39 also shows data with respect to the theoretical and thermodynamics.
40 permittivity and permeability of NiNPs from 15 The theoretical work shows that metal
41 to 111 nm with and without an oxide layer NPs will grow until all precursor is consumed,
42
43
without the wax matrix, showing the NiO layer and their final size will then be dependent on
44 suppresses the permeability and permittivity. the initial concentration of the solution, and the
45 For the dielectric both the real and the nucleation process. Classical nucleation theory
46 imaginary components rise sharply with size, says that the nucleation step is instantaneous,
47 whereas for the permeability, the real and then growth occurs on the nuclei to form NPs.
48 imaginary components reach a maximum just This agrees with the data from the laser
49
50 above the single domain size (~20 nm). The absorption and UV–vis experiments, which
51 NiNPs, as analyzed in the VNA, show that the show the conversion of the precursor into NPs
52 oxidation layer makes a pronounced difference at rates that correspond with the increase in
53 to the final measured results—once the oxide power, lower powers having slower formation
54 layer is accounted for, theory and experiment times. The laser absorption data also confirm
55
56
match. that NPs made in a MW-assisted reaction
57 follow Finke–Watzky theory, with a sigmoidal
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dependence of the growth of NPs from solution. temperature was ramped to 280 °C at 300-W
4
5 The UV–visible data allow us to extract k1 and power, held at 280 °C for 8 min, and cooled by
6 k2 values from the reactions, giving us more forced air to 55 °C. NPs were isolated from the
7 insight into the kinetics of the reaction. reaction mixture by magnetic separation from
8 the solution, sonication in 10 mL toluene to re-
9
The observation that the enhanced
reaction rate for a metal grown in a MW cavity suspend the Ni, and a second magnetic
10
11 arises from increased MW interactions with the separation. The resultant solid was dispersed in
12 growing NP may actually provide the 10 mL methanol with sonication and
13 thermodynamic basis for the observed magnetically separated. The washing procedure
14 was repeated two more times, then the NPs
improvement in metal NP formation within a
15 were dried at room temperature under
16 MW reported in Au and Fe/Pt,10,53 and supports
the findings of Liu et.al.54 for growth of silver vacuum.
17
18 NPs in a MW cavity. Thus the dielectric
19 arguments leading to MW enhanced reaction Synthesis of AuNP. The AuNP were formed by
20 rates can be tied to the autocatalytic process by creating a 0.01 M solution of chloroauric acid
21 in 36.8 mL of oleylamine. This solution was
22
measuring the rate of reaction as a function of
power. heated to 60 °C and degassed under vacuum.
23
24 For each reaction, 4 mL of the precursor
25 Experimental Section. solution was added to a microwave vial with a
26 Materials. The NiNP standards, and 15-, 25-, stir bar. The vials were then placed into a CEM
27 microwave using a frequency of 2.45 GHz at
and 40-nm fcc-NiNPs were prepared and
28 constant power of 150 W to reach varying
29 characterized previously (Figure SI7),41 and the
30 94- and 111-nm NiNPs were synthesized as temperatures ranging between 120 and 150 °C.
31 described below. Nickel acetylacetonate When the microwave reached temperature, the
32 (Ni(acac)2), 70% oleylamine (OAm), and 90% temperature was held for 1 second, then
33 immediately air cooled to 55 °C.
34
oleic acid (OA) were purchased from Sigma–
35 Aldrich. Paraffin wax and solvents were used
without further purification. Characterization. The 94- and 111-nm NiNPs
36
37 (Figure SI8) and the AuNPs were fully
38 Synthesis of Ni standards (94 and 111 nm). characterized by pXRD and TEM. The 94- and
39
Spherical fcc-NiNPs 94 and 111 nm in diameter 111-nm NiNPs can be indexed to the fcc
40 structure (card PDF#01-08-7128) measured on
41 were synthetically prepared using MW-assisted
decomposition of Ni(acac)2 in a 5:1 OAm-to- a Rigaku DMAX 300 Ultima III Powder X-ray
42
43
diffractometer (using Cu Kα λ = 1.5418 Å
OA mole ratio medium. The synthetic
44 radiation). The AuNPs can be indexed to the fcc
preparation of the spherical, 94- (111-) nm fcc-
45 structure (card PDF#98-000-0056) measured
46
Ni was carried out by mixing 3 mmol (6 mmol)
on a Rigaku DMAX 300 Ultima III Powder X-
of Ni(acac)2, 50 mmol of OAm and 10 mmol of
47 ray diffractometer (using Cu Kα λ = 1.5418 Å
48 OA in a round-bottom flask and degassing radiation). The size, size dispersity and
49 under vacuum at 110 °C. Nine mL of the clear,
50 morphology were measured by transmission
deep blue solution was transferred under electron microscopy (TEM) with a JEM-
51
52 ambient conditions into a G30 (30-mL) Anton ARM200cF electron microscope at 200-kV
53 Paar MW vessel and capped. No stir bar or inert accelerating voltage. Diluted NP samples were
54 atmosphere was used in the reaction vessel. The drop-cast from dispersion in toluene onto 300-
55 vessel was placed into the Anton Paar
56
mesh copper grids and left to dry under reduced
Monowave 300-MW system and the reaction pressure overnight. Histograms generated from
57
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image capture of >300 nanocrystals in ImageJ power were monitored actively during the
4
5 was used to generate the size distribution reaction. The in situ measurement was
6 curves. Solution absorption spectra were validated by UV–visible measurements from
7 obtained using a Varian Cary 50 UV–visible 400 to 1000 nm at defined time intervals (120 s,
8 spectrophotometer in a 1-cm quartz cuvette. 240 s, and final reaction time dependent on
9 power used).
10
11
Complex Dielectric Measurements. Complex
12 dielectric measurements at 2.45 GHz (298 K) The AuNP reaction dynamics were measured at
13 were performed on isolated NiNPs (15, 25, 40, 2.45 GHz at 150 W in a single mode cavity
14 94 and 111 nm) using a vector network analyzer (CEM). The change in plasmon absorption at
15 (Anritsu Lightning E model 37347E) 530 nm was monitored by UV-Vis absorption
16
impedance matched to a coaxial cavity at static time points (0, 81, 101, 110, 126, 139,
17
18 manufactured by Damaskos, Inc. (M07T). The and 141 s) using separate MW reaction vessels.
19 measurements were performed on isolated To measure the absorption changes, a 0.1 mL
20 Ni@NiO NPs (15 nm, 25 nm, 40 nm, 94 nm, aliquot was diluted in toluene. For sizing, TEM
21 and 111 nm) blended in a 5% v/v ratio with images were measured on the AuNPs isolated
22 paraffin wax, and molded into a toroidal shape form he reaction mixture using about 5 mL of
23
24
that fit into the coaxial cavity made by toluene and 1 mL of methanol. This process
25 Damaskos, Inc. The Nicholson–Ross–Weir was repeated four times with sonication
26 algorithm in the Damaskos software was used occurring after each toluene addition.
27 to calculate the complex permittivity and
28 permeability of the composites at 2.45 GHz. ASSOCIATED CONTENT
29
To calculate the permittivity and Supporting information is available free of
30
31 permeability, effective medium theory (EMT) charge at http://pubs.acs.org. Detailed
32 is employed for this calculation. The Maxwell derivations of equations used in the theoretical
33 Garnett theorem is ideal for a metallic inclusion calculations, figures of setup and additional
34 in an insulator,55,56 and is thus the EMT is used supporting images for the characterization of
35 for this calculation as well. the Ni samples are provided (PDF).
36
37
38 Growth Kinetics. The formation rate of NiNPs AUTHOR INFORMATION
39 was monitored under MW irradiation at 2.45
40 GHz at 1500 W, 1600 W, and 1700 W using Corresponding Authors
41 single-wavelength absorption spectroscopy at *E-mail: strouse@chem.fsu.edu.
42
43
488 nm (Ar+ ion laser). The change in
44 absorption intensity at 488 nm was monitored Author Contributions. B.A. measured the
45 on a Si diode (ThorLabs DET10A) connected power-dependent MW reactions, carried out the
46 to an oscilloscope (LeCroy WaveRunner 6051) dielectric measurements and theoretical
47 with data points recorded every 2.5 s for 450 s. derivations and assisted in the writing of the
48 The measurements were performed on a 0.01 M manuscript. C.D. carried out the AuNP
49
50 solution of Ni(acac)2 in OAm. MW reactions, while P.V. and B.L. prepared the Ni
51 measurements were performed in a resonant standards. P.V. and C.D. characterized the
52 cavity (TE013) coupled to a Gerling MW source NPs. J.O. And J.T. assisted in the experimental
53 with 10 mL of reaction solution contained in a design and interpretation. G.F.S. designed the
54 project, assisted in interpretation and
square (1.4 cm x 1.4 cm) quartz reactor vessel.
55
56 Figure SI1 shows the setup. Temperature and conclusions and in the writing of the
57 manuscript. All authors revised the manuscript.
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3 Nucleation and Crystal Growth is Accelerated by
4
Notes. The authors declare no competing Microwave Irradiation? Chem. Eur. J. 2007, 13,
5
6 financial interests. 4410-4417.
7 4. Gawande, M. B.; Shelke, S. N.; Zboril, R.;
8 Varma, R. S., Microwave-Assisted Chemistry:
ACKNOWLEDGEMENTS
9 Synthetic Applications for Rapid Assembly of
10 Nanomaterials and Organics. Acc. Chem. Res. 2014,
11
Funding. We (G.F.S., B.A., P.V.) wish to thank 47, 1338-1348.
12 the National Science Foundation CHE- 5. Washington, A. L.; Strouse, G. F.,
13 1608364: SusChEM: Understanding Microwave Synthesis of CdSe and CdTe
14 Microwave Interactions to Control Magnetic Nanocrystals in Nonabsorbing Alkanes. JACS.
15 Nanocrystal Growth from a Single Source 2008, 130, 8916-8922.
16 6. Zedan, A. F.; Sappal, S.; Moussa, S.; El-
17
Precursor. This project was supported
(B.A., J.O.) in part by an appointment to the Shall, M. S., Ligand-Controlled Microwave
18
19 Research Participation Program at the Air Force Synthesis of Cubic and Hexagonal CdSe
20 Civil Engineer Center administered by the Oak Nanocrystals Supported on Graphene.
21 Photoluminescence Quenching by Graphene. J.
Ridge Institute for Science and Education
22 Phys. Chem. C 2010, 114, 19920-19927.
B.B.L. and J.B.T. acknowledge NSF grant 7. Gerbec, J. A.; Magana, D.; Washington, A.;
23
24 CBET-1605699. Strouse, G. F., Microwave-Enhanced Reaction
25 The TEM imaging at FSU is supported Rates for Nanoparticle Synthesis. JACS 2005, 127,
26 by the Florida State University Research 15791-15800.
27 Foundation, and through the National High 8. Siramdas, R.; McLaurin, E. J., InP
28 Magnetic Field Laboratory National Science Nanocrystals with Color-Tunable Luminescence by
29 Microwave-Assisted Ionic-Liquid Etching. Chem.
30
Foundation Cooperative Agreement DMR-
1157490, the State of Florida, and Florida State Mater. 2017, 29, 2101-2109.
31
32 University. TEM imaging at NC State was 9. Muthuswamy, E.; Iskandar, A. S.; Amador,
33 performed at the Analytical Instrumentation M. M.; Kauzlarich, S. M., Facile Synthesis of
34 Germanium Nanoparticles with Size Control:
Facility (AIF), which is supported by the State
35 Microwave Versus Conventional Heating. Chem.
of North Carolina and the National Science Mater. 2012, 25, 1416-1422.
36
37 Foundation (award number ECCS-1542015). 10. Carnevale, D. J.; Shatruk, M.; Strouse, G.
38 The AIF is a member of the North Carolina F., Ligand Passivated Core–Shell FePt@ Co
39 Research Triangle Nanotechnology Network Nanomagnets Exhibiting Enhanced Energy
40 (RTNN), a site in the National Nanotechnology Product. Chem. Mater. 2016, 28, 5480-5487.
41 Coordinated Infrastructure (NNCI). 11. Bilecka, I.; Niederberger, M., Microwave
42 Chemistry for Inorganic Nanomaterials Synthesis.
43
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