www.acsanm.

org Article

Uniform Gold Nanoclusters Supported on Mesoporous Polymer

Beads Decorated with Polyaminophosphine Patches for the
Catalytic Reduction of 4‑Nitrophenol
Xiaoqiu Yao, Ming Jin, Jiang Du, and Decheng Wan*

Cite This: ACS Appl. Nano Mater. 2023, 6, 6653−6661 Read Online
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ACCESS Metrics & More Article Recommendations

Downloaded via CONICET on October 20, 2023 at 13:30:46 (UTC).

ABSTRACT: In the jigsaw puzzle of quality gold nanoclusters (AuNCs), those protected by weak ligands or coligands are still
rarely available. Here, we provide an example in the case of supported AuNCs. Branched polyethylenimine (PEI, diameter of 1.86
nm) is introduced as discrete molecular patches onto the support of mesoporous polymer beads. Each patch is derived into
polyaminophosphine with 2-(diphenylphosphino) benzaldehyde (dppb). The molecular patch is of nanoscale and uniform size. The
polymer beads after PEI loading bear unimodal pores (3.9 nm), and the specific surface area is of 390 m2 g−1. AuNCs are obtained
by mildly heating the mixture of the functionalized beads and aqueous chloroauric acids. Uniform AuNCs with a diameter of 1.2 ±
0.2 nm (∼53 Au atoms) are obtained when each PEI patch bears 17 dppb ligands, smaller than that of 3.5 nm in the absence of any
dppb, suggesting that dppb enhances the nucleation of AuNCs. The heteroleptic AuNCs show ultrahigh catalytic performance (TOF
= 391 h−1) for the reduction of 4-nitrophenol, where the dppb ligands hardly suppress the catalytic activity. The catalyst is well
recoverable and durable for the reduction of 4-nitrophenol.
KEYWORDS: gold nanocluster, molecular patch, polyethylenimine, ligand, support, catalyst, synergy

1. INTRODUCTION multiligands such as polymers and dendrimers generally show

Gold nanoclusters (AuNCs), as the much smaller counterparts high catalytic performance due to the good accessibility to
of nanoparticles (AuNPs), have evoked much interest for their substrates.16−21 Meanwhile, some polymers can direct the self-
quantum effect, high surface/volume ratio, and catalytic assembly of metal nanoparticles.22−24 Currently, AuNCs
activity for a variety of chemical reactions.1−3 Size control of protected by weak ligands alone are still rarely available.
AuNCs is important because the catalytic performance is Supporting suppresses the aggregation of noble metal
dependent on the size. In fact, some catalytic property is nanoparticles, favors their stability, and facilitates their
exclusive for specifically sized AuNCs.4−12 Most quality recovery. Supported metal catalysts are among the most
AuNCs have to be prepared through abundant strong ligands, popular ones in the industrial field.25 The effects of particle
where thiolates are the most available ones. AuNCs protected size, nature of the supports, and metal−ligand interfacial
by strong ligands tend to suffer from lower catalytic activity microenvironment on the performance of metal nanoparticles
and a narrower catalytic spectrum.3 Partial or complete are themes of recent research activities. Inorganic oxides are
removal of the strong ligands by the thermal treatment could
significantly enhance the catalytic activity of AuNCs.13,14 It is Received: January 24, 2023
also found that replacing one type of strong ligand with Accepted: March 13, 2023
another one significantly improves the catalytic property of the Published: March 20, 2023
catalyst, suggesting that the metal−ligand interfacial micro-
environment is critical to the catalytic behaviors.15 AuNPs/
AuNCs and other noble metal nanoparticles stabilized by weak

© 2023 American Chemical Society https://doi.org/10.1021/acsanm.3c00351

6653 ACS Appl. Nano Mater. 2023, 6, 6653−6661
ACS Applied Nano Materials www.acsanm.org Article

popular supports, and noble metal nanoparticles are usually 2. EXPERIMENTAL SECTION
supported through postsynthesis treatment. For example, 2.1. Materials. Chloroauric acid (HAuCl4), 4-nitrophenol (4-
AuNCs were mediated with abundant phosphine ligands, NP), methylene blue, poly(vinyl alcohol)1788 (PVA), styrene (St),
allowed to be adsorbed on mesoporous ceria, and subjected to and divinylbenzene (DVB, 80%) were purchased from Aladdin
calcination at 300 °C to strip the ligands to yield ceria- (China). 2-(Diphenylphosphino)benzaldehyde (dppb), azodiisobu-
supported AuNCs.26 Doping of AuNPs/AuNCs during tyronitrile (AIBN, 96%), and sodium borohydride (NaBH4) were
calcination could occur but is usually desired.27 Supported purchased from Sinopharm Chemical Reagent Co., Ltd. AIBN was
recrystallized and stored at 4 °C prior to use. Branched
catalysts still suffer from ripening and detaching from the polyethylenimine (PEI, Mw = 2000, PDI = 1.1, 50% in H2O) and
support upon calcination and application. Resorting to metal 4-vinylbenzyl chloride (VBC, 90%) were obtained from Sigma-
organic frameworks (MOFs),28,29 covalent organic frameworks Aldrich. PEI was dehydrated by distillation followed by azeotropic
(COFs),30 colloidal assembly,,31,32 organic cages,33,34 and distillation with cyclohexane.
protein cages35 is reported for stable metal nanoclusters. These 2.2. Measurement. Transmission electronic micrograph (TEM)
strategies favor the stability of metal nanoclusters by spatial and high-resolution transmission electron micrograph (HRTEM)
were recorded on a JEM-2011F transmission electronic microscopy
isolation of the particles. operating at an acceleration voltage of 200 kV. Samples were prepared
Organic and polymeric supports are causing attention for by adding a drop of the subject dispersed in ethanol to a carbon-
their self-organizing ability, ready chemical processability, and coated copper grid before the solvent was evaporated. The average
durability in rigorous chemical environments. Zero-valent size of AuNCs was determined with the software of Nano Measurer
noble metal clusters could be incarcerated by polymers, by counting up to 300 particles. The lattice of crystalline Au was
which simultaneously act as supports.36 Microencapsulation analyzed using a digital micrograph based on fast Fourier trans-
and cross-linking of polymers37 or encapsulation by magnetic formation (FFT). The particle size of mesoporous polymer beads was
measured in water by a laser particle size analyzer of a Beckman
polymer nanocomposite can also facilitate recovery.38 It was Coulter LS330. Brunauer−Emmett−Teller (BET) nitrogen adsorp-
reported in a case that certain polymeric support enabled 100% tion isotherms were recorded on an Autosorb-Nova 2200e
conversion of the substrate and influenced the reaction (Qutantachrome Instruments), and the pore size distribution was
mechanism,39 meaning the electronic property of the polymer analyzed by the Barrett−Joyner−Halenda (BJH) method. Ultraviolet/
support played an extra role. Polymer supports could be visible (UV/vis) spectra were obtained using a Mapada UV-6300
conferred with mesoporosity while possessing a bulky spectrophotometer (Shanghai Mapada Instruments Co., Ltd.). Field
emission scanning electron microscopy (SEM) was recorded on a
morphology.40 Polymerized high internal phase emulsion Magellan 400 (FEI Co., Ltd.). The CHN element content was
provides a facile way to three-dimensional (3D) porous measured with a Vario MACRO Cube. X-ray photoelectron
polymeric materials41 and has been successfully used to spectroscopy (XPS) data was obtained by using a Thermo Scientific
support metal catalysts.42,43 A polymer surfactant, unlike a Kα spectrometer and analyzed by commercially available software
small surfactant, robustly adheres to the support and can act as (XPSpeak41). High-performance liquid chromatography spectra were
a permanent functional surface. Ye et al.23 used a reverse obtained on a Primaide (Shanghai Hitachi Instruments Co., Ltd.)
micelle-like dendritic surfactant, with a AuNP incarcerated in with a mobile phase of methanol/acetonitrile = 9/1 (volume ratio).
Thin-layer chromatography (TLC) was carried out with methylene
the core, as a stabilizer to mediate the synthesis of an emulsion- dichloride as the mobile phase. Inductively coupled plasma optical
based 3D porous monolith, resulting in a durable and well- emission spectroscopy (ICP-OES) was conducted using an Agilent
recyclable catalyst. Platinum nanocatalyst was similarly 5110. High-angle annular dark-field scanning transmission electron
prepared.22 micrographs (HAADF STEM) were recorded on a Thermo Scientific
In situ supporting represents a straightforward method to a Themis Z.
supported nanocatalyst, but the heterogeneous nature of the 2.3. Synthesis. 2.3.1. Synthesis of Porous Polymer Beads as
Support. The synthesis by suspension polymerization is carried out in
process renders the control of the size and size distribution of the literature.45 Typically, to a water phase composed of poly(vinyl
metal nanoparticles a general challenge. Very recently, we alcohol) solution (0.5%, 400 mL), sodium chloride (8 g), and
highlighted the role of a molecular patch on in situ supporting methylene blue solution (0.1%, 8 mL), an oil solution composed of
uniform AuNCs.44 Unlike the unstable and uneven patches DVB (12 mL), VBC (36 mL), AIBN (0.2 g), and toluene (48 mL)
prepared through self-assembly of amphiphilic polymers, a was dropped in under rigorous stirring (400 rpm). The suspension
molecular patch is featured with good stability, uniformity, and system was heated at 70 °C for 3 h followed by heating at 80 °C for 3
h before the beads were separated and extracted in sequence with
a nanoscale size. PEI belongs to a family of globular acetone, dilute hydrochloric acid (pH 5−6), and ethanol and finally
macromolecules with a series of sizes available and is one- dried in a vacuum oven to a constant weight (yield 21.1 g, 88%).
step available and bears dense active amino groups. These 2.3.2. Functionalization of the Support with PEI (s-PEI). The
features render PEI a good candidate for the molecular patch. synthesis is based on a literature procedure.44 Typically, a solution of
Heteroleptic metal nanoparticles are less available and less PEI (dehydrated, 1.77 g, 40.7 mmol NH) in ethanol (30 mL) is
studied, especially those with a designable ratio of the two mixed with the polymer beads (15 g, ∼72 mmol benzyl chloride) and
types of coligands. Can the coligands undergo certain synergy heated at 80 °C for 6 h under stirring and under a N2 atmosphere.
The beads were separated by filtration, fully washed in sequence with
to mediate quality AuNC in terms of size and property (?). aqueous NaOH (5 wt %), deionized water, and absolute ethanol, and
Here, we show that with functional groups core through shell, dried in vacuum to yield beads (15.30 g, 91%). Elemental analysis: C,
a PEI molecular patch can be functionalized with the desired 79.22%, N, 3.10%, and H, 7.08%.
ratio of phosphine ligands. Interestingly, the coligand favors 2.3.3. Modification of PEI Patches with dppb (s-PEI-dppb-x, x
the formation of uniform AuNCs while hardly suppressing Denoting the Fraction (%) of Amino Groups Being Functionalized
by dppb). Typically, for the synthesis of s-PEI-dppb-36, a solution of
their catalytic activity. The catalyst is very stable in a reductive dppb (0.238 g, 0.82 mmol) in ethanol (30 mL) was mixed with s-PEI
environment and thus is mainly suitable for a reduction beads (1 g, 2.21 mmol NH) suspended in ethanol (10 mL). The
reaction such as the reduction of the industrially important 4- mixture was stirred at room temperature for 4 h, followed by refluxing
nitrophenol. for 3 h. The consumption of dppb was monitored by thin-layer

6654 https://doi.org/10.1021/acsanm.3c00351
ACS Appl. Nano Mater. 2023, 6, 6653−6661
ACS Applied Nano Materials www.acsanm.org Article

chromatography (TLC) until no signal of dppb was detectable in the preparation of porous beads bearing appropriate pores and
liquid phase. The beads were separated by filtration and washed with functional groups. Suspension copolymerization of DVB-VBC
ethanol before drying (0.95 g, 77%). Other samples of s-PEI-dppb-9 in water yields polymer beads (Figure 1A) with a diameter of
and s-PEI-dppb-18 were similarly prepared.
2.3.4. Mediation of AuNCs with s-PEI-dppb (Au-s-PEI-dppb). The
140−210 μm, and the beads are porous (Figure 1B). PEI can
feeding was based on N/Au = 32:1 (molar ratio). Typically, a solution be covalently immobilized on the beads by reacting with the
of HAuCl4 (1.5 mL, 20 mmol L−1, Au: 0.03 mmol) was mixed with s- VBC moieties. In view that PEI is a globular molecule with a
PEI-dppb (0.5 g, 0.96 mmol N) suspended in water (8.5 mL) under diameter of 1.86 nm, the pores of the beads should be larger
stirring. After decoloration of the water (∼1 min), the mixture was than this size so that blocking of the pores by PEI can be
heated at 80 °C for 0.5 h. The beads were separated by filtration, mostly avoided. On the other hand, the pores should be as
followed by washing with ethanol and drying to yield 0.48 g (96%) of small as enough so that a high specific surface area is available
solid. The Au content on the support was calculated to be 6.0 × 10−5 for the beads. It is interesting to experimentally find that, in
mol/g based on the yield.
2.3.5. Catalytic Reduction of 4-NP with Au-s-PEI-dppb. A case the feeding ratio for suspension polymerization is of
solution containing NaBH4 (60 mmol L−1) and 4-NP (0.06 mmol DVB/VBC/toluene = 1/3/4 (volume ratio), the ideal pore size
L−1) (100 mL) was bubbled with N2 for 30 min; Au-s-PEI-dppb is available. As shown in Figure 2A and Table 1, BET analysis
(0.020 g) charged in a Teflon bag (with hydrophilic and 45 μm pores shows that the specific surface area of the beads is 470 m2 g−1,
on the bag) was dropped in. The reduction process was monitored and BJH analysis shows the unimodal pores centering on 3.9
with a UV/vis spectrometer by measuring aliquots at a certain time nm (Figure 2B), where almost all pores are larger than the
interval. The aliquots were poured back into the reaction vessel once diameter of PEI. The reason for the production of pores is
the spectral scanning was finished.
For recycling, the catalytic material was fished out, sucked with
related to two factors, one is toluene in the system that acts as
paper, and used in the next reaction cycle. a porogen and the other is microphase separation during
polymerization,45 where the dosage of DVB is critical to the
3. RESULTS AND DISCUSSION gelation. After PEI loading, the specific surface area slightly
3.1. Synthesis and Characterization of Polymer Beads decreases to 390 m2 g−1 (Table 1) and the pores remain at 3.9
Functionalized by Molecular Patches of Polyamino- nm on average, supporting that most pores remain open rather
phosphine. The strategy for the preparation of the targeted than being blocked by PEI. PEI loaded on the support equals
material is outlined in Scheme 1. The first step involves the 95 mg g−1, as derived from elemental analysis. This equals 2.21
mmol of NH (or 0.048 mmol of PEI molecules) per g of s-PEI.
Scheme 1. Outline of the Procedure for Mesoporous Bead- Taking the specific surface area into account, one can derive
Supported AuNCs that the density of PEI on the support is 0.074 molecule nm−2.
Assuming PEI as a globe, the projected area of a PEI molecule
on a two-dimensional plane is 2.72 nm2. With the above data,
one can derive that 20% of the support surface is covered by
PEI. The experiment shows that s-PEI is well water-wettable.
Phosphine molecules are introduced into PEI patches by
treating s-PEI with dppb in ethanol. The mixture is subjected
to stirring at room temperature for several hours followed by
refluxing for several hours until no residual dppb in the liquid
phase was detectable with TLC. Dppb can attach to PEI via
either primary amines or secondary amines. Since excess NH2
and NH groups are present in the system and no free dppb
molecules are detectable in the liquid phase after the above
treatment, it is regarded that dppb is quantitatively introduced
into the PEI patch.
3.2. AuNC Synthesis and Characterization. The PEI-
dppb-functionalized beads (s-PEI-dppb) can readily mediate in
situ supporting of AuNCs. To a solution of chloroauric acid
under mild stirring, s-PEI-dppb is dropped in. Primary tests

Figure 1. SEM of polymer beads (A) and the magnified porous structure of one bead (B). The inset in panel (A) shows the volume fraction
contributed by size-specified particles.

6655 https://doi.org/10.1021/acsanm.3c00351
ACS Appl. Nano Mater. 2023, 6, 6653−6661
ACS Applied Nano Materials www.acsanm.org Article

Figure 2. Nitrogen sorption/desorption isotherms for the as-prepared mesoporous beads (A) and pore size distribution of the beads (B).

Table 1. Evolution of the Specific Surface Areas and the Table 2. Dependence of AuNP/AuNC Sizes on Phosphine
Pore Diameter of the Beads along with Derivation Levels
beads specific surface area (m2 g−1) pore diameter (nm) Au-s-PEI-dppb-x AuNC/AuNP diameter (nm)
s 470 3.9 Au-s-PEI-dppb-0 3.5 ± 0.5
s-PEI 390 3.9 Au-s-PEI-dppb-9 2.8 ± 0.3
Au-s-PEI-dppba 291 4.3 Au-s-PEI-dppb-18 2.1 ± 0.3
a Au-s-PEI-dppb-36 1.2 ± 0.2
dppb- and Au-loaded beads (see the next part).

show that the recipe of N/Au = 32 (molar ratio) is favorable The structure of the ultrafine AuNCs is discernible in
for sufficient adsorption of the gold ions by s-PEI and also HRTEM. As shown in Figure 4, the interplanar spacing of
favorable for the production of uniform AuNPs/AuNCs. 0.236 nm is visible for the lattice structure, corresponding to
Therefore, in the following work, the recipe is adopted for any the 111 crystal facet of AuNCs. Electron diffraction pattern
AuNC preparation. The characteristic red color of chloroauric also well agrees with the 111 facet of a single crystal. HAADF
acid soon recedes within seconds upon mixing with s-PEI- STEM shows a clear fine structure of AuNCs. These facts
dppb, as evidenced by the UV/vis spectral monitoring. The suggest that a AuNC is formed through atoms one by one
mixture was subjected to stirring for several hours at room rather than by the aggregation of small AuNCs. XPS (Figure 5)
temperature followed by refluxing for several hours before the detection of Au-s-PEI-dppb shows a signal of phosphine (131.4
beads were separated, during which the water was kept eV, P 2p signal); the signal due to phosphorous oxide (134.1
colorless. Regarding the fate of the gold species, the level of the eV)46 was hardly detectable (phosphine groups probably
residual gold species in water was detected with ICP-OES to involve in the reduction of gold ions as well as amines, but
be around 5.3 ppm (0.9% of Au charged in the system), their molar dosage in the system is about 11.7-fold that of gold
suggesting that over 99% of gold species are on the support. ions). The signals at 83.9 and 87.7 eV correspond to zero-
TEM detection shows ultrafine and homogeneously distributed valent Au (4f7/2 and 4f5/2).44 Energy dispersive X-ray (EDX)
AuNCs on the support, as shown in Figure 3, and the size mapping (Figure 6 and Table 3) shows very weak signals of
distributions are collected in Table 2. elements N, P, and Au because their content on the support is

Figure 3. TEM of AuNPs/AuNCs mediated with s-PEI-dppb-x (x represents the fraction (%) of amino groups being functionalized with dppb
groups), x = 0 (a), x = 9 (b), x = 18 (c), and x = 36 (d). The insets show the size and size distribution.

6656 https://doi.org/10.1021/acsanm.3c00351
ACS Appl. Nano Mater. 2023, 6, 6653−6661
ACS Applied Nano Materials www.acsanm.org Article

Figure 4. HRTEM, FFT analysis, and electron diffraction pattern of Au-s-PEI-dppb-36 (a) and Au-s-dppb-0 (b), and HAADF STEM of Au-s-PEI-
dppb-36.

Figure 5. XPS spectra of s-PEI, s-PEI-dppb, and Au-s-PEI-dppb (A), enlarged signal of element P before (blue) and after (black) gold loading (B),
and signal of element Au (C) in which best-fitting lines are also shown.

Figure 6. SEM of ground Au-s-PEI-dppb-36 (a) and signal of elements carbon (b), oxygen (c), nitrogen (d), phosphorus (e), and gold (f).

2.21, 0.8, and 0.07 mmol/g or 3.1, 2.5, and 1.4 wt %, reduces the crystal sizes. In the case of Au-s-PEI-dppb-36,
respectively, which is low. AuNCs as small as 1.2 ± 0.2 nm (∼53 Au atoms) are obtained.
3.3. AuNC Formation Mechanism. One can find from Meanwhile, the patch-mediated AuNPs/AuNCs are uniform or
Figure 3 and Table 2 that the AuNC sizes are sensitive to the almost uniform. The discrete patches contribute to uniform
dppb level in the patch. Increasing the dppb level significantly AuNCs. As shown in Figure 3, neat PEI patch alone in the
6657 https://doi.org/10.1021/acsanm.3c00351
ACS Appl. Nano Mater. 2023, 6, 6653−6661
ACS Applied Nano Materials www.acsanm.org Article

Table 3. Abundance of Several Elements in Au-s-PEI-dppb- nm. When much excess sodium borohydride is charged in the
36 as Detected by EDX system, the following equation (eq) stands
element CK NK OK PK AuL ln(Ct /C0) = ln(A t /A 0) = kt (1)
wt % 88 1 7 0 1 where C0 and Ct represent the concentration of 4-NP at
atom % 92 1 5 1 0 reaction times 0 and t, respectively, and A0 and At represent the
UV/vis absorbance of 4-NP at 400 nm at reaction times 0 and
t, respectively; k represents the apparent rate constant (s−1).
The turnover frequency (TOF) can be derived from eq 2, in
beads mediated AuNPs seized at 3.5 ± 0.5 nm. In contrast, in
which the conversion (%) is derived from eq 3
case the PEI was continuous on the surface, AuNPs of size 8.5
± 1.8 nm were obtained.23 The contribution of patches can be TOF = [4 NP]0 × conversion/([Au] × t ) (2)
understood from two aspects. On one hand, each patch
captures chloroauric acids by electrostatic interaction, render- conversion = (1 A t /A 0) × 100 (3)
ing gold ions relatively homogeneously distributed on the where [4-NP]0 is the initial concentration of 4-NP and [Au] is
support, favoring the focusing effect (equal probability to form the equivalent concentration of Au species.
nuclei and grow). On the other hand, patches suppress the As shown in Figure 7, when Au charged in the system is
fusion and ripening of AuNPs/AuNCs. Regarding the equivalent to 2.36 ppm, the reduction proceeds quickly, as
decreasing AuNC sizes along with the dppb level, it is evidenced by the quick recession of absorbance at 400 nm.
known that Au−P interaction is stronger than Au−N The quasi-linear relationship between ln(Ct/C0) and t implies
interaction, thus enhancing nucleation, leading to smaller that the reaction kinetics complies with the Langmuir−
AuNCs. The strong Au−P interaction also suppresses Ostwald Hinshelwood model,47 and k = 0.013 s−1 and TOF = 391
ripening, favoring the formation of uniform AuNCs. There is h−1 are derived. To evaluate the catalytic activity, k is
still one concern regarding why 1.2 nm sized AuNC is normalized and compared with other systems where the
obtained. From the feed ratio, one can derive that the quota for reduction of 4-NP by AuNPs/AuNCs is involved, as shown in
each molecular patch is 1.45 gold atoms on average, while Table 4. One can find from Table 4 that our catalyst shows
finally AuNCs consisting of 53 atoms form, which means
finally only 2.7% of patches are pregnant with AuNCs. Table 4. Comparison of the Catalytic Performance of
Probably, phosphine is not strong enough to prevent the AuNPs/AuNCs from Normalized Apparent Rate Constants
abortion of the nuclei. The advantage is that dppb hardly of knor (knor = k/[Au])a
suppresses the catalytic activity of AuNCs, as shown in the
following part. catalyst knor/(s−1 mM−1)
3.4. Catalytic Performance of Au-s-PEI-dppb. To AuNCs 0.0017
evaluate the catalytic performance of the supported catalyst, YC7 peptide@AuNPs 0.12
Au-s-PEI-dppb-36 is used to catalyze the reduction of 4-NP. Au-DA-polyHIPE 0.14
Reduction of 4-NP is a well-known model reaction, character- Au-PDA/RGO 0.20
istic of several features including ignorable reduction without Pir-HNTs-NH2-Au 0.50
catalyst, facile monitoring of the reaction, and rare side Au MCN 0.56
reactions. The catalytic activity of AuNPs/AuNCs is sensitive P-S1-Au (AuNC) 5.17
to the ligand nature, at least in the case of 4-NP. For example, Au@TR-HCP-TPMT (AuNC) 5.83
the presence of trace thioethers could suppress the catalytic Au-s-PEI-dppbb 10.8
activity.44 The reduction of 4-NP is employed to evaluate a
Data from ref 44 and ref cited therein. bThis work.
whether phosphine ligands suppress the catalytic performance
of Au-s-PEI-dppb.
The reduction of 4-NP by sodium borohydride can be outstanding catalytic performance. The ultrahigh catalytic
monitored from UV/vis absorbance at a wavelength of 400 activity probably arises from two factors. One is the AuNCs are

Figure 7. UV/vis spectra of 4-NP upon Au-s-PEI-dppb-36-catalyzed reduction (A) and the apparent rate constant thus derived (B). Conditions:
[4-NP]0 = 0.06 mmol/L; [NaBH4]0 = 60 mmol/L; Au at 0.2 equiv of 4-NP, equaling to a dosage of 2.36 ppm in the system.

6658 https://doi.org/10.1021/acsanm.3c00351
ACS Appl. Nano Mater. 2023, 6, 6653−6661
ACS Applied Nano Materials www.acsanm.org Article

protected by weak and medium ligands, which rarely suppress Combination of eqs 4−6 leads to
the catalytic activity; the other is the catalyst has a relatively TOF2 /TOF1 = kD2 /D1 (7)
high specific surface area (291 m2 g−1, Table 1). TOF values
are usually used to evaluate a catalyst. As shown in Table 5, for Thus, the linear relationship in Figure 8 implies that dppb, as a
most Au particles supported on 102 micron sized support, TOF stronger ligand than amine, hardly suppresses the catalytic
values fall in 0.1−10 h−1, while our catalyst has a TOF value of activity of AuNCs, at least for the substrate of 4-NP. This is
391 h−1, about 2 orders higher. very different from the coligand of thioether, which actually
suppresses the catalytic activity.44
Table 5. Typical TOF Values of Noble Metal Nanoparticles Recycling 8 times leads to no appreciable degeneration of
on Support Sizea the catalytic performance (Figure 9), and the stability should
support size/μm TOF/h−1
170 391 (this work)
≥100 10−1−101
∼1 102
<0.1 103−105
a
For the reduction of 4-nitrophenol, data from ref 44.

Other catalysts of Au-s-PEI-dppb-x are similarly evaluated,

and the results are collected in Figure 8. One can find from

Figure 9. Recycling of the catalyst Au-s-PEI-dppb-36. Conditions: see

Figure 7.

be attributed to several factors. One is that in a reductive

environment, Au exclusively exists as Au(0), and solubility of
Au(0) in water is limited (around 1 ppb, as detected with ICP-
OES). Another probable factor is that the patches somewhat
suppress the ripening of AuNCs.
Figure 8. Dependence of TOF values on diameters of Au-s-PEI-dppb.
4. CONCLUSIONS
Globular PEI molecules are introduced onto a porous support
Figure 8 that the smaller the size of AuNCs, the higher the as uniform and nanoscale molecular patches. The suspension-
TOF values. Interestingly, TOF values linearly depend on the mediated mesoporous support retains a high specific surface
diameter sizes of AuNCs. To understand this phenomenon, area after PEI loading because PEI is smaller than the pores.
one needs to learn the prerequisites for the appearance of the The patch is functionalized with a designed amount of dppb.
linear relationship. Assuming that each catalytic site is of equal The PEI patch and dppb synergically mediate the supported
activity, and the number of catalytic sites is proportional to the AuNCs, where dppb enhances the nucleation of AuNCs and
surface area of AuNCs, then for samples 1 and 2 of AuNC, the patch favors the formation of uniform AuNCs. It is found
TOF will be linearly dependent on the surface area of AuNCs, that the stronger ligand of dppb hardly suppresses the catalytic
as the following equation shows performance of AuNCs. The ultrahigh activity, good stability,
TOF2 /TOF1 = kS2/S1 (4) and recyclability of the AuNCs appear potential for industrial
application.
where k is a constant, and the subscripts 1 and 2 stand for We wish to emphasize that in the jigsaw puzzle of a noble
samples 1 and 2, respectively. metal nanocluster, those protected by weak and medium
When a certain amount of bulk gold is split into smaller ligands, or those protected by coligands, are still rarely
globes (n1 particles with average diameter D1), or still smaller available, where our method appears promising to prepare
globes (n2 particles with average diameter D2), its volume such materials.
remains intact
n1(1/6) D13 = n2(1/6) D2 3
where D1 and D2 represent the diameters of AuNC of samples
(5) ■ AUTHOR INFORMATION
Corresponding Author
1 and 2, respectively, and n1 and n2 represent the number of Decheng Wan − Department of Polymer Materials, School of
particles, respectively. Materials Science and Engineering, Tongji University,
The ratio of surface areas (S1 and S2) of samples 1 and 2 is Shanghai 201804, China; orcid.org/0000-0002-5749-
6153; Phone: 86 21 69580143; Email: wandecheng@
S1/S2 = D12 / D2 2 (6) tongji.edu.cn
6659 https://doi.org/10.1021/acsanm.3c00351
ACS Appl. Nano Mater. 2023, 6, 6653−6661
ACS Applied Nano Materials www.acsanm.org Article

Authors (11) Berr, M. J.; Schweinberger, F. F.; Döblinger, M.; Sanwald, K. E.;
Xiaoqiu Yao − Department of Polymer Materials, School of Wolff, C.; Breimeier, J.; Crampton, A. S.; Ridge, C. J.; Tschurl, M.;
Materials Science and Engineering, Tongji University, Heiz, U.; Jäckel, F.; Feldmann, J. Size-Selected Subnanometer Cluster
Shanghai 201804, China Catalysts on Semiconductor Nanocrystal Films for Atomic Scale
Insight into Photocatalysis. Nano Lett. 2012, 12, 5903−5906.
Ming Jin − Department of Polymer Materials, School of (12) Zhang, J.; Li, Z.; Huang, J.; Liu, C.; Hong, F.; Zheng, K.; Li, G.
Materials Science and Engineering, Tongji University, Size Dependence of Gold Clusters with Precise Numbers of Atoms in
Shanghai 201804, China; orcid.org/0000-0002-8014- Aerobic Oxidation of D-Glucose. Nanoscale 2017, 9, 16879−16886.
2812 (13) Sudheeshkumar, V.; Shivhare, A.; Scott, R. W. J. Synthesis of
Jiang Du − Department of Polymer Materials, School of Sinter-Resistant Au@Silica Catalysts Derived from Au-25 Clusters.
Materials Science and Engineering, Tongji University, Catal. Sci. Technol. 2017, 7, 272−280.
Shanghai 201804, China (14) Dasog, M.; Hou, W.; Scott, R. W. J. Controlled Growth and
Catalytic Activity of Gold Monolayer Protected Clusters in Presence
Complete contact information is available at: of Borohydride Salts. Chem. Commun. 2011, 47, 8569−8571.
https://pubs.acs.org/10.1021/acsanm.3c00351 (15) Wan, X. K.; Wang, J. Q.; Nan, Z. A.; Wang, Q. M. Ligand
effects in catalysis by atomically precise gold nanoclusters. Sci. Adv.
Author Contributions 2017, 3, No. e1701823.
The manuscript was written through contributions of all (16) Wang, F.; Richards, V. N.; Shields, S. P.; Buhro, W. E. Kinetics
authors. All authors have given approval to the final version of and Mechanisms of Aggregative Nanocrystal Growth. Chem. Mater.
the manuscript. 2014, 26, 5−21.
(17) Crooks, R. M.; Zhao, M.; Sun, L.; Chechik, V.; Yeung, L. K.
Funding Dendrimer-Encapsulated Metal Nanoparticles: Synthesis, Character-
The National Natural Science Foundation of China ization, and Applications to Catalysis. Acc. Chem. Res. 2001, 34, 181−
(51873155) is gratefully acknowledged. 190.
Notes (18) Shifrina, Z. B.; Matveeva, V. G.; Bronstein, L. M. Role of
Polymer Structures in Catalysis by Transition Metal and Metal Oxide
The authors declare no competing financial interest. Nanoparticle Composites. Chem. Rev. 2020, 120, 1350−1396.

■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
(19) Zhang, M.; Xu, Y.; Wang, S.; Liu, M.; Wang, L.; Wang, Z.; Li,
X.; Wang, L.; Wang, H. Polyethylenimine-Modified Bimetallic Au@
Rh Core-Shell Mesoporous Nanospheres Surpass Pt for Ph-Universal
Hydrogen Evolution Electrocatalysis. J. Mater. Chem. A 2021, 9,
Foundation of China (No. 51873155). 13080−13086.

■ REFERENCES
(1) Jin, R.; Li, G.; Sharma, S.; Li, Y.; Du, X. Toward Active-Site
(20) Dai, Y.; Yu, P.; Zhang, X.; Zhuo, R. Gold nanoparticles
stabilized by amphiphilic hyperbranched polymers for catalytic
reduction of 4-nitrophenol. J. Catal. 2016, 337, 65−71.
Tailoring in Heterogeneous Catalysis by Atomically Precise Metal (21) Li, D.; Dai, Y.; Chen, X.; Zhang, X.; Yue, D.; Wang, J.; Guo, Y.
Nanoclusters with Crystallographic Structures. Chem. Rev. 2021, 121, Stability and Catalytic Activity of Hyperbranched Polyglycerol
567−648. Stabilized Gold Nanofluids. J. Mol. Liq. 2022, 354, No. 118848.
(2) Du, Y.; Sheng, H.; Astruc, D.; Zhu, M. Atomically Precise Noble (22) Liu, H.; Wan, D.; Du, J.; Jin, M. Dendritic Amphiphile
Metal Nanoclusters as Efficient Catalysts: A Bridge between Structure Mediated One-Pot Preparation of 3D Pt Nanoparticles-Decorated
and Properties. Chem. Rev. 2020, 120, 526−622. PolyHIPE as a Durable and Well-Recyclable Catalyst. ACS Appl.
(3) Guan, Z. J.; Li, J. J.; Hu, F.; Wang, Q. M. Structural Engineering Mater. Interfaces 2015, 7, 20885−20892.
toward Gold Nanocluster Catalysis. Angew. Chem., Int. Ed. 2022, 61, (23) Ye, Y.; Jin, M.; Wan, D. One-Pot Synthesis of Porous Monolith-
No. e202209725. Supported Gold Nanoparticles as An Effective Recyclable Catalyst. J.
(4) Imaoka, T.; Kitazawa, H.; Chun, W. J.; Yamamoto, K. Finding Mater. Chem. A 2015, 3, 13519−13525.
the Most Catalytically Active Platinum Clusters With Low Atomicity. (24) Yi, C.; Yang, Y.; Liu, B.; He, J.; Nie, Z. Polymer-Guided
Angew. Chem., Int. Ed. 2015, 54, 9809−9815. Assembly of Inorganic Nanoparticles. Chem. Soc. Rev. 2020, 49, 465−
(5) Haruta, M. Size- and support-Dependency in the Catalysis of 508.
Gold. Catal. Today 1997, 36, 153−166. (25) Grirrane, A.; Corma, A.; García, H. Gold-Catalyzed Synthesis
(6) Crampton, A. S.; Rötzer, M. D.; Ridge, C. J.; Schweinberger, F. of Aromatic Azo Compounds from Anilines and Nitroaromatics.
F.; Heiz, U.; Yoon, B.; Landman, U. Structure Sensitivity in the Science 2008, 322, 1661−1664.
Nonscalable Regime Explored via Catalysed Ethylene Hydrogenation (26) Chong, H.; Li, P.; Xiang, J.; Fu, F.; Zhang, D.; Ran, X.; Zhu, M.
on Supported Platinum Nanoclusters. Nat. Commun. 2016, 7, Design of an Ultrasmall Au Nanocluster-CeO2 Mesoporous Nano-
No. 10389. composite Catalyst for Nitrobenzene Reduction. Nanoscale 2013, 5,
(7) Crampton, A. S.; Roetzer, M. D.; Schweinberger, F. F.; Yoon, B.; 7622−7628.
Landman, U.; Heiz, U. Controlling Ethylene Hydrogenation (27) Fu, J.; Dong, J.; Si, R.; Sun, K.; Zhang, J.; Li, M.; Yu, N.; Zhang,
Reactivity on Pt-13 Clusters by Varying the Stoichiometry of the B.; Humphrey, M. G.; Fu, Q.; Huang, J. Synergistic Effects for
Amorphous Silica Support. Angew. Chem., Int. Ed. 2016, 55, 8953− Enhanced Catalysis in a Dual Single-Atom Catalyst. ACS Catal. 2021,
8957. 11, 1952−1961.
(8) Heiz, U.; Sanchez, A.; Abbet, S.; Schneider, W. D. Catalytic (28) Guo, Z.; Xiao, C.; Maligal-Ganesh, R. V.; Zhou, L.; Goh, T. W.;
Oxidation of Carbon Monoxide on Monodispersed Platinum Li, X.; Tesfagaber, D.; Thiel, A.; Huang, W. Pt Nanoclusters Confined
Clusters: Each Atom Counts. J. Am. Chem. Soc. 1999, 121, 3214− within Metal-Organic Framework Cavities for Chemoselective
3217. Cinnamaldehyde Hydrogenation. ACS Catal. 2014, 4, 1340−1348.
(9) Herzing, A. A.; Kiely, C. J.; Carley, A. F.; Landon, P.; Hutchings, (29) Zhu, Y.; Qiu, X.; Zhao, S.; Guo, J.; Zhang, X.; Zhao, W.; Shi, Y.;
G. J. Identification of Active Gold Nanoclusters on Iron Oxide Tang, Z. Structure Regulated Catalytic Performance of Gold
Supports for CO Oxidation. Science 2008, 321, 1331−1335. Nanocluster-MOF Nanocomposites. Nano Res. 2020, 13, 1928−1932.
(10) Hayashi, T.; Tanaka, K.; Haruta, M. Selective Vapor-Phase (30) Lu, S.; Hu, Y.; Wan, S.; McCaffrey, R.; Jin, Y.; Gu, H.; Zhang,
Epoxidation of Propylene over Au/TiO2 Catalysts in the Presence of W. Synthesis of Ultrafine and Highly Dispersed Metal Nanoparticles
Oxygen and Hydrogen. J. Catal. 1998, 178, 566−575. Confined in a Thioether-Containing Covalent Organic Framework

6660 https://doi.org/10.1021/acsanm.3c00351
ACS Appl. Nano Mater. 2023, 6, 6653−6661
ACS Applied Nano Materials www.acsanm.org Article

and Their Catalytic Applications. J. Am. Chem. Soc. 2017, 139, 3 was reworded; labels were added to the panels of Figure 6;
17082−17088. and reference numbers were corrected in the footnotes for
(31) Chen, C.; Nan, C.; Wang, D.; Su, Q.; Duan, H.; Liu, X.; Zhang, Tables 4 and 5. The corrected version was reposted on April 6,
L.; Chu, D.; Song, W.; Peng, Q.; Li, Y. Mesoporous Multicomponent 2023.
Nanocomposite Colloidal Spheres: Ideal High-Temperature Stable
Model Catalysts. Angew. Chem., Int. Ed. 2011, 50, 3725−3729.
(32) Bai, F.; Wang, D.; Huo, Z.; Chen, W.; Liu, L.; Liang, X.; Chen,
C.; Wang, X.; Peng, Q.; Li, Y. A Versatile Bottom-Up Assembly
Approach to Colloidal Spheres from Nanocrystals. Angew. Chem., Int.
Ed. 2007, 46, 6650−6653.
(33) Wang, D.; Xie, T.; Peng, Q.; Li, Y. Ag, Ag2S, and Ag2Se
Nanocrystals: Synthesis, Assembly, and Construction of Mesoporous
Structures. J. Am. Chem. Soc. 2008, 130, 4016−4022.
(34) Inomata, T.; Konishi, K. Gold Nanocluster Confined within A
Cage: Template-Directed Formation of A Hexaporphyrin Cage and
Its Confinement Capability. Chem. Commun. 2003, 1282−1283.
(35) Maity, B.; Abe, S.; Ueno, T. Observation of Gold Sub-
Nanocluster Nucleation within A Crystalline Protein Cage. Nat.
Commun. 2017, 8, No. 14820.
(36) Miyamura, H.; Morita, M.; Inasaki, T.; Kobayashi, S. Aerobic
Oxidation of Amines Catalyzed by Polymer-Incarcerated Au Nano-
clusters: Effect of Cluster Size and Cooperative Functional Groups in
the Polymer. Bull. Chem. Soc. Jpn. 2011, 84, 588−599.
(37) Kobayashi, S.; Miyamura, H. Polymer-Incarcerated Metal(0)
Cluster Catalysts. Chem. Rec. 2010, 10, 271−290.
(38) Weiss, E.; Dutta, B.; Schnell, Y.; Abu-Reziq, R. Palladium
Nanoparticles Encapsulated in Magnetically Separable Polymeric
Nanoreactors. J. Mater. Chem. A 2014, 2, 3971−3977.
(39) Udumula, V.; Tyler, J. H.; Davis, D. A.; Wang, H.; Linford, M.
R.; Minson, P. S.; Michaelis, D. J. Dual Optimization Approach to
Bimetallic Nanoparticle Catalysis: Impact of M1/M2 Ratio and
Supporting Polymer Structure on Reactivity. ACS Catal. 2015, 5,
3457−3462.
(40) Richter, F. H.; Meng, Y.; Klasen, T.; Sahraoui, L.; Schüth, F.
Structural Mimicking of Inorganic Catalyst Supports with Poly-
divinylbenzene to Improve Performance in the Selective Aerobic
Oxidation of Ethanol and Glycerol in Water. J. Catal. 2013, 308, 341−
351.
(41) Zhang, T.; Sanguramath, R. A.; Israel, S.; Silverstein, M. S.
Emulsion Templating: Porous Polymers and Beyond. Macromolecules
2019, 52, 5445−5479.
(42) Tan, L.; Tan, B. Functionalized Hierarchical Porous Polymeric
Monoliths as Versatile Platforms to Support Uniform and Ultrafine
Metal Nanoparticles for Heterogeneous Catalysis. Chem. Eng. J. 2020,
390, No. 124485.
(43) Barkan-Ö ztürk, H.; Menner, A.; Bismarck, A.; Woodward, R. T.
Simultaneous Hypercrosslinking and Functionalization of Polyhipes
for Use as Coarse Powder Catalyst Supports. Chem. Eng. Sci. 2022,
264, No. 118151.
(44) Li, C.; Xu, S.; Jin, M.; Wan, D. Trace Thioether Inserted
Polyamine Patches on A Support Mediate Uniform Gold Nano-
clusters as Ultrahigh Active Catalysts. J. Mater. Chem. A 2021, 9,
15714−15723.
(45) Ahn, J. H.; Jang, J. E.; Oh, C. G.; Ihm, S. K.; Cortez, J.;
Sherrington, D. C. Rapid Generation and Control of Microporosity,
Bimodal Pore Size Distribution, and Surface Area in Davankov-Type
Hyper-Cross-Linked Resins. Macromolecules 2006, 39, 627−632.
(46) Zhang, J.; Zhao, D.; Xiao, D.; Ma, C.; Du, H.; Li, X.; Zhang, L.;
Huang, J.; Huang, H.; Jia, C. L.; Tománek, D.; Niu, C. Assembly of
Ring-Shaped Phosphorus within Carbon Nanotube Nanoreactors.
Angew. Chem., Int. Ed. 2017, 56, 1850−1854.
(47) Thawarkar, S. R.; Thombare, B.; Munde, B. S.; Khupse, N. D.
Kinetic investigation for the catalytic reduction of nitrophenol using
ionic liquid stabilized gold nanoparticles. RSC Adv. 2018, 8, 38384−
38390.

■ NOTE ADDED AFTER ASAP PUBLICATION

This paper was published on March 20, 2023. The heading for
section 2.3.3 was revised; a description in the caption of Figure
6661 https://doi.org/10.1021/acsanm.3c00351
ACS Appl. Nano Mater. 2023, 6, 6653−6661