Ultra-Low Loading Ruthenium on Alumina Monoliths for Facile ...

S1

Ultra‐Low Loading Ruthenium on Alumina Monoliths

for Facile, Highly Recyclable Reduction of p‐

Nitrophenol Lorianne R. Shultz1,2, Corbin Feit2,3, Jordan Stanberry1, Zhengning Gao2,3, Shaohua Xie2,4, Vasileios A.

Anagnostopoulos1, Fudong Liu2,4,5, Parag Banerjee2,3,5,*, and Titel Jurca1,2,5,*

1 Department of Chemistry, University of Central Florida, 4111 Libra Drive, Orlando, FL, 32816, USA;

[email protected] (L.R.S.); [email protected] (J.S.), Vasileios Anagnostopoulos (V.A) 2 Renewable Energy and Chemical Transformations Cluster, University of Central Florida, 4353 Scorpius Street,

Orlando, FL, 32816, USA. 3 Department of Materials Science and Engineering, University of Central Florida, Orlando, FL, 32816, USA;

[email protected] (C.F.) [email protected] (Z.G.) 4 Department of Civil, Environmental, and Construction Engineering, University of Central Florida, Orlando, FL,

32816, USA; [email protected] (S.X.) ; [email protected] (F.L.) 5 NanoScience Technology Center, University of Central Florida, Orlando, FL, 32826, USA.

* Correspondence: [email protected] (P.B.); [email protected](T.J.)

Table of Contents

XPS analysis of model Ru on Al2O3……………………………………………………………………………S2

UV‐Vis spectra and kinetics for the reduction of 4NP (Ru50@Al2O3 and Ru75@Al2O3)………….……S3‐S5

UV‐Vis spectra for the blank Al2O3 sphere test for reduction of 4NP …………………..………..………..S5

Reduction of Azo dyes and Amino‐nitrophenols (Ru75@Al2O3)………........................................………S6‐S8

Reduction of 4NP (Ru50@Al2O3) under various stirring rates……………………………………….……S9‐S10

S2

Figure S1: Fine spectra of Ru 3d of 50 cycles Ru ALD at 185°C onto a 10 nm Al2O3 ALD

film on silicon.

Table S1: The 3d5/2 peak position of each species, area and full‐width at half‐max

(FWHM) for Ru0, Ru4+ and the 1s peak position, area and FWHM for C‐C for 50 cycles

Ru ALD at 185°C onto a 10 nm Al2O3 ALD film on silicon.

ALD at 185°C Species:

BE (eV): FWHM: Area: Atomic Percent of only Ru species (%):

Ru (0) 279.930 0.62 19507.210 43.22

Ru (IV) 280.466 1.28 25631.960 56.78

Ru (IV) satellite 282.015 2.5 9479.835 ‐‐

C‐C 284.50 2 3648.847 ‐‐

S3

Figure S2: UV‐Vis spectra plotted as At – At,initial for enhanced visualization of the max =

400 nm (4NP*) decrease and absorbance at 310 nm (4AMP*) increase; spectra for the

reduction of 4NP using Ru50@Al2O3 (30.6 mg for trial 1, left, and 29.3 mg for trial 2, right),

each catalyst recycled over five serial tests (top to bottom) with DIW rinsing in between.

Reduction was monitored at 1 min intervals for 60 min. First order and zero order kinetics

are shown for each trial, corresponding to max = 400 nm (right of each spectrum).

S4

Figure S3: UV‐Vis spectra plotted as At – At,initial for enhanced visualization of the max =

400 nm (4NP*) decrease and absorbance at 310 nm (4AMP*) increase; spectra for the

reduction of 4NP using Ru75@Al2O3 (28.6 mg for trial 1, left, and 26.9 mg for trial 2, right),

each catalyst recycled over five serial tests (top to bottom) with DIW rinsing in between.

Reduction was monitored at 1 min intervals for 60 min. First order and zero order kinetics

are shown for each trial, corresponding to max = 400 nm (right of each spectrum).

S5

Trial_ Run First order rate [min‐1(g Ru)‐1] Zeroth order rate [min‐1(g Ru)‐1]

1_1 15056.1 30691.1

1_2 9832.3 20265.8

1_3 10410.3 21039.6

1_4 10215.7 20460.7

1_5 9832.3 20076.8

2_1 17944.5 30643.8

2_2 8051.1 16934.4

2_3 9661.3 19958.7

2_4 8918.1 18346.1

2_5 8859.1 18346.1

Table S2: Pseudo‐first and zeroth order kinetics for the reduction of 4NP with

Ru50@Al2O3.

Trial_ Run First order rate [min‐1(g Ru)‐1] Zeroth order rate [min‐1(g Ru)‐1]

1_1 38862.6 38862.6

1_2 20277.2 36610.1

1_3 8636.1 18398.5

1_4 9575.5 19524.7

1_5 7696.8 16711.7

2_1 44852.3 54387.4

2_2 5828.1 13065.3

2_3 4060.5 9181.6

2_4 7065.5 14656.2

2_5 4590.8 10242.1


Ru75@Al2O3.

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Figure S4: UV‐Vis spectra for the 1 min interval monitoring for 60 scans the of 4NP

solution with a blank Al2O3 spheres showing no reaction.

To further validate the broader substrate scope and potential for our catalyst system, as

a proof of concept, we tested the single run activity of Ru75@Al2O3 towards the reduction

of 2‐amino‐5‐nitrophenol (2A5NP) and 4‐amino‐2‐nitrophenol (4A2NP). Moving beyond

nitro groups, we tested for the reduction of azo moieties in common dyes Methyl Orange

(MO) and Methyl Red (MR) towards their constituent anilines (Scheme S1). Further

details are provided in the captions of Figures S4‐S7 below.

catalyst

NaBH4DIW

NO2

H2N

OH

NH2

HO

NO22A5NP 4A2NP

N

NN

SO3Na

MODMPD4ABS

N

NN

HO OMR

catalyst

NaBH4DIW

O3S

NH2

N

NH2

+

catalyst

NaBH4DIW

DMPDN

NH2

+

NH2OOCABA

catalyst

NaBH4DIW

NH2

H2N

OH

NH2

HO

NH2

Scheme S1: Expanded scope of catalytic testing of Ru75@Al2O3.

S7

Figure S5: UV‐Vis spectra for the 1 min interval monitoring of the reduction of 2‐amino‐5‐nitrophenol (0.39 µmol in 3 mL DIW) under excess NaBH4 conditions (0.2 mmol) using

Ru75@Al2O3 (masses shown on plots) over two trials. First order and zero order kinetics are

shown for each trial, corresponding to max = 460 nm; providing averages of 55054 5349 and 32567 1739 min‐1(g Ru)‐1 respectively.

Figure S6: UV‐Vis spectra for the 1 min interval monitoring of the reduction of 4‐amino‐2‐nitrophenol (0.39 µmol in 3 mL DIW) under excess NaBH4 conditions (0.2 mmol) using

Ru75@Al2O3 (masses shown on plots) over two trials. First order and zero order kinetics are

shown for each trial, corresponding to max = 480 nm; providing averages of 40643 475 and 18136 1507 min‐1(g Ru)‐1 respectively.

S8

Figure S7: UV‐Vis spectra for the 1 min interval monitoring of the reduction of methyl orange

(0.34 µmol in 3 mL DIW) under excess NaBH4 conditions (0.2 mmol) using Ru75@Al2O3 (masses shown on plots) over two trials. First order and zero order kinetics are shown for each trial,

corresponding to max = 465 nm; providing averages of 225990 63554 and 114330 10163 min‐1(g Ru)‐1 respectively.

Figure S8: UV‐Vis spectra for the 1 min interval monitoring of the reduction of methyl red (0.33

µmol in 3 mL DIW) under excess NaBH4 conditions (0.2 mmol) using Ru75@Al2O3 (masses shown on plots) over two trials. First order and zero order kinetics are shown for each trial,

corresponding to max = 430 nm; providing averages of 14131 7283 and 763 164 min‐1(g Ru)‐1 respectively.

S9

Figure S9: UV‐Vis spectra and kinetics for the reduction of 4NP using Ru50@Al2O3 that

was pre‐treated in 3 mL of 0.2 mmol NaBH4 for 10 min, followed by a several milliliters

of DIW rinse. Kinetics were obtained using max = 400 nm (4NP*), monitored at 1 min

intervals; providing pseudo‐first and zeroth order rates of 29305 and 22257 min‐1(g Ru)‐1

respectively.

Figure S10: UV‐Vis spectra and kinetics for the reduction of 4NP (2.34 μmol) with NaBH4

(1.2 mmol) in 18 mL DIW using Ru50@Al2O3 (masses shown on plots) at different stir rates

(RPMs shown on spectra). Reaction was monitored at 5 min intervals using a dip‐probe

attachment. Kinetics were obtained using max = 400 nm (4NP*). To reduce perturbation and

improve analysis, spectra was smoothed using OriginLab Savitzky‐Golay function with 40 points

of window, normalized to the baseline of the initial scan, and standardized by subtracting

absorbances by a constant factor to bring the baseline down to zero.

S10

Stir rate (RPM) First order rate [min‐1(g Ru)‐1] Zeroth order rate [min‐1(g Ru)‐1]

0 4797 4619

250 11796 11260

500 18231 13941

1000 23927 15395


Ru50@Al2O3 at different stir rates pertaining to spectra and kinetics shown in Figure S10.

Ultra-Low Loading Ruthenium on Alumina Monoliths for Facile ...

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