Polymer United Fe2O3 nano-spheroids for Water Oxidation and the

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Polymer United Fe2O3 nano-spheroids for Water Oxidation and the Green Synthesis of 2,3-Dihydro-phthalazine-1,4-dione Dongliang Huang, Xiu-Lin Fang, Qiu-Yun Chen, Qiang Wang, and Jing Gao ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/acssuschemeng.8b00528 • Publication Date (Web): 20 Jul 2018 Downloaded from http://pubs.acs.org on July 23, 2018

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ACS Sustainable Chemistry & Engineering

Polymer United Fe2O3 Nano-spheroids for Water Oxidation and

the

Green

Synthesis

of

2,3-Dihydro-phthalazine-1,4-dione Dong-liang Huang,† Xiu-Lin Fang, † Qiu-Yun Chen,*，†,Qiang Wang, ‡ Jing Gao, ‡ †

School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang,

Jingkou District, Xuefu Road 212013, People’s Republic of China. ‡

School of Pharmacy, Jiangsu University; Zhenjiang, Jingkou District, Xuefu Road

212013, People’s Republic of China.

Contact information of the corresponding author is as follows: Qiu-Yun Chen: School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, Jingkou District, Xuefu Road 212013, People’s Republic of China.*E-mail address: [email protected] (Q.Y. Chen).

1

ACS Paragon Plus Environment

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Abstract Artificial photosynthesis by catalysts for water oxidation and organic reaction will push the development of sustainable chemistry. To develop economic and eco-friendly catalysts for water oxidation and poly(p-aminobenzoic

one

step

acid-aniline)@Fe2O3

oxidation-cyclization,

(labelled

as

herein,

PPaba@Fe2O3)

nano-spheroids were synthesized by Fe3+ catalyzed oxidation-polymerization in one step hydrothermal process. Results demonstrate that PPaba@Fe2O3 can be both catalyst and electron acceptor during photo-driven water oxidation process. In particular, 2,3-dihydro-phthalazine-1,4-dione(Dpd) was synthesized by one step oxidation-cyclization of benzyl alcohol and hydrazine in water containing PPaba@Fe2O3 / [Ru(bpy)3]Cl2. Therefore, the catalyst can be applied in the sustainable synthesis of Dpd derivatives. KEYWORDS:

Photosynthesis,

water

oxidation,

2,3-dihydro-phthalazine-1,4-dione

2


cyclization,

sustainable,

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INTRODUCTION Molecular catalysts for water oxidation, CO2 reduction or transforming light energy into chemical energy will give great dedication to the development of new energy and green chemistry.1-3 Light-activated water oxidation to dioxygen is the crucial step of light energy transformation in natural or artificial photosynthetic system. Because of its abundance, green, and low-cost, the fascinating design of iron-based water oxidation catalyst (WOC) is very attractive. Haematite (alpha-Fe2O3) is a potential candidate for photo-electrochemical water splitting.4Amorphous iron oxide materials are active toward to the oxygen evolution reaction because surface iron vacancies can enhance the activity of haematite in the photo-electrochemical reaction and the decompose of FeOO and Fe-OOH intermediates quickly leads to the formation of O2.5-8 Dyes doped or conjugated metal nanoparticles can be effective catalysts for light driven water oxidation.9-11Therefore, based on adsorption and catalytic properties of porous Fe2O3 (nanosorbcats), it has been used for photocatalytic degradation of contaminants.12-14 An important factor for catalyzed water oxidation is the electron acceptor. Na2S2O8 is a widely used scarified electron acceptor during water oxidation process.15 Up to now, reusable electron acceptor has been a challenge.16 Recently, polyaniline supported iron nanoparticles have been used as catalysts for the conversion of lower olefins.17 Polyaniline doped iron nanoparticles have good photochemical properties.18-19 Therefore, it is possible that polyaniline derivatives doped haematite can be reusable catalyst and electron acceptors for water oxidation or catalyzed oxidation reaction.

To develop economic and environmental friendly 3



multifunctional catalysts for water oxidation and oxidation cyclization reactions, herein, a new kinds of poly(p-aminobenzoic acid-aniline)@Fe2O3 (labelled as PPaba@Fe2O3) nano-spheres were synthesized by Fe3+ catalyzed polymerization in one step hydrothermal process. In particular, PPaba@Fe2O3 / [Ru(bpy)3]2+ system was further applied as reusable catalyst for water oxidation and the synthesis of Dpd derivatives.

Dpd derivatives were important intermediates for the synthesis of

pharmacological compounds such as, sulfonamide derivatives.20 Heterocycles containing phthalazine moiety show some pharmacological and biological activities.21-22 Generally, Dpd derivatives were synthesized via the condensation reaction of aromatic aldehydes with 1,3-dicarbonyl compounds and phthalhydrazide in the presence of catalysts, such as dodecylphosphonic acid (DPA) or zirconium oxide nanoparticles, reported by Kidwai, M, Piltan, M and Tayade, Y A et al. (Scheme 1).23-26 In contrast to traditional synthetic methods, this method uses LED light as energy source without heat while ensuring sufficient yield. Eco-friendly synthesis process is still a challenge. Moreover, there is no report for the synthesis of phthalazine-1,4-dione derivatives using benzyl alcohol as starting materials. Herein, we report a new catalyst (PPaba@Fe2O3) and an eco-friendly oxidation-cyclization method for the synthesis of Dpd.

Scheme 1. Strategies for the synthesis of Diketone-phthalazine The conventional methods:

4


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……………………………………………………………………………...

This work:

EXPERIMENTAL SECTIION Materials and Characterization. p-Aminobenzoic acid (Paba), sodium hydroxide, hexahydrate and ferric chloride, concentrated hydrochloric acid, o-xyleneglycol, hydrazine hydrate, sodium dihydrogen phosphate and sodium phosphate were provided from Sinopharm Chemical Reagent Co. Ltd. (China). The Nicolet-470 spectrophotometer was used for infrared spectra with a wavenumber range from 4000 to 400 cm-1 by using KBr pellets. Varian CARY 50-BIO UV–VIS spectrophotometer for electronic absorption spectra was recorded by the range from 900 to 190 nm. XRD measurements for PPaba and PPaba-Fe2O3 was measured by Bruker D8 diffractometer (40 kV, 40 mA). Scanning electron microscopy (SEM) images and energy-dispersive X-ray (EDX) analysis were performed using Hitachi SU8020 and Zeiss Merlin Compact microscopes. The EPR spectra of PPaba dissolved in CH3CN were gotten by Bruker biospin GmbH instrument. HORIBA Jobin Yvon, Longjumeau Cedex was ICP-AES text for the content of iron in the PPaba-Fe2O3. The 5



Page 6 of 24

NMR (400MHz) data for Dpd was measured on Bruker AVANCEI I400MHz spectrometer by using (CD3)2SO as solvent. Synthesis of Poly(p-aminobenzoic acid-aniline) Modified Iron Oxide (PPaba-Fe2O3). p-Aminobenzoic acid (1 mmol, 137 mg) was mixed with the aqueous solution of sodium hydroxide (0.1 mM, 10 ml) and aqueous solution of FeCl3·6H2O (0.1 mM, 10 ml).The mixture was heated for 6 h at 160 °C, and then it was cooled naturally. After separation by centrifugation, the brick-red solid was washed three times by water. Yield, 362 mg (88%). IR (KBr, cm-1): 3281, 2532, 1680, 1581, 1413, 565. Synthesis

of

Poly(p-aminobenzoic

acid-aniline)

(labelled

as

PPaba).

Poly(p-aminobenzoic acid-aniline) modified iron oxide (100 mg) (PPaba-Fe2O3) was dispersed in hydrochloric acid solution (1 mM, 10 ml) by ultrasound for 30 min. After neutralization with NaOH to pH 5, excess EDTA was added. The dark purple solid (PPaba) was obtained by centrifugation and washed three times with deionized water. The resulting solid was dried in a vacuum. Catalytic

Synthesis

of

2,3-Dihydrophthalazine-1,4-dione

(Dpd).

In

photocatalytic reactor, PPaba-Fe2O3 (200 mg), RuII(bpy)32+ (0.1 M, 200 µL) aqueous solution, O-xyleneglycol (1 mmol,138 mg) and hydrazine hydrate (1.2 mmol, 70 mg) (or its derivatives) were mixed in water (5 ml). The resulting mixture was stirring under illumination by the LED lamp (450-550 nm) for 24 h. Then the product was obtained by filtered through hot ethanol, followed by separation with silica gel chromatography. Dpd (3a), yield: 88%. 1H NMR (400 MHz, (CD3)2SO) δ 11.56 (s, 2H), δ8.76-8.09 (m, 4H). 13C NMR (100 MHz, (CD3)2SO) δ 155.15, 132.97, 127.63, 6


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125.58. IR (v/cm-1) 3169 (vs), 3024 (vs), 2899 (m), 2583 (w), 1667 (vs), 1307 (s). MS (ESI, m/z) 163.1 (M + H+), 185.1 (M + Na+). Water Oxidation Experiments. The water oxidation was catalyzed by PPaba-Fe2O3 system and PPaba-Fe2O3/Ru(bpy)3Cl2 system. For α-Fe2O3/RuII(bpy)32+ system, (0.1 M, 200 µL) RuII(bpy)32+ and 10 mg α-Fe2O3 were added into 5 ml PB (pH=7.0) with blue LED (3W) irradiation at 298 K. The oxygen volume is directly collected by custom U-tube with scale value. The obtained oxygen was detected by gas chromatography (GC-TCD).

RESULTS AND DISCUSSION Characterization of PPaba-Fe2O3. XRD spectra of PPaba (a) and PPaba-Fe2O3 (b) are shown in Figure 1A. the broad peak which belong to the pure PPaba (a) at 2θ=20-30° indicate the amorphous behavior,27 while the characteristic diffraction peaks for PPaba-Fe2O3 at angles 2θ= 21.15°, 32.99°, 40.85°, 49.45°, 54.09°, 57.58°, 62.31°, 64.01°, 71.88° and 75.33° are in agreement with that of α-Fe2O3 standard card (PDF24-0072).28 It demonstrates that the metal structure of PPaba-Fe2O3 is similar to the hematite α-Fe2O3. In the IR spectrum of PPaba-Fe2O3, the peaks appeared at 1510 cm-1 and 565 cm-1 are the characteristic peaks of the aromatic ring C=C in PPaba and the characteristic absorption peaks of Fe-O, indicating the formation of PPaba-Fe2O3 (Figure 1B). The disappeared peak at 565 cm-1 indicating that free PPaba was obtained. The peak at 1680 cm-1 is the characteristic absorption peak of -COOH. This indicates that -COOH is present in PPaba and PPaba-Fe2O3.Two peaks at 1581 and

7



1413 cm-1 which are shown at the lines A, B and C, are characteristic peaks from the benzene ring. The PPaba-Fe2O3 is a uniform spindle-shaped particle with the size of about 350 nm (Figure 1C).

1200

a

1000 Counts

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800

b 600

20

30

40

50

60

70

80

2 Theat

Figure 1A. X-ray Diffraction of PPaba (a) and PPaba-Fe2O3 (b).

A

B

C

4000 3500 3000 2500 2000 1500 1000

500

Wavenember(nm-1)

Figure 1B. FTIR spectra of Paba (A), PPaba (B), and PPaba-Fe2O3 (C). 8


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Figure 1C. SEM images of PPaba-Fe2O3.

In the UV spectrum of PPaba-Fe2O3 (Figure 1D), the two peaks at 331 nm and 583 nm of PPaba-Fe2O3 belong to the π-π* transitions on the benzene ring and the electronic transitions from the benzene ring to the quinone ring in PPaba, respectively.29 From the UV spectrum of PPaba, it can be illustrated that the characteristic peak of α-Fe2O3 disappears at 210 nm and the other two peaks shift to 314 nm and 561 nm. This is probably due to the disappearance of iron ions after acidification, which led to the change of the electron density. The peaks at 314 nm and 561 nm also demonstrated that there are the oxidized unit (quinonediimine) in poly(p-aminobenzoic acid-aniline) (PPaba) formed during the hydrothermal synthesis process. The ESR spectrum show the existence of single electron in PPaba. In 1HNMR spectra, chemical shifts at 5.77 ppm, 6.16 ppm-6.08 ppm, 7.53-7.55 ppm, 7.97 ppm - 7.99 ppm and 9.52 ppm show the existence of -NH-, H-C=C, H-Ar, the hydrogen of quinone ring and –COOH, respectively (Figure S1-S3). Therefore, there are both quinonediimine unit and the phenylenediamine unit in PPaba.

9



1.25 a

1.00 Absorbance (AU)

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0.75 b

0.50

0.25 300

400

500

600

700

800

Wavelength (nm)

Figure 1D. UV spectra of PPaba-Fe2O3 (a) and PPaba (b).

In Resonance Raman spectrum of PPaba-Fe2O3 (Figure 1E), peaks at 227, 302, 394, 630 and 1380 cm-1 belong to the Raman vibration of α-Fe2O3 single crystal D63d space group. Raman modes vibration A1g appeared at 227 and Raman modes vibration of Eg appeared at 302, 394, and 630 cm-1. These absorption peaks do not completely coincide with the characteristic absorption of pure α-Fe2O3 (Figure S4). This indicates that the PPaba-modified Fe2O3 characteristic functional group is not completely the same as pure α-Fe2O3. While the peak at 839 cm-1 belongs to the in-plane quinone ring deformation peak and the peak at 1250 cm-1 is the characteristic absorption peak of C-N.30 The absorption peak shown in 1549 cm-1 is the vibration absorption belong to the iron-coordinated carboxylate group (Fe-OOC-), which confirms the coordination between PPaba and metal Fe(III).

10


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80 1380 1549

60 Raman Intensity

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


1250

40

20

0

630 394 539 227 302

500

839

1000

1500 -1 Raman shift (cm )

2000

Figure 1E. Resonance Raman spectrum of PPaba-Fe2O3. The weight percentage of PPaba-Fe2O3 was quantitatively determined by TGA (Figure 1F). The about 3-5% weight loss below 100 OC is likely from the loss of absorbed water. With the temperature increases, the weight decreases distinctly from 100 to 500 O

C，which is caused by the decarboxylation process. Peaks sharply decreased from 500 O

to 700 C, owning to the decompose of poly(p-aminobenzoic acid-aniline). Based on the TGA curve, the final product of heat-treating PPaba-Fe2O3 above 700 OC is pure α-Fe2O3, but the curve goes up significantly. This may be due to that PPaba transform Fe3+ to Fe2+ in the heating process. As the polymer decomposes, the oxidation of Fe2+ increases the mass at elevated temperatures.31 According to the weight loss in the range 100-700 OC, the content of α-Fe2O3 in the PPaba-Fe2O3 nanocomposite is approximately 55.9 wt%. The EDX data confirm that there are Fe, N, C and O elements in PPaba-Fe2O3 (Figure S5).

11



100 90 % weight loss

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80 70 60 50 0

200

400 600 Temperature °C

800

1000

Figure 1F. TGA curves of PPaba-Fe2O3 in 0-1000 oC.

Water oxidation.

The water oxidation capacity of α-Fe2O3/ RuII(bpy)32+/ Na2S2O8

system and PPaba-Fe2O3/RuII(bpy)32+ system under irradiation with blue LED light was carried out. Experimental results indicate that the PPaba-Fe2O3/RuII(bpy)32+ system has good water oxidation ability and longer duration (Figure S6), whereas PPaba-Fe2O3, like Fe2O3, is most active at pH=9.32-34 The TON values of our synthesized nanoparticles and reported α-Fe2O3 with different size were compared (Table S1). For example, the TON of α-Fe2O3 (200 nm, reported by Townsend, T. K. et. al.) is 63.60,35 which is larger than the TON values of α-Fe2O3 with the size of 900 nm (TON 32. 03, this work) and 5.4 nm (TON, 1.13, reported by Zhu, J. X. et al.) 36, respectively. The PPaba-Fe2O3 (350 nm) is a uniform spindle-shaped particle with the TON value of 71.26 . Results indicate that the size and effective energy transfer have 12


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some effect to the TON of catalysts. The calculated energy bandgap (Eg) of PPaba-Fe2O3 is equal to 2.0 eV (Figure S7). The lower energy bandgap (Eg) favors the electron transition from the VB to the CB, whereas the PL spectra of α-Fe2O3 and PPaba-Fe2O3 also indicate PPaba-Fe2O3 has a lower electron-hole pair recombination rate than α-Fe2O3 (Figure S8). So PPaba-Fe2O3 has higher oxidation activity than α-Fe2O3. As shown in the table 1, the TON of PPaba-Fe2O3/RuII(bpy)32+ is 71.26 and the TOF value is 0.51 h-1. The results show that PPaba-Fe2O3/RuII(bpy)32+ has good water oxidation activity. In order to confirm the role of PPaba as an electron acceptor, α-Fe2O3/ RuII(bpy)32+ was used as the control group, and the α-Fe2O3/ RuII(bpy)32+/ PPaba was used as the experimental group. From Figure 2.1, we can see that the α-Fe2O3/ RuII(bpy)32+ without PPaba can’t catalyze the water oxidation, but the α-Fe2O3/ RuII(bpy)32+/ PPaba system can obviously catalyze water oxidation. It indicates that the quinonediimine unit of PPaba can effectively accept the excited electrons, and PPaba can be the electron acceptor. Moreover, after 5 times recycle， the PPaba-Fe2O3 still catalyze the water oxidation while its water oxidation capacity slightly decreased because it was hard to recycle the catalyst in quantity when it was used in small scale (Figure S9). Results demonstrate that PPaba-Fe2O3 can be used as both reusable catalyst and electron acceptor for water oxidation. The possible mechanism of water oxidation and the transfer of electrons were shown in Figure 2.2. Ru(bpy)32+ becomes excited *Ru(bpy)32+ with blue LED light irradiation. Then *Ru(bpy)32+ give the high energy electron to PPaba and *Ru(bpy)32+ is converted to 13



Ru(bpy)33+, which causes the electron transition from VB to CB and form electron-hole pairs. Holes (h+) on the surface of nanoparticles can oxidize water into oxygen.

Table 1. TON and TOF values O2 (µmol) TONa

system

TOF (min-1)

α-Fe2O3/ RuII(bpy)32+/ Na2S2O8

44.8

32.03

0.45

PPaba-Fe2O3/RuII(bpy)32+

99.68

71.26

0.51

a

TON= nO2 (µmol) /n(Fe3+) (µmol), TOF = TON / time (min).

a b

140 120 O2 Evolved (µ mol)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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100 80 60 40 20 0 0

20

40

60

80 100 120 140 160 180 Time (min)

Figure 2.1. a) Water oxidation catalyzed by (a)α-Fe2O3/ RuII(bpy)32+/ PPaba and (b) α-Fe2O3/ RuII(bpy)32+ under irradiation with blue light at 298 K. Conditions: (a) 14


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RuII(bpy)32+ (0.1 M, 200 µL): m (catalyst) =10 mg, m(PPaba)=10 mg, V (H2O) =5 ml.; (b) RuII(bpy)32+ (0.1 M, 200 µL): m (catalyst) =10 mg, V (H2O) =5 ml.

Figure 2.2. The mechanism of water oxidation and electron transfer.

Synthesis of the Bisketophthalazine. In order to study the synthesis of the bisketophthalazine derivatives catalyzed by PPaba-Fe2O3/ RuII(bpy)32+, we use o-xyleneglycol (1a) and hydrazine hydrate (2a) as the starting materials, PPaba-Fe2O3 as catalyst, RuII(bpy)32+ as a photosensitizer and acetonitrile-water (1:1) as a solvent. The mixture was irradiated with blue LED light (10W). The bisketophthalazine derivative 3a was obtained in 70% yield (Figure 3.1).

Figure 3.1. The synthesis of bisketophthalazine (Dpd).

15



It is found that water is a key factor for the synthesis of 3a catalyzed by PPaba-Fe2O3/ RuII(bpy)32+. Less compounds could be produced without water (Table S2). In addition, results demonstrate that the temperature has some effect on the yield. The yield of Dpd can reach 88% when the reaction (molar ratio of 1a:2a=1:1.2) was carried out in pure water, constant temperature 75 °C for 48 h. Above all, we have succeeded in the synthesis of Dpd by eco-friendly oxidation-cyclization method with PPaba@Fe2O3 as a catalyst. Next, we explored the possible mechanism of the reaction. The PPaba-Fe2O3/ RuII (bpy)32+ system has good water oxidation ability with the production of hydroxyl radical (Figure S10). For RuII(bpy)32+, the electronic transition from valence band to conduction band happened under irradiation, or when the electron acceptor exists (PPaba), the excited electron could leave from the electron acceptor to form the electron hole, and the electron hole will be able to transfer the surrounding water molecules into reactive oxygen species (ROS). Reactive oxygen species (ROS) molecules can extract hydrogens from orthoxylene resulting aldehydes (Fig S11), which combined with hydrazine derivatives forming bisketophthalazine compounds (Figure 3.2).

Figure.3.2. Proposed mechanistic pathway for photocatalytic oxidation-cyclization reaction.

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CONCLUSIONS In summary, a polymer united metal nano-spheres (PPaba@Fe2O3) were synthesized by Fe3+ catalyzed polymerization and oxidation of p-aminobenzoinc acid in one step hydrothermal process. In particular, PPaba@Fe2O3 can be both catalyst and electron acceptor during photo-driven water oxidation process. PPaba@Fe2O3/ [Ru(bpy)3]2+ system was applied as reusable catalyst for water oxidation and the synthesis of Dpd derivative. Therefore, the synthesis of Dpd derivatives can be carried out using benzyl alcohol and hydrazine as starting materials in water. PPaba@Fe2O3is an eco-friendly catalyst for the synthesis of Dpd derivatives by light driven oxidation-cyclization reactions.

Supporting Information Table for showing synthesis details, ESR spectrum of PPaba-Fe2O3, NMR spectra, figures on water oxidation, energy band gap calculation and hydroxyl radical trapping. ■ AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. ORCID Qiuyun Chen: 0000-0002-0437-8663 Notes 17



The authors declare no competing financial interest. ■ ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (Grant 21571085) and Postgraduate Research Practice Innovation Program of Jiangsu Province (no. KYCX_1804).

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For Table of Contents Use Only

PPaba@Fe2O3 nano-spheroids used as both catalyst and electron acceptor for the synthesis of 2,3-dihydro-phthalazine-1,4-dione.

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Polymer United Fe2O3 nano-spheroids for Water Oxidation and the

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