Catalytic decomposition of ammonium perchlorate on hollow mesoporous CuO microspheres

Accepted Manuscript Catalytic decomposition of ammonium perchlorate on hollow mesoporous CuO microspheres Yinghui Hu, Shimin Yang, Bowen Tao, Xiaolong Liu, Kaifeng Lin, Yulin Yang, Ruiqing Fan, Debin Xia, Dongyu Hao PII:

S0042-207X(18)31559-8

DOI:

10.1016/j.vacuum.2018.10.020

Reference:

VAC 8293

To appear in:

Vacuum

Received Date: 12 August 2018 Revised Date:

30 September 2018

Accepted Date: 8 October 2018

Please cite this article as: Hu Y, Yang S, Tao B, Liu X, Lin K, Yang Y, Fan R, Xia D, Hao D, Catalytic decomposition of ammonium perchlorate on hollow mesoporous CuO microspheres, Vacuum (2018), doi: https://doi.org/10.1016/j.vacuum.2018.10.020. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Catalytic Decomposition of Ammonium Perchlorate on Hollow Mesoporous CuO Microspheres Yinghui Hu a; Shimin Yang b; Bowen Tao c; Xiaolong Liu a; Kaifeng Lin a; Yulin Yang *; Ruiqing Fan a; Debin Xia a*; Dongyu Hao a

a

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a

MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion

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and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of

b

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Technology, Harbin 150001, PR China

Shanghai Space Propulsion Technology Research Institute, Shanghai 201100, PR

China c

Science and Technology on Aerospace Chemical Power Laboratory, No. 58, Qinghe

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Road, Xiangyang 441003, PR China

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Abstract

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* Corresponding author, e-mail: [email protected] and [email protected]

Hollow mesoporous CuO microspheres (CuO-HM) have been prepared by a

hard-template method and their structure properties as well as catalytic performance in ammonium perchlorate (AP) decomposition were fully investigated by XRD, SEM, XPS, TG/DSC and TG/F-TIR methods. The results indicated that CuO-HM could be described as CuO micro-sized spheres composed of self-assembled nanoparticles, possessing hollow and mesoporous structure. Compared with CuO nanoparticles and 1

ACCEPTED MANUSCRIPT CuO microspheres, CuO-HM has significantly improved catalytic efficiency in AP decomposition due to large surface area, easily accessible porous and hollow structure. Typically, CuO-HM could decrease the AP decomposition temperature by 105.7 oC

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and enhance the heat production by 735 J/g. TG/FT-IR results indicated that CuO-HM accelerated the thermal decomposition of AP mainly at the high temperature decomposition stage with the releasing of N2O, NO, NH3, H2O, HCl, O2 et al. This

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application in solid fuel rockets propellants.

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study demonstrated that hollow and mesoporous CuO was a promising catalyst for the

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Graphical Legend

Key words: Ammonium Perchlorate; hollow mesoporous; CuO microspheres;

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decomposition; TG/FT-IR

1. Introduction

Ammonium perchlorate (AP) powder is often used as oxidizer in propellants of solid fuel rockets (over 60 w.t.% content) [1-3]. High thermal decomposition efficiency of AP is desirable for getting powerful impetus for rockets. The thermal decomposition of AP was mainly divided into low temperature decomposition stage 2

ACCEPTED MANUSCRIPT (LDS) and high temperature decomposition stage (HDS) [4]. In LDS, the main process includes the formation of HClO4 (g) and NH3 (g) [5], while in HDS, HClO4 (g) and NH3 (g) can further react to produce gas mixture, including N2O, NO2, H2O, HCl,

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Cl2 et al [6-8]. Catalysts, mainly including transition metal oxides (TMOs) (Fe2O3 [9, 10], CuO [11], Co3O4 [12], MnO2 [13]), are mandatory for increasing the decomposition efficiency of AP. The catalytic mechanism of TMOs on the thermal

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decomposition of AP is often attributed to their semiconductor properties (degree of p

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or n nature), charge transfer process and electron transfer process [14, 15]. Among these TMOs, CuO is one of the most investigated catalysts [16]. The catalytic performance of CuO on AP decomposition can be improved by using nanoparticles due to their large surface area. For example, Kranthi Chatragadda

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et al [17] used 2 w.t. % CuO nanoparticles to catalyze AP decomposition and decreased AP decomposition temperature from 445 oC to 335 oC.

Zhikun Zhang et al

[18] successfully synthesized the CuO mixture of nano- and microspheres (its

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diameter ranges from sub-100-nm to hundreds of micrometers) and found that the

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decomposition temperature of AP was at 344 oC with 2 w.t. % of CuO used. In many cases, nano structure CuO showed more catalytic decomposition activity than micro CuO. For these nanoscaled particles, however, they might suffer from the aggregation problem, which prevents part of active sites from interacting with AP thus leading to decreased catalytic activity [19, 20]. In order to overcome such disadvantages, the nanoparticles CuO are often loaded onto inert supports to isolate the nanoparticles from each other. For instance, CuO nanoparticles were successfully loaded onto 3

ACCEPTED MANUSCRIPT graphene and they could catalyze AP decomposition at 321oC, which was lower than that of unsupported CuO nanoparticles [21]. Moreover, constructing a micro-nano structured catalyst, which contains micron-sized particles composed of self-assembled

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nanoparticles, is considered as an alternative effective approach to achieve a capable catalyst.

Besides nanoparticles, the structure modification of CuO is an another effective

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way to improve their catalytic performance in AP decomposition, such as hollow or

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porous structure. These structures play the critical role in providing large surface area and uptaking gases thus leading to second catalytic effect [12, 22, 23]. Jimin Yang[24] found that the hollow porous NiO-ZnO composite showed excellent catalytic activities for the decomposition of AP. Yin et al [25] prepared peanut shaped hollow

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CuO, which was effective for decreasing AP decomposition temperature. Given these contributions, CuO with not only hollow but also mesoporous structure should be an another better catalyst for AP decomposition. Although the

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CuO with both hollow and mesoporous structures are not rare [26, 27], their

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application in AP decomposition has not been investigated. In this study, therefore, hollow and mesoporous nano-assembled CuO microspheres have been in-situ constructed by a hard-template approach and their structure properties and catalytic performance in AP decomposition were comprehensively investigated by XRD, FTIR, SEM, XPS, TG/DSC and TG/FT-IR methods. Compared with CuO nanoparticles and microspheres obtained from traditional precipitating method under alkaline conditions, hollow mesoporous CuO microspheres displayed superior catalytic activity in 4

ACCEPTED MANUSCRIPT catalyzing AP decomposition. 2. Experiment 2.1. Catalysts preparation

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The hollow mesoporous CuO microspheres denoted as CuO-HM were prepared by using carbon spheres as the hard-template. The carbon spheres were firstly prepared by hydrothermally treating 1.2 g cellulose (AR grate, Aladdin) in 20 mL

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de-ionized water at 160 oC for 12 h. Carbon spheres with the diameter of 1 µm were

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obtained after being washed with distilled water and ethanol for 5 times and dried in a vacuum oven at 60 oC overnight (Fig. S1a). The hollow mesoporous CuO spheres were prepared by adding 0.1 g carbon spheres and 0.2 g cellulose into Cu(NO3)2 (AR grate, Aladdin) solution with stirring for 2 h at room temperature followed by

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hydrothermal treatment at 160 oC in an oven for 16 h. The final product was obtained upon washing, drying and calcining (600 oC, 5 oC/min in air) [28]. The CuO nanoparticles denoted as CuO-N were prepared as following: 0.32 g

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Cu(NO3)2•3H2O and 0.15 mL NH3•H2O (25-28 w.t. %, Sinopharm) were added into

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20 mL of de-ionized water/ethanol (v/v=1:1) with stirring for 2 h at room temperature followed by hydrothermal treatment at 100 oC in an oven for 16 h. The precipitations were separated by centrifuge and then washed by water and ethanol for 5 times. After drying in a vacuum oven at 60 oC for 12 h, CuO-N powders were obtained. The CuO micro particles denoted by CuO-M were obtained by using more ammonia aqueous solution (0.45 mL). 2.2. Catalytic performance test 5

ACCEPTED MANUSCRIPT The catalytic performance and by-products analysis in decomposition of AP with the obtained CuO were investigated by TG/DSC and TG/FT-IR under the same conditions, respectively. Typically, AP (AR grade, ~100 µm, Dalian Gaojia Chemical)

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or/and aluminum (Al, Guangzhou Jiechuang Technology co., Ltd.) were mixed with different catalysts in cyclohexane solvent and stirred for 6 h. After the solvent was evaporated by a rotary evaporator, 5 mg of the mixture of AP and CuO catalyst was

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separately analyzed by TG/DSC (Netsch STA449F3) and TG/FTIR (Netsch

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STA449F3 couplet with Bruker TENSOR27 spectrometer) with conditions that heating from room temperature to 600 oC with the rate of 10 oC min-1 in N2 atmosphere. 2.3. Catalyst characterization

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Fourier Transform Infrared spectroscopy (FTIR) was recorded in Thermo fisher Nicolet iS8facilities with the range of 400-4000 cm-1. Powder X-ray diffraction (XRD) patterns were performed with a Bruker Advance D8 instrument equipped with CuKα

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radiation. Scanning electron microscope (SEM) images were collected by Hitachi

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SU8000 to characterize the morphologies and element distribution of the samples. Energy-dispersive spectrometer (EDS) combined with SEM (Rili SU 8000HSD) were used for analyzing element content and distribution. Tri Star II 3020 surface Analyzer was used to determine the specific surface area (BET) of the simple by nitrogen adsorption. X-ray photoelectron spectroscopy (XPS) measurement was performed with ESCALAB 250Xi to estimate the valence state of elements. 3. Results and discussion 6

ACCEPTED MANUSCRIPT 3.1. Structure properties of CuO catalysts Pure CuO phase was obtained in all samples as confirmed by XRD patterns (Fig. 1a) [29]. The templates in CuO-HM, including cellulose or carbon nanoparticles, were

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completely removed through calcining samples at 600 oC in air, which could be confirmed from FTIR spectra where no cellulose or carbon nanoparticles characteristic peaks showed up (Fig. S2) [30]. What’s more, pure CuO generated was

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also verified by the TG/DSC carves (Fig. S3) that all the carbon spheres have been

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burned out before 550 oC. The surface Cu species in all samples was shown in XPS spectra where typical peaks of Cu 2p1/2 at 954.17 eV and Cu 2p3/2 at 934.17 eV with respective satellite peaks located at 962.17 and 942.17 eV were attributed to Cu2+ (Fig. 1b) [31]. The sample surface elemental analysis of XPS and SEM/EDS (Fig. S4) and

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the specific atomic content of Cu and O element in CuO-M, CuO-H and CuO-HM were listed in Table 1. The obtained results showed that atomic concentration ratio of

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copper and oxygen were ~1:1, which further confirmed pure CuO formation.

Fig.1. XRD patterns (a) and XPS spectra of Cu (b) of prepared CuO samples. 7

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Table 1 The specific atomic content of Cu and O elements in prepared samples. Cu element

O element

(atomic content %)

(atomic content %)

EDS analysis

XPS analysis

EDS analysis

CuO-M

49.3

49.5

50.7

50.5

CuO-H

50.1

49.8

49.9

CuO-HM

49.6

49.7

50.4

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XPS analysis

50.2

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50.3

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CuO-N prepared with less amount of NH3•H2O consisted of irregular nanoparticles with size of 200-400 nm (Fig. 2a-b), whereas CuO-M with excess amount of NH3•H2O was composed of spherical particles with size of 4-8 µm (Fig.

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2c-d). When carbon spheres obtained from cellulose under hydrothermal conditions (with the diameter of 1 µm) were utilized as hard-templates, uniform hollow spheres with ~2 µm thickness were successfully achieved (Fig. 2e-l). The hollow mesoporous

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structure of CuO-HM could also be verified by the images of the grinded samples (Fig.

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S5). The formation mechanism of this hollow structure was as follows: the surface of the carbon sphere is hydrophilic due to a large number of OH and C=O groups [28]. During the hydrothermal process, Cu2+ and cellulose in the carbon spheres suspension were adsorbed by the surface of carbon spheres through coordination or electrostatic interactions. After hydrothermal reaction, the obtained sample was the mixture of Cu2+/carbon spheres (~5 µm diameter) and carbon spheres (~1 µm diameter) (Fig. S1b). During the calcination process, the carbon spheres are gradually removed by O2

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microspheres. As shown in Fig.2e-l, the obtained CuO microspheres are ~20 µm and composed of self-assembled nanoparticles with the diameter of 200-600 nm, that is,

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the hollow spheres possess a unique microstructure.

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Fig.2. SEM images of prepared a-b) CuO-N, c-d) CuO-M, c-i) CuO-HM; and

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EDS-mapping of Cu j), O k) and C l) in CuO-HM.

The obtained hollow CuO microspheres was further characterized by nitrogen

adsorption/desorption in order to check if some textural pores were present or not. As shown in Fig. 3, CuO-HM showed typical type IV isotherms, indicating the presence of mesoporous structure. The porous diameter was 2.28 nm by a BJH model (Fig. 3, insert), which further confirmed the mesoporous structure presence [32]. Based on the 9

ACCEPTED MANUSCRIPT preparation procedure, the mesopores might be created during the calcination of carbon spheres, which normally generates abundant CO2 gas as pore-forming agent. The BET surface area of CuO-HM was 68.9 m2/g, which is much larger than that of

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CuO-M (0.2 m2/g) and CuO-N (2.1 m2/g). Thus, hollow and mesoporous CuO

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microspheres were successfully prepared from the hard-template method.

Fig.3. Nitrogen adsorption-desorption isotherms of prepared CuO samples and

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pore size distributions of CuO-HM (insert).

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3.2. Catalytic performance for AP decomposition All of the obtained CuO samples with different morphologies and structures

were applied for catalytic decomposition of AP through TG/DSC test. The lower decomposition temperature and higher heat release indicate the better catalytic performance of CuO [33]. Fig. 4a showed the catalytic performance of CuO samples on AP decomposition. The pure AP decomposition behavior was divided into three stages: 1) the phase transition from the orthorhombic to cubic occurred at 247.4 oC 10

ACCEPTED MANUSCRIPT with an endothermic peak; 2) the low temperature decomposition of AP at 293.4 oC with an exothermic peak and finally 3) the high temperature decomposition of AP at 435.2 oC with an endothermic peak. These three stages were also observed by

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previous research [34]. It has been suggested that the endothermic peak at high temperature resulting from the competition between sublimation (endothermic) and thermal decomposition (exothermic) [35]. The crystallographic transition temperature

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of AP was not affected by the presence of CuO catalysts, however, the AP

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decomposition at high temperature was decreased by 89.7 oC, 81.4oC and 105.7 oC due to CuO-N, CuO-M and CuO-HM catalytic effect, respectively. For the heat produced, CuO-HM could increase the heat produced from 378 J/g (pure AP without catalysts) to 1113 J/g, which was larger than 1028 J/g for CuO-M and 1046 J/g for

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CuO-N. As expected, CuO-HM with hollow and mesoporous structure was superior to nanoparticle CuO-N and microparticle CuO-M in decreasing AP decomposition

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temperature and heat release.

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Fig.4. a) DSC curves for the thermal decomposition of AP with prepared CuO samples (The peaks go up to the endothermic peak and go down to the exothermic

mesoporous CuO.

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peak.) and b) catalysis thermal decomposition mechanism of AP by hollow

The catalytic performance of CuO-HM in this study was also compared with that

of CuO in previous reports to display the superiority of hollow and mesoporous structure. As shown in Table 2, the CuO-HM in this study could catalyze AP decomposition at lower temperature than that of other pure CuO samples with different morphologies and structures, but the heat release was not the highest. The CuO loading on g-C3N4 or graphene was better than CuO-HM in AP decomposition 12

ACCEPTED MANUSCRIPT temperature and heat release due to the synergistic effect between g-C3N4 or graphene and CuO. These comparisons further proved that hollow and mesoporous structures were helpful to increasing the catalytic performance of CuO in AP decomposition.

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Tabel 2 The comparison in catalytic performance of different type of CuO in AP decomposition in terms of decomposition temperature and heat release

Catalyst systems

Mass %

AP decomposition temperature (oC)

Hollow mesoporous CuO

5

329.5, 272.6

1113

This work

CuO nanoparticle

5

345.5

1046

This work

CuO microparticle

5

353.8, 271.5

1028

This work

Spherical CuO

5

386

----

Flower-like CuO

5

362

----

Cross-like CuO

5

352

----

5

351

----

Elliptical-like CuO

5

329

----

Hollow CuO microsphere

2

347

----

[37]

Peanut shaped hollow CuO

2

337

----

[25]

CuO microflowers

2

353.17

1211

[38]

CuO nano/microspheres

2

344

----

[18]

CuO nanoparticles

5

338

----

[17]

CuO nanoparticles

5

341.2

1486.0

[11]

CuO nanocrystals

2

361 to 344

----

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Leaf-like CuO

Heat release (J/g)

Ref.

[36]

[39] Commercial CuO Shuttle-like CuO

4

344

----

2

361

----

13

[40]

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2

369

----

CuO nanosheet

4

335

----

CuO nanosheet

2

349

----

CuO dendrite

2

354

Graphene/CuO

4

321

Graphene/CuO

1.8

325

g-C3N4/CuO

2

319.6

mpg-C3N4/CuO

2

335.1

[41]

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Flower-like CuO nanocrystal

[42]

----

[21]

----

[43]

----

[19]

1664.0

[16]

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1893

For the reason why hollow and mesoporous structure was beneficial to increase the catalytic activity in AP decomposition, we proposed that the higher surface area

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and improved accessibility of the reactants could facilitate more AP interact with catalyst surface, and may accelerate the decomposition reactions by promoting absorption and desorption of gases produced from AP decomposition thus leading to second catalytic effect (Fig. 4b). What’s more, it has been reported the produced

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gaseous products of AP could adsorb on the inner and outer surfaces of the hollow catalysts, which provided more active site and catalytic area for catalytic reaction [23,

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27]. Those results could be further verified by the results that the AP decomposition temperature of the mixtures of hollow mesoporous and nanoparticles (335.6 oC) located between the CuO-HM (329.5 oC) and CuO-N (345.5 oC) (Fig. S6). The hollow mesoporous CuO possess the characterizers of micro-sized spheres composed of self-assembled nanoparticles, which made it with the advantages of nanoparticle but without agglomeration. Notably, the hollow and mesoporous structure of CuO-HM remained unchanged after the catalytic reaction (Fig. S7), indicating that their structure was robust enough to play their role during the catalytic process. The effect of CuO-HM content on AP decomposition was also investigated as 14

ACCEPTED MANUSCRIPT shown in Fig. 5. As expected, the AP decomposition temperature decreased and the produced heat increased with the increase of CuO-HM used. When the content of CuO-HM was over 3 w.t. %, however, the decomposition temperature and heat release

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CuO-HM was 3 w.t.% from economical benefit standpoint.

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only slightly decreased and increased, respectively. Thus, the optimal content of

Fig. 5. a) DSC curves for the thermal decomposition of AP and b) comparisons of decomposition temperature and heat release with different content of CuO-HM

peak.)

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sample. (The peaks go up to the endothermic peak and go down to the exothermic

In the real rocket propellant, Ammonium perchlorate (AP) and Aluminum (Al)

are the two important components because they are used as oxidant and fuel, respectively. In order to evaluate the effect of CuO-HM on thermal decomposition of the real propellant, CuO-HM was used to catalyze the Al/AP based propellant and the results were listed in Fig. 6. The mass ratio of Al:AP was ~18:68 consistent with the 15

ACCEPTED MANUSCRIPT actual proportion of rocket propellant [17]. And the mass ratio of CuO-HM to AP/Al propellant were from 5 % to 25 %. The low temperature decomposition peak (295.6 o

C) and high temperature decomposition peak (378.5 oC) of AP in AP/Al propellant

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were immerged into one peak for all CuO-Al/AP samples (Fig. 6). This could be ascribed to the vast heat release though thermite reaction between CuO and Al that rapidly catalyzed the AP decomposition [44, 45]. With the increase usage of CuO-HM,

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the AP decomposition temperature decreased and heat release increased. The optimum

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content of CuO-HM was 15 w.t.% because the decomposition temperature was

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relative low while the heat release arrived the maximum value.

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Fig. 6. a) DSC curves for the thermal decomposition of Al/AP propellant a and b)

comparisons of decomposition temperature and heat release with different content of CuO-HM sample. (The peaks go up to the endothermic peak and go down to the exothermic peak.)

In order to figure out the difference of decomposition process between pure AP and CuO-HM/AP, TG/FT-IR were employed to determine the decomposed gas products during AP decomposition, and the results were displayed in Fig. 7. The 16

ACCEPTED MANUSCRIPT FT-IR spectra of decomposed gas products at high decomposition temperature were also singled out (Fig. 7b, 7d) and were summarized in Table 3. For the pure AP and CuO-HM/AP, the main gas products are NO, N2O, O2, H2O, HCl and NH3. The

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higher content of CO2 and H2O may result from the external environment because the catalysts could not generate such amount. The ratio of N2O/NO decreased with temperature increasing for pure AP and CuO-HM/AP (Fig. 7a, 7c), indicating N2O

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could be oxidized into NO with further catalyzing the decomposition of AP. There

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was not obvious difference in low temperature decomposition stage. However, at high temperature decomposition stage, CuO-HM/AP showed faster NO producing and shorter temperature gap in NO and N2O generation between low and high temperature decomposition stage when compared with pure AP (Fig. 7a, 7c). These results implied

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that CuO-HM accelerates the thermal decomposition of AP mainly at the high temperature decomposition stage as supposed by adsorption of N2O in hollow mesoporous structure and supply active oxygen atoms to promote the oxidation of

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N2O to produce NO species increasingly [46, 47].

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Fig. 7. a) Real-time FT-IR spectra and b) FT-IR spectra of decomposed gas products at different decomposition temperatures of cure AP; and c) Real-time FT-IR

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spectra and d) FT-IR spectra of decomposed gas products at different decomposition

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temperatures of 5 w.t.% CuO-HM-AP.

Table 3 Summary of decomposed gas products of AP. Gas products [46, 47]

1269, 1313, 2204, 2237

N2O

1559, 1630

NO

1595

O2

2800-2950

HCl

1690, 3000-3400

H2O

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Peaks (cm-1)

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NH3

4. Conclusion

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CuO microspheres with hollow and mesoporous structure (CuO-HM) were successfully prepared by hydrothermal method. The micro-sized CuO spheres were characterized to be composed of self-assembled CuO nanoparticles. The AP

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decomposition at high temperature was decreased by 105.7 oC over CuO-HM catalyst

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and the heat produced could be increased from 378 J/g (pure AP without catalysts) to 1113 J/g, which was larger than 1028 J/g for CuO microspheres and 1046 J/g for CuO nanoparticles. The high surface area, easily accessible mesoporous and micro-nano structure were the origin of its higher catalytic performance in AP decomposition.

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TG/FT-IR results implied that CuO-HM accelerates the thermal decomposition of AP mainly at the high temperature decomposition stage. Notably, the micro-sized spheres could retain their macroscopical morphology during the catalytic procedure, which

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suggests that CuO-HM is a promise and stable catalyst for AP decomposition.

Acknowledgement

This work was supported by the National Natural Science Foundation of China

(Grant No. 21571042, 51603055), Science Foundation of Aerospace (Grant No. 6141B0626020201, 6141B0626020101), the Natural Science Foundation of Heilongjiang Province (Grant No. QC2017055), the China Postdoctoral Science Foundation (Grant No. 2016M601424, 2017T100236), the Postdoctoral Foundation of 19

ACCEPTED MANUSCRIPT Heilongjiang Province (Grant No. LBH-Z16059) and Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University), Ministry of Education.

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Highlights: 1. Hollow mesoporous micro-nano CuO that prepared by using carbon spheres as hard-template was applied in catalyzing ammonium

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perchlorate decomposition. 2. Large surface area and easily accessible porous structure contributes to an improved catalytic activity.

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3. Hollow mesoporous CuO microspheres accelerate the thermal

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decomposition of AP by oxidating N2O to NO species increasingly.