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Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water
international journal of hydrogen energy xxx (xxxx) xxx
Available online at www.sciencedirect.com
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Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water Fei Xiao a, Rongjie Yang a,b,*, Jianmin Li a,b a
School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China Key Laboratory of Ministry of Education of High Energy Density Material, Beijing Institute of Technology, Beijing, 100081, China
b
highlights Activated Bi-NPs@GO/Al and Bi-NPs/Al are prepared. Bi-NPs@GO/Al composite shows the better hydrogen generation performance. Graphene oxide can promote the hydrolysis of aluminum.
article info
abstract
Article history:
The bismuth nanoparticles modified graphene oxide composites (Bi-NPs@GO) and bismuth
Received 27 September 2019
nanoparticles (Bi-NPs) were prepared by a hydrothermal method. The activated aluminum/
Received in revised form
bismuth nanoparticles Bi-NPs@GO/Al and Bi-NPs/Al were prepared. Their hydrolysis re-
10 December 2019
action performance were studied. The experimental results show that the composite of
Accepted 16 December 2019
aluminum and Bi-NPs@GO can react rapidly with water. The 4-h milled Bi-NPs@GO/Al
Available online xxx
composite shows better hydrogen generation performance and reacted with tap water even at 0 C. The Bi-NPs@GO/Al composite exhibits high hydrogen generation rate at room
Keywords:
temperature. The enhancement of aluminum hydrolysis in the composite may be due to
Hydrogen generation
that the addition of nano-scale Bi and graphene oxide.
Bismuth nanoparticles
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Graphene oxide Aluminum-water reaction
Introduction Energy has become one of the most important issues in the global energy crisis [1]. Due to its non-polluting combustion products, a wide range of sources, low density and high calorific value, hydrogen is attracting more and more attention [2,3]. Hydrogen has been produced industrially. However,
conventional hydrogen generation methods have problems such as storage and transportation [4,5]. Recently, hydrogen produced by the reaction of aluminum and H2O has received great attention [6e10]. More importantly, the method for preparing hydrogen by aluminum hydrolysis is simple, avoiding various shortcomings of hydrogen transportation [11e13]. 1 g of Al releases 1360 mL of hydrogen by hydrolysis at 298.15 K and 1 atm.
* Corresponding author. School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China. E-mail address: [email protected] (R. Yang). https://doi.org/10.1016/j.ijhydene.2019.12.105 0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved. Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
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However, aluminum cannot react directly with water due to the outer alumina shell of aluminum particles. In recent years, many studies have focused on methods for catalyzing the hydrolysis of aluminum [14e18]. These methods include ball milling, alloying, and gas atomization [19e24]. In addition, the combination of a hydride, a low melting point metal, a metal oxide and a carbon material with an aluminum matrix can improve its hydrolysis performance [25e27]. Although there have been many researches on the hydrolysis reaction of Al materials, most of these materials have a low hydrogen generation rate and cannot meet the demand of the application. In recent years, a large number of studies disclose that the metal Bi can catalyze hydrolysis of aluminum [27e31]. The BieAl alloys or composites can form many micro-galvanic cells during their hydrolysis reaction. Bi acts as the positive electrode of the micro-galvanic cell, and Al acts as the negative electrode of the micro-galvanic cell [32]. However, a large number of literatures only report the influence of micron Bi on the hydrolysis performance of Al. There is no study on the effect of nano Bi on the hydrolysis performance of Al. Meanwhile, researches have shown that the addition of carbon material can promote the hydrolysis performance of aluminum [33e36]. However, the hydrogen generation rate is still unsatisfactory. Graphene oxide (GO) is widely used in various fields due to its good dispersibility in water, large surface area, excellent electrical conductivity and mechanical properties [37e39]. Since the surface of graphene oxide has many carboxyl groups and hydroxyl groups, it has been widely used as a carrier for many nanoparticles [40]. Meanwhile, GO is a good electron acceptor that promotes charge separation and migration [41]. In this article, based on the good electrical conductivity and good water solubility of GO, the spheroidal bismuth modified GO was prepared by hydrothermal method, and the activated aluminum/bismuth nanoparticle modified graphene oxide composites (Bi-NPs@GO/Al) were prepared. Ideally, the excellent electrical conductivity of graphene oxide can promote the hydrolysis reaction of aluminum. Meanwhile, the bismuth nanoparticles can form more micro-galvanic cells with Al. The effect of Bi-NPs@GO on hydrogen generation by AleH2O reaction was studied in detail. For comparison, the hydrolysis performance of the Bi-NPs/Al composite prepared from the synthesized nano-Bi was also investigated.
Experimental Chemicals Graphene oxide (GO) was purchased from Xianfeng Nano Ltd. Aluminum powder (5 mm) was purchased from Hengda Aluminum Industry Co., Ltd. (99.0% purity). Bi(NO3)3$5H2O was purchased from J&K Scientific Ltd. Ethylene glycol was purchased from Tongguang Chemical Company Co., Ltd.
concentration of 1.4 mol/L, and the prepared solution was added to the graphene oxide dispersion solution. The resulting solution was then added into a 250 mL stainless steel autoclave and heated at 150 C for 8 h. After completion of the reaction, the product was filtered and washed three times with deionized water, and finally dried under vacuum at 50 C to obtain a composite Bi-NPs@GO [42]. The composite Bi-NPs was prepared by dissolving 4.5 g of Bi(NO3)3$5H2O in 10 mL of nitric acid, and the solution was added in ethylene glycol. The solution was then heated at 150 C for 8 h and dried under vacuum at 50 C to obtain the Bi-NPs. The composites Bi-NPs@GO/Al and Bi-NPs/Al were prepared by a KQM-D/B planetary ball mill. For the composites Bi-NPs@GO/ Al and Bi-NPs/Al, the mass ratio of aluminum to Bi-NPs@GO or BiNPs in the composite was 9:1. The ball-to-powder ratio of the milling experiment was 10:1 and the milling rotation speed was 800 rpm/min. The ball milling time was set to 4 h. The milling balls and the milling jar were made of stainless steel, and the diameter of the milling balls was 5.1 mm. N-hexane was used as the process control agent in the ball milling process, and there is no inert gas protection during the milling. The hydrolysis properties of the different composites were tested by hydrogen generation experiments. The reaction device was designed by our laboratory [28]. The experiment device consists of a stainless steel tank, heating jacket, gas flow meter, and data acquisition device. The aluminum composite and water were added to the stainless steel tank and the initial water temperature could be controlled by the reactor. In each experiment, aluminum composite (200 mg) was directly added to water (20 mL), and then a hydrogen generation curve was obtained by a gas flow meter (Sevenstar 2000). The gas flow rate of hydrogen is collected by the data acquisition device on a computer. To further study the hydrolysis reaction temperature of these composites, the reaction temperature was recorded using an T450sc infrared thermal detector (FLIR). Briefly, 2 mL of water was added to 500 mg of the aluminum composite, and then the temperature of the aluminum composite was observed by an infrared thermal detector.
Characterization The microstructure of all composites was observed by a FE-SEM S4800 scanning electron microscopy. The surface of the sample was gold-coated to increase its conductivity prior to taking the SEM image. X-ray diffraction was studied by Cu-Ka radiation using an X'Pert PRO MPD Diffractometer with a scan range of 5o-90 . The atom binding energies in different composites were studied by a PHI QUANTERA-II SXM X-ray photoelectron spectroscopy. The TEM images were taken using a Tecnai G2 F30 field emission transmission electron microscope.
Results and discussion Preparation Characterization of Bi-NPs@GO and Bi-NPs Bi-NPs@GO and Bi-NPs were prepared by hydrothermal method. Briefly, 200 mg of graphene oxide was dispersed in 200 mL of ethylene glycol by ultrasonic method. Then, 4.5 g of Bi(NO3)3$5H2O was dissolved in 10 mL of HNO3 with a
Fig. 1 shows the morphologies of the prepared composites BiNPs@GO and Bi-NPs. As shown in Fig. 1(a), the nano-Bi particles are grown on the graphene oxide. It can be seen that the
Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
international journal of hydrogen energy xxx (xxxx) xxx
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Fig. 1 e SEM images of (a) Bi-NPs@GO, (b) Bi-NPs, and (c) magnified images of Bi-NPs. particle size of the nanoparticles is relatively uniform, about 200 nm. The EDS spectrum of the nanoparticles indicates that the nanoparticles contains Bi, C, and O elements. Fig. 1(b and c) are the SEM images of Bi-NPs, which reveals that Bi nanoparticles also exhibit a smooth and regular spherical shape. However, the distribution of nanoparticles is broad and some of the nanoparticles are agglomerated, and the particle size of the nanoparticles is larger than that of Bi-NPs@GO. Fig. 2 shows the TEM images of Bi-NPs@GO. As can be seen from the figure, the prepared nanoparticles have a regular spherical structure and are grown on the surface of graphene oxide. In addition, it can be seen from the enlarged view of the particles that the surface of particles is smooth. Fig. 3 shows the XPS characterization of the composite BiNPs@GO to investigate the chemical states of the elements. The results show the presence of C, O, and Bi elements in the map. Fig. 3(b) shows the spectra of Bi 4f, and the two peaks at 157.4 eV and 162.6 eV are attributed to Bi 4f7/2 and Bi 4f5/2, respectively. The results also reveal that the synthesized nanoparticles are composed of the Bi elements. Meanwhile, Fig. 3(c) exhibits the XPS spectra of C 1s. The C 1s peak can be
ascribed to the CeO peak, CeC peak, and C]O peak of graphene oxide, respectively. The XRD results of the prepared samples Bi-NPs@GO and BiNPs are shown in Fig. 4. All samples show crystallization peaks at 27.1 , 37.9 , 39.6 , 44.5 , and 46.0 , which are the characteristic peaks of Bi (JCPDS file 05e0519). For the sample Bi-NPs@GO, a broad peak at around 25 e30 is the crystalline peak of graphene oxide. According to the EDS spectra and XPS data, it can be inferred that the prepared nanoparticles are nano Bi.
Characterization of Bi-NPs@GO/Al and Bi-NPs/Al Fig. 5 shows the morphologies of the prepared Bi-NPs@GO/Al and Bi-NPs/Al. The particles of the sample Bi-NPs@GO/Al and the sample Bi-NPs/Al exhibit a random morphology, and their particle size increases compared with the original aluminum powder. During the milling process, the milling ball can squeeze the aluminum particles. In addition, the aluminum particles can be cold welded due to the its good ductility, resulting in an increase in particle size. Fig. 6 shows the XRD patterns of the composites Bi-NPs@GO/Al and Bi-NPs/
Fig. 2 e TEM images of Bi-NPs@GO. Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
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Fig. 3 e (a) Survey XPS spectra, (b) spectra of Bi 4f, and (c) spectra of C 1s of Bi-NPs@GO. also indicates that the particle size of the composite particles becomes larger after milling. The smaller median particle size of Bi-NPs@GO/Al may be due to that the addition of graphene can inhibit the cold welding between aluminum particles.
Hydrolysis performance of Bi-NPs@GO/Al and Bi-NPs/Al
Fig. 4 e XRD patterns of the Bi-NPs@GO and Bi-NPs.
Al. The composites Bi-NPs@GO/Al and Bi-NPs/Al both exhibit distinct aluminum characteristic peaks and weak peaks of metal Bi, and aluminum does not form alloys with Bi during ball milling process. For the sample Bi-NPs@GO/Al, no crystallization peak of graphene oxide was observed due to its lower content and poor crystallinity. Fig. 7 is the particle size distribution of Bi-NPs@GO/Al and Bi-NPs/Al. As can be seen from the figure, the particle sizes of both composites show a normal distribution. The median particle sizes of Bi-NPs@GO/ Al and Bi-NPs/Al are 17.3 mm and 22.9 mm, respectively. This
In order to investigate the hydrolysis of Bi-NPs@GO/Al and BiNPs/Al, their hydrogen generation curves were recorded. Fig. 8 is the hydrogen generation curves of these composites in water at 0 C, 10 C, 20 C, and 30 C, respectively. The results show that both Bi-NPs@GO/Al and Bi-NPs/Al can react rapidly with water. The hydrogen generation rate of the samples increases as temperature increases. Meanwhile, the results show that both composites can be completely hydrolyzed even below 0 C. Theoretically, 1 g of the prepared composites can be hydrolyzed to produce 1224 mL of hydrogen. For the sample Bi-NPs@GO/Al, the hydrogen productions per gram of the prepared composite at 0 C, 10 C, 20 C, and 30 C were 940 mL, 966 mL, 961 mL, and 966 mL, respectively. For the sample Bi-NPs/Al, the hydrogen productions per gram of sample at 0 C, 10 C, 20 C, and 30 C were 910 mL, 950 mL, 960 mL, and 950 mL, respectively. From the above results, it can be seen that the initial reaction temperature has little effect on the amount of hydrogen generation of these samples. The hydrogen productions of Bi-NPs@GO/Al and Bi-NPs/ Al are relatively close. The hydrolysis kinetics of Bi-NPs@GO/Al and Bi-NPs/Al composite were investigated. The maximum hydrogen generation rate (MHGR) of the sample Bi-NPs@GO/Al at 0 C, 10 C, 20 C, and 30 C were 3.5 mL s1 g1, 10.5 mL s1 g1,
Fig. 5 e SEM images of (a) Bi-NPs@GO/Al and (b) Bi-NPs/Al. Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
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Fig. 6 e XRD patterns of the Bi-NPs@GO/Al and Bi-NPs/Al.
Fig. 7 e The particle size distribution of Bi-NPs@GO/Al and Bi-NPs/Al.
17.2 mL s1 g1, and 24.5 mL s1 g1, respectively. While for the sample Bi-NPs/Al, the MHGR at 0 C, 10 C, 20 C, and 30 C were 1.3 mL s1 g1, 4.0 mL s1 g1, 12.3 mL s1 g1, and
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27.1 mL s1 g1. The results show that the Bi-NPs@GO/Al composite can react rapidly with water and the hydrolysis reaction rate is higher. From the above results, it can be seen that graphene oxide can indeed increase the hydrolysis rate of active aluminum. In addition, both Bi-NPs@GO/Al and Bi-NPs/ Al exhibit a high hydrogen generation rate, which is higher than the hydrogen generation rate of 1.83 mL s1 g1 of AleBi (micron-sized metal Bi) composite at 20 C reported in our previous work [28]. It is also higher than the fastest hydrogen generation rate of Al-30 wt %Bi-10 wt%C compound (4.5 mL s1 g1 at 60 C) reported by Zhang's group [34]. The hydrogen generation curves of these composites at different temperatures were obtained, and the MHGR at each temperature was calculated. The activation energies of these composites were then calculated by the Arrhenius equation, as shown in Fig. 8(c). The results exhibit that the sample BiNPs@GO/Al has a lower activation energy (32.6 kJ/mol) than that of Bi-NPs/Al (71.1 kJ/mol). The better hydrolysis properties of Bi-NPs@GO/Al composite may be due to the fact that many micro-galvanic cells can be formed between Al and Bi. The nano-Bi particles prepared on the graphene oxide can form more micro-galvanic cells with aluminum than the micron-sized Bi, which can accelerate the hydrolysis reaction of aluminum. Zhang et al. found that after adding graphite to aluminum, the interface between graphite and aluminum could act as a channel for water, which could increase the rate of electrocorrosion reaction. At the same time, the low plasticity of graphite could accelerate the cracking of aluminum particles in the hydrolysis reaction, thereby increasing the hydrolysis reaction rate of aluminum particles [34]. Meanwhile, our previous research found that the carbon materials can be transferred into the aluminum matrix by milling, which helps to form a multilayer structure inside the aluminum particles [28]. Therefore, during the hydrolysis of the aluminum particles, the carbon materials are desorbed from the aluminum matrix, and the new aluminum inside is exposed, so that the contact area of the reaction of aluminum with water is increased. Therefore, it can be deduced that graphene oxide in an aluminum matrix can accelerate the hydrolysis of aluminum by a similar mechanism. Bi-NPs@GO can be transferred into the aluminum matrix by ball milling. During the hydrolysis process, the interface between graphene oxide and aluminum can become a channel for water. At the same time, the
Fig. 8 e Hydrogen generation curves of (a) Bi-NPs@GO/Al and (b) Bi-NPs/Al at different temperatures in water; (c) Arrhenius plot of Bi-NPs@GO/Al and Bi-NPs/Al. Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
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Fig. 9 e Infrared thermal images of (1e8) Bi-NPs@GO/Al and (9e16) Bi-NPs/Al.
graphene oxide will gradually separate from the aluminum matrix along with the reaction process, and the newly exposed spots can accelerate the corrosion of aluminum. In addition, the excellent electrical conductivity of graphene oxide is also beneficial to the galvanic cell reaction between Al and Bi. In order to further study the temperature change during the hydrolysis reaction of the aluminum composite, the surface temperature change of the aluminum composite during the hydrolysis process was recorded by an infrared thermal detector. In the experiment, 2 mL of water was added to 500 mg of the aluminum composite, and then the temperature change of the reaction zone was recorded as shown in Fig. 9. Fig. 10 shows the temperature change in the reaction zone of Bi-NPs@GO/Al and Bi-NPs/Al during their hydrolysis reactions. As can be seen from Fig. 9, point 2 represents the temperature change of the hydrolysis reaction zone. It can be seen that when water is added, the temperatures of the hydrolysis reaction zone of the two samples changes slowly. As time increases, the temperature of the reaction zone gradually increases. When the temperature reaches a certain value, the reaction begins to become intense, and the temperature of the reaction zone rises rapidly. Fig. 10 shows that the temperature rise rate of the reaction zone of the sample Bi-NPs@GO/Al is higher than that of Bi-NPs/Al. The time to reach the maximum temperature is also shorter than that of the sample Bi-NPs/Al. For the sample Bi-NPs@GO/Al, the reaction zone temperature did not change in the early 30 s, and the temperature in the reaction zone begins to increase slowly after 30 s, reaching 54 C at 40 s. The hydrolysis reaction then begins to become
intense, accompanied by a sharp increase in temperature. The temperature of the reaction area reaches the maximum value of 99.2 C at 46 s and then begins to decrease. For the sample Bi-NPs/Al, the reaction progress is similar to the sample BiNPs@GO/Al, while the temperature increasing rate is relatively slow. The temperature of the reaction zone reaches 47.6 C at 66 s, and then the reaction temperature begins to increase intensely, reaching a maximum of 90.8 C at 72 s.
Fig. 10 e Reaction area temperature change of Bi-NPs@GO/ Al and Bi-NPs/Al during their hydrolysis reactions.
Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
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Conclusions The bismuth nanoparticle modified graphene oxide composite (Bi-NPs@GO) and bismuth nanoparticles (Bi-NPs) were prepared by hydrothermal method, and the aluminum composites Bi-NPs@GO/Al and Bi-NPs/Al were prepared. BiNPs@GO/Al and Bi-NPs/Al have good hydrolysis reaction performance and can be hydrolyzed even at 0 C. Due to the synergistic effect of graphene oxide and nano Bi, Bi-NPs@GO/ Al exhibits better hydrogen generation performance. These reactive aluminum composites have the potential to be used in mobile hydrogen sources for fuel cells.
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Available online at www.sciencedirect.com
ScienceDirect journal homepage: www.elsevier.com/locate/he
Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water Fei Xiao a, Rongjie Yang a,b,*, Jianmin Li a,b a
School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China Key Laboratory of Ministry of Education of High Energy Density Material, Beijing Institute of Technology, Beijing, 100081, China
b
highlights Activated Bi-NPs@GO/Al and Bi-NPs/Al are prepared. Bi-NPs@GO/Al composite shows the better hydrogen generation performance. Graphene oxide can promote the hydrolysis of aluminum.
article info
abstract
Article history:
The bismuth nanoparticles modified graphene oxide composites (Bi-NPs@GO) and bismuth
Received 27 September 2019
nanoparticles (Bi-NPs) were prepared by a hydrothermal method. The activated aluminum/
Received in revised form
bismuth nanoparticles Bi-NPs@GO/Al and Bi-NPs/Al were prepared. Their hydrolysis re-
10 December 2019
action performance were studied. The experimental results show that the composite of
Accepted 16 December 2019
aluminum and Bi-NPs@GO can react rapidly with water. The 4-h milled Bi-NPs@GO/Al
Available online xxx
composite shows better hydrogen generation performance and reacted with tap water even at 0 C. The Bi-NPs@GO/Al composite exhibits high hydrogen generation rate at room
Keywords:
temperature. The enhancement of aluminum hydrolysis in the composite may be due to
Hydrogen generation
that the addition of nano-scale Bi and graphene oxide.
Bismuth nanoparticles
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Graphene oxide Aluminum-water reaction
Introduction Energy has become one of the most important issues in the global energy crisis [1]. Due to its non-polluting combustion products, a wide range of sources, low density and high calorific value, hydrogen is attracting more and more attention [2,3]. Hydrogen has been produced industrially. However,
conventional hydrogen generation methods have problems such as storage and transportation [4,5]. Recently, hydrogen produced by the reaction of aluminum and H2O has received great attention [6e10]. More importantly, the method for preparing hydrogen by aluminum hydrolysis is simple, avoiding various shortcomings of hydrogen transportation [11e13]. 1 g of Al releases 1360 mL of hydrogen by hydrolysis at 298.15 K and 1 atm.
* Corresponding author. School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China. E-mail address: [email protected] (R. Yang). https://doi.org/10.1016/j.ijhydene.2019.12.105 0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved. Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
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However, aluminum cannot react directly with water due to the outer alumina shell of aluminum particles. In recent years, many studies have focused on methods for catalyzing the hydrolysis of aluminum [14e18]. These methods include ball milling, alloying, and gas atomization [19e24]. In addition, the combination of a hydride, a low melting point metal, a metal oxide and a carbon material with an aluminum matrix can improve its hydrolysis performance [25e27]. Although there have been many researches on the hydrolysis reaction of Al materials, most of these materials have a low hydrogen generation rate and cannot meet the demand of the application. In recent years, a large number of studies disclose that the metal Bi can catalyze hydrolysis of aluminum [27e31]. The BieAl alloys or composites can form many micro-galvanic cells during their hydrolysis reaction. Bi acts as the positive electrode of the micro-galvanic cell, and Al acts as the negative electrode of the micro-galvanic cell [32]. However, a large number of literatures only report the influence of micron Bi on the hydrolysis performance of Al. There is no study on the effect of nano Bi on the hydrolysis performance of Al. Meanwhile, researches have shown that the addition of carbon material can promote the hydrolysis performance of aluminum [33e36]. However, the hydrogen generation rate is still unsatisfactory. Graphene oxide (GO) is widely used in various fields due to its good dispersibility in water, large surface area, excellent electrical conductivity and mechanical properties [37e39]. Since the surface of graphene oxide has many carboxyl groups and hydroxyl groups, it has been widely used as a carrier for many nanoparticles [40]. Meanwhile, GO is a good electron acceptor that promotes charge separation and migration [41]. In this article, based on the good electrical conductivity and good water solubility of GO, the spheroidal bismuth modified GO was prepared by hydrothermal method, and the activated aluminum/bismuth nanoparticle modified graphene oxide composites (Bi-NPs@GO/Al) were prepared. Ideally, the excellent electrical conductivity of graphene oxide can promote the hydrolysis reaction of aluminum. Meanwhile, the bismuth nanoparticles can form more micro-galvanic cells with Al. The effect of Bi-NPs@GO on hydrogen generation by AleH2O reaction was studied in detail. For comparison, the hydrolysis performance of the Bi-NPs/Al composite prepared from the synthesized nano-Bi was also investigated.
Experimental Chemicals Graphene oxide (GO) was purchased from Xianfeng Nano Ltd. Aluminum powder (5 mm) was purchased from Hengda Aluminum Industry Co., Ltd. (99.0% purity). Bi(NO3)3$5H2O was purchased from J&K Scientific Ltd. Ethylene glycol was purchased from Tongguang Chemical Company Co., Ltd.
concentration of 1.4 mol/L, and the prepared solution was added to the graphene oxide dispersion solution. The resulting solution was then added into a 250 mL stainless steel autoclave and heated at 150 C for 8 h. After completion of the reaction, the product was filtered and washed three times with deionized water, and finally dried under vacuum at 50 C to obtain a composite Bi-NPs@GO [42]. The composite Bi-NPs was prepared by dissolving 4.5 g of Bi(NO3)3$5H2O in 10 mL of nitric acid, and the solution was added in ethylene glycol. The solution was then heated at 150 C for 8 h and dried under vacuum at 50 C to obtain the Bi-NPs. The composites Bi-NPs@GO/Al and Bi-NPs/Al were prepared by a KQM-D/B planetary ball mill. For the composites Bi-NPs@GO/ Al and Bi-NPs/Al, the mass ratio of aluminum to Bi-NPs@GO or BiNPs in the composite was 9:1. The ball-to-powder ratio of the milling experiment was 10:1 and the milling rotation speed was 800 rpm/min. The ball milling time was set to 4 h. The milling balls and the milling jar were made of stainless steel, and the diameter of the milling balls was 5.1 mm. N-hexane was used as the process control agent in the ball milling process, and there is no inert gas protection during the milling. The hydrolysis properties of the different composites were tested by hydrogen generation experiments. The reaction device was designed by our laboratory [28]. The experiment device consists of a stainless steel tank, heating jacket, gas flow meter, and data acquisition device. The aluminum composite and water were added to the stainless steel tank and the initial water temperature could be controlled by the reactor. In each experiment, aluminum composite (200 mg) was directly added to water (20 mL), and then a hydrogen generation curve was obtained by a gas flow meter (Sevenstar 2000). The gas flow rate of hydrogen is collected by the data acquisition device on a computer. To further study the hydrolysis reaction temperature of these composites, the reaction temperature was recorded using an T450sc infrared thermal detector (FLIR). Briefly, 2 mL of water was added to 500 mg of the aluminum composite, and then the temperature of the aluminum composite was observed by an infrared thermal detector.
Characterization The microstructure of all composites was observed by a FE-SEM S4800 scanning electron microscopy. The surface of the sample was gold-coated to increase its conductivity prior to taking the SEM image. X-ray diffraction was studied by Cu-Ka radiation using an X'Pert PRO MPD Diffractometer with a scan range of 5o-90 . The atom binding energies in different composites were studied by a PHI QUANTERA-II SXM X-ray photoelectron spectroscopy. The TEM images were taken using a Tecnai G2 F30 field emission transmission electron microscope.
Results and discussion Preparation Characterization of Bi-NPs@GO and Bi-NPs Bi-NPs@GO and Bi-NPs were prepared by hydrothermal method. Briefly, 200 mg of graphene oxide was dispersed in 200 mL of ethylene glycol by ultrasonic method. Then, 4.5 g of Bi(NO3)3$5H2O was dissolved in 10 mL of HNO3 with a
Fig. 1 shows the morphologies of the prepared composites BiNPs@GO and Bi-NPs. As shown in Fig. 1(a), the nano-Bi particles are grown on the graphene oxide. It can be seen that the
Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
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Fig. 1 e SEM images of (a) Bi-NPs@GO, (b) Bi-NPs, and (c) magnified images of Bi-NPs. particle size of the nanoparticles is relatively uniform, about 200 nm. The EDS spectrum of the nanoparticles indicates that the nanoparticles contains Bi, C, and O elements. Fig. 1(b and c) are the SEM images of Bi-NPs, which reveals that Bi nanoparticles also exhibit a smooth and regular spherical shape. However, the distribution of nanoparticles is broad and some of the nanoparticles are agglomerated, and the particle size of the nanoparticles is larger than that of Bi-NPs@GO. Fig. 2 shows the TEM images of Bi-NPs@GO. As can be seen from the figure, the prepared nanoparticles have a regular spherical structure and are grown on the surface of graphene oxide. In addition, it can be seen from the enlarged view of the particles that the surface of particles is smooth. Fig. 3 shows the XPS characterization of the composite BiNPs@GO to investigate the chemical states of the elements. The results show the presence of C, O, and Bi elements in the map. Fig. 3(b) shows the spectra of Bi 4f, and the two peaks at 157.4 eV and 162.6 eV are attributed to Bi 4f7/2 and Bi 4f5/2, respectively. The results also reveal that the synthesized nanoparticles are composed of the Bi elements. Meanwhile, Fig. 3(c) exhibits the XPS spectra of C 1s. The C 1s peak can be
ascribed to the CeO peak, CeC peak, and C]O peak of graphene oxide, respectively. The XRD results of the prepared samples Bi-NPs@GO and BiNPs are shown in Fig. 4. All samples show crystallization peaks at 27.1 , 37.9 , 39.6 , 44.5 , and 46.0 , which are the characteristic peaks of Bi (JCPDS file 05e0519). For the sample Bi-NPs@GO, a broad peak at around 25 e30 is the crystalline peak of graphene oxide. According to the EDS spectra and XPS data, it can be inferred that the prepared nanoparticles are nano Bi.
Characterization of Bi-NPs@GO/Al and Bi-NPs/Al Fig. 5 shows the morphologies of the prepared Bi-NPs@GO/Al and Bi-NPs/Al. The particles of the sample Bi-NPs@GO/Al and the sample Bi-NPs/Al exhibit a random morphology, and their particle size increases compared with the original aluminum powder. During the milling process, the milling ball can squeeze the aluminum particles. In addition, the aluminum particles can be cold welded due to the its good ductility, resulting in an increase in particle size. Fig. 6 shows the XRD patterns of the composites Bi-NPs@GO/Al and Bi-NPs/
Fig. 2 e TEM images of Bi-NPs@GO. Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
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Fig. 3 e (a) Survey XPS spectra, (b) spectra of Bi 4f, and (c) spectra of C 1s of Bi-NPs@GO. also indicates that the particle size of the composite particles becomes larger after milling. The smaller median particle size of Bi-NPs@GO/Al may be due to that the addition of graphene can inhibit the cold welding between aluminum particles.
Hydrolysis performance of Bi-NPs@GO/Al and Bi-NPs/Al
Fig. 4 e XRD patterns of the Bi-NPs@GO and Bi-NPs.
Al. The composites Bi-NPs@GO/Al and Bi-NPs/Al both exhibit distinct aluminum characteristic peaks and weak peaks of metal Bi, and aluminum does not form alloys with Bi during ball milling process. For the sample Bi-NPs@GO/Al, no crystallization peak of graphene oxide was observed due to its lower content and poor crystallinity. Fig. 7 is the particle size distribution of Bi-NPs@GO/Al and Bi-NPs/Al. As can be seen from the figure, the particle sizes of both composites show a normal distribution. The median particle sizes of Bi-NPs@GO/ Al and Bi-NPs/Al are 17.3 mm and 22.9 mm, respectively. This
In order to investigate the hydrolysis of Bi-NPs@GO/Al and BiNPs/Al, their hydrogen generation curves were recorded. Fig. 8 is the hydrogen generation curves of these composites in water at 0 C, 10 C, 20 C, and 30 C, respectively. The results show that both Bi-NPs@GO/Al and Bi-NPs/Al can react rapidly with water. The hydrogen generation rate of the samples increases as temperature increases. Meanwhile, the results show that both composites can be completely hydrolyzed even below 0 C. Theoretically, 1 g of the prepared composites can be hydrolyzed to produce 1224 mL of hydrogen. For the sample Bi-NPs@GO/Al, the hydrogen productions per gram of the prepared composite at 0 C, 10 C, 20 C, and 30 C were 940 mL, 966 mL, 961 mL, and 966 mL, respectively. For the sample Bi-NPs/Al, the hydrogen productions per gram of sample at 0 C, 10 C, 20 C, and 30 C were 910 mL, 950 mL, 960 mL, and 950 mL, respectively. From the above results, it can be seen that the initial reaction temperature has little effect on the amount of hydrogen generation of these samples. The hydrogen productions of Bi-NPs@GO/Al and Bi-NPs/ Al are relatively close. The hydrolysis kinetics of Bi-NPs@GO/Al and Bi-NPs/Al composite were investigated. The maximum hydrogen generation rate (MHGR) of the sample Bi-NPs@GO/Al at 0 C, 10 C, 20 C, and 30 C were 3.5 mL s1 g1, 10.5 mL s1 g1,
Fig. 5 e SEM images of (a) Bi-NPs@GO/Al and (b) Bi-NPs/Al. Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
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Fig. 6 e XRD patterns of the Bi-NPs@GO/Al and Bi-NPs/Al.
Fig. 7 e The particle size distribution of Bi-NPs@GO/Al and Bi-NPs/Al.
17.2 mL s1 g1, and 24.5 mL s1 g1, respectively. While for the sample Bi-NPs/Al, the MHGR at 0 C, 10 C, 20 C, and 30 C were 1.3 mL s1 g1, 4.0 mL s1 g1, 12.3 mL s1 g1, and
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27.1 mL s1 g1. The results show that the Bi-NPs@GO/Al composite can react rapidly with water and the hydrolysis reaction rate is higher. From the above results, it can be seen that graphene oxide can indeed increase the hydrolysis rate of active aluminum. In addition, both Bi-NPs@GO/Al and Bi-NPs/ Al exhibit a high hydrogen generation rate, which is higher than the hydrogen generation rate of 1.83 mL s1 g1 of AleBi (micron-sized metal Bi) composite at 20 C reported in our previous work [28]. It is also higher than the fastest hydrogen generation rate of Al-30 wt %Bi-10 wt%C compound (4.5 mL s1 g1 at 60 C) reported by Zhang's group [34]. The hydrogen generation curves of these composites at different temperatures were obtained, and the MHGR at each temperature was calculated. The activation energies of these composites were then calculated by the Arrhenius equation, as shown in Fig. 8(c). The results exhibit that the sample BiNPs@GO/Al has a lower activation energy (32.6 kJ/mol) than that of Bi-NPs/Al (71.1 kJ/mol). The better hydrolysis properties of Bi-NPs@GO/Al composite may be due to the fact that many micro-galvanic cells can be formed between Al and Bi. The nano-Bi particles prepared on the graphene oxide can form more micro-galvanic cells with aluminum than the micron-sized Bi, which can accelerate the hydrolysis reaction of aluminum. Zhang et al. found that after adding graphite to aluminum, the interface between graphite and aluminum could act as a channel for water, which could increase the rate of electrocorrosion reaction. At the same time, the low plasticity of graphite could accelerate the cracking of aluminum particles in the hydrolysis reaction, thereby increasing the hydrolysis reaction rate of aluminum particles [34]. Meanwhile, our previous research found that the carbon materials can be transferred into the aluminum matrix by milling, which helps to form a multilayer structure inside the aluminum particles [28]. Therefore, during the hydrolysis of the aluminum particles, the carbon materials are desorbed from the aluminum matrix, and the new aluminum inside is exposed, so that the contact area of the reaction of aluminum with water is increased. Therefore, it can be deduced that graphene oxide in an aluminum matrix can accelerate the hydrolysis of aluminum by a similar mechanism. Bi-NPs@GO can be transferred into the aluminum matrix by ball milling. During the hydrolysis process, the interface between graphene oxide and aluminum can become a channel for water. At the same time, the
Fig. 8 e Hydrogen generation curves of (a) Bi-NPs@GO/Al and (b) Bi-NPs/Al at different temperatures in water; (c) Arrhenius plot of Bi-NPs@GO/Al and Bi-NPs/Al. Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
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Fig. 9 e Infrared thermal images of (1e8) Bi-NPs@GO/Al and (9e16) Bi-NPs/Al.
graphene oxide will gradually separate from the aluminum matrix along with the reaction process, and the newly exposed spots can accelerate the corrosion of aluminum. In addition, the excellent electrical conductivity of graphene oxide is also beneficial to the galvanic cell reaction between Al and Bi. In order to further study the temperature change during the hydrolysis reaction of the aluminum composite, the surface temperature change of the aluminum composite during the hydrolysis process was recorded by an infrared thermal detector. In the experiment, 2 mL of water was added to 500 mg of the aluminum composite, and then the temperature change of the reaction zone was recorded as shown in Fig. 9. Fig. 10 shows the temperature change in the reaction zone of Bi-NPs@GO/Al and Bi-NPs/Al during their hydrolysis reactions. As can be seen from Fig. 9, point 2 represents the temperature change of the hydrolysis reaction zone. It can be seen that when water is added, the temperatures of the hydrolysis reaction zone of the two samples changes slowly. As time increases, the temperature of the reaction zone gradually increases. When the temperature reaches a certain value, the reaction begins to become intense, and the temperature of the reaction zone rises rapidly. Fig. 10 shows that the temperature rise rate of the reaction zone of the sample Bi-NPs@GO/Al is higher than that of Bi-NPs/Al. The time to reach the maximum temperature is also shorter than that of the sample Bi-NPs/Al. For the sample Bi-NPs@GO/Al, the reaction zone temperature did not change in the early 30 s, and the temperature in the reaction zone begins to increase slowly after 30 s, reaching 54 C at 40 s. The hydrolysis reaction then begins to become
intense, accompanied by a sharp increase in temperature. The temperature of the reaction area reaches the maximum value of 99.2 C at 46 s and then begins to decrease. For the sample Bi-NPs/Al, the reaction progress is similar to the sample BiNPs@GO/Al, while the temperature increasing rate is relatively slow. The temperature of the reaction zone reaches 47.6 C at 66 s, and then the reaction temperature begins to increase intensely, reaching a maximum of 90.8 C at 72 s.
Fig. 10 e Reaction area temperature change of Bi-NPs@GO/ Al and Bi-NPs/Al during their hydrolysis reactions.
Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105
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Conclusions The bismuth nanoparticle modified graphene oxide composite (Bi-NPs@GO) and bismuth nanoparticles (Bi-NPs) were prepared by hydrothermal method, and the aluminum composites Bi-NPs@GO/Al and Bi-NPs/Al were prepared. BiNPs@GO/Al and Bi-NPs/Al have good hydrolysis reaction performance and can be hydrolyzed even at 0 C. Due to the synergistic effect of graphene oxide and nano Bi, Bi-NPs@GO/ Al exhibits better hydrogen generation performance. These reactive aluminum composites have the potential to be used in mobile hydrogen sources for fuel cells.
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Please cite this article as: Xiao F et al., Aluminum composites with bismuth nanoparticles and graphene oxide and their application to hydrogen generation in water, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.12.105