Advanced Energy Materials
·
2017
·Vol. 7
·期 19
·1700299
·
IF 16.721
Liuzhang Ouyang,Wei Chen,Jiangwen Liu,Michael Felderhoff,Hui Wang,Min Zhu
Sodium borohydride (NaBH 4 ) is regarded as an excellent hydrogen-generated material, but its irreversibility of hydrolysis and high cost of regeneration restrict its large-scale application. In this study a convenient and economical method for NaBH 4 regeneration is developed for the first time without hydrides used as starting materials for the reduction process. The real hydrolysis by-products (NaBO 2 · 2H 2 O and NaBO 2 · 4H 2 O), instead of dehydrated sodium metaborate (NaBO 2 ), are applied for the regeneration of NaBH 4 with Mg at room temperature and atmospheric pressure. Therefore, the troublesome heat-wasting process to obtain NaBO 2 using a drying procedure at over 350 °C from NaBO 2 · x H 2 O is omitted. Moreover, the highest regeneration yields of NaBH 4 are achieved to date with 68.55% and 64.06% from reaction with NaBO 2 · 2H 2 O and NaBO 2 · 4H 2 O, respectively. The cost of NaBH 4 regeneration shows a 34-fold reduction compared to the previous study that uses MgH 2 as the reduction agent, where H 2 is obtained from a separate process. Furthermore, the regeneration mechanism of NaBH 4 is clarified and the intermediate compound, NaBH 3 (OH), is successfully observed for the first time during the regeneration process.
研究领域:
氢能
·
材料化学
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可持续能源
·
无机合成
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DOI
高影响因子
Journal of Materials Chemistry A
·
2019
·Vol. 7
·期 17
·10723-10728
·
IF 10.733
Hao Zhong,Liuzhang Ouyang,Meiqin Zeng,Jiangwen Liu,Hui Wang,Huaiyu Shao,Michael Felderhoff,Min Zhu
The regeneration of sodium borohydride (NaBH4) is crucial to form a closed cycle after it either supplies hydrogen energy via a hydrolysis process or provides energy through electron transfer at the anode of direct borohydride fuel cells (DBFCs). In both of these cases, the spent fuels are NaB(OH)4 from NaBO2 aqueous solution. However, the current regeneration process from (NaB(OH)4)·xH2O to form NaBH4 by reduction reaction and calcination at high temperature with metal hydrides as reducing agents is very expensive. In this work, we developed a simple regeneration process via ball milling with Mg–Al alloys as the reducing agent for NaB(OH)4 under an argon atmosphere. Under optimized conditions, a high yield of about 72% of NaBH4 could be obtained. Mechanistic study showed that all the hydrogen atoms from NaB(OH)4 remain in NaBH4 and no additional hydrogen sources are needed for the reduction process. The inexpensive Mg–Al alloy works as a reducing agent transforming the H+ to H− in NaBH4. This approach demonstrates a ∼20-fold cost reduction compared with the method using metal hydrides. This opens the door to the commercial implementation of simple ball milling processes for the regeneration of spent NaBH4 from NaB(OH)4 with cheap reducing agents.
研究领域:
化学工程
·
能源材料科学
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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2022
·Vol. 47
·期 84
·35737-35746
·
IF 7.139
Heng Lu,Jianbo Li,Tianyu Xie,Yu'an Chen,Yangfan Lu,Zhongqing Liu,Qian Li,Fusheng Pan
While borohydrides , such as NaBH 4 , were often used as supplements to improve hydrogen storage properties of Mg/MgH 2 systems, they have long suffered from high decomposition temperature and irreversible dehydrogenation process. Here, we report that NaBH 4 can reversibly serve as a hydrogen storage host and reactant for Mg/MgH 2 systems under mild reaction conditions with the help of Al/AlH 3 . 90 wt%MgH 2 –5 wt.%AlH 3 –5 wt.%NaBH 4 (M-5AB) has been successfully synthesized using the conventional mechanical alloying technique. The dehydrogenation activation energy and enthalpy are 20% and 9% reduced than those of pure Mg/MgH 2 . After 10 hydrogen absorption and desorption cycles, the hydrogen storage capacity of M-5AB can reach 6.35 wt%. The X-ray diffraction (XRD) and the transmission electron microscope (TEM) measurements revealed that the interface of additives and Mg/MgH 2 decompose to Mg 17 Al 12 , MgAlB 4 and NaH phases. The Mg 17 Al 12 and MgAlB 4 phases reduces the barrier of free energies of hydrogenated and dehydrogenated states, helping NaBH 4 to recover after rehydrogenation. These discoveries indicate that Al species can boost the decomposition and reformation of NaBH 4 , providing a wider degree of freedom for the material design of Mg-based hydrogen storage materials .
研究领域:
材料科学
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氢气储存
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能源材料
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固态化学
✓ 已验证
DOI
高影响因子
RSC Advances
·
2013
·Vol. 4
·期 5
·2550-2556
·
IF 2.562
Liuting Zhang,Xuezhang Xiao,Xiulin Fan,Shouquan Li,Hongwei Ge,Qidong Wang,Lixin Chen
A simple approach to dramatically enhance the dehydrogenation properties of sodium borohydride is achieved by ball milling NaBH4 with fluorographite (FGi). It was found that the ball-milled NaBH4–FGi composite starts to release hydrogen without impurity gas at a lower temperature of 125 °C, and obtains a hydrogen desorption capacity of ca. 4.8 wt% below 130 °C in seconds, which is improved markedly compared to the ball-milled pristine NaBH4. The significant thermodynamic and kinetic improvement of the NaBH4–FGi composite can be ascribed to the reaction between NaBH4 and FGi as well as the formation of micro-scale NaBH4. Moreover, since the dehydrogenation process of NaBH4–FGi composite is exothermal, the fully reverse reaction is not feasible. In-depth investigations show that the partial rehydrogenation is due to the formation of Na2B12H12 and another new borohydride.
研究领域:
材料科学
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能源化学
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纳米科技
·
物理化学
✓ 已验证
DOI
高影响因子
Cleaner Engineering and Technology
·
2021
·
IF 0
Bang Li,Jia Li,Zhenming Xu
Recovery valuable metals such as lithium and cobalt from spent lithium ion batteries presents great economic significance as well as environmental benefits. The present work explores a mechanochemical reaction of the most widely used cathode materials, LiCoO 2 , into easily separable lithium and nano-sized cobalt species by grinding LiCoO 2 with NaBH 4 . The optimum lithium leaching rate of nearly 100% can be achieved from the sample milled at NaBH 4 to LiCoO 2 mass ratio at 2.5:10 (g/g), milling time for 90 min when Ball-to-powder mass ratio is fixed at 65:1 (g/g), and rotary speed of the planetary ball mill fixed at 400 rpm. The crystal information suggests the grain refinement and chemical transformation of LiCoO 2 . CoO or metallic Co is produced when different NaBH 4 dosage is applied. Whereas lithium is released as soluble LiOH. The results also prove the role of NaBH 4 dosage in determine the reaction path. Microscopic observation confirms the grain refinement during the milling process. Nano-sized cobalt species are also observed. This solid phase mechanochemical reaction provides an effective and short route from waste to potentially high-value added material.
研究领域:
环境科学
·
材料科学
✓ 已验证
DOI
Catalysts
·
2024
·Vol. 15
·期 1
·11
·
IF 3.8
Wen Guo,Chizhong Wang,Lei Qiu,Fanghua Liu,Sizhe Chen,Huazhen Chang
CoFe-based catalysts have shown excellent activity for the oxygen evolution reaction (OER), with the oxidation states of the active sites playing a crucial role in determining catalytic performance. However, how to effectively increase the oxidation state of these active sites remains a key challenge. In this work, a facile treatment with NaBH4solution was employed to modulate the surface state of CoFeOxHycatalysts, inducing an enhanced OER activity. The overpotential at 10 mA cm−2for the NaBH4-treated CoFe catalyst was reduced to 270 mV, indicating improved OER activity. X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) results reveal that NaBH4treatment induced a phase reconstruction of the CoFe oxalate framework, a critical step in enhancing its catalytic properties. The strong reducing ability of NaBH4strengthened the Co-Fe interaction, allowing the retention of low-valence Co species while facilitating the formation of high-valence Fe sites. This dual modulation of Co and Fe oxidation states significantly accelerated charge transfer kinetics, ultimately boosting OER performance. These findings highlight the importance of improving the oxidation states of active sites in CoFe-based catalysts, providing insights for developing efficient catalysts for electrochemical water splitting.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2013
·
IF 3.473
Jie Feng,Li Su,Yanhua Ma,Cuiling Ren,Qing Guo,Xingguo Chen
In this paper, we discovered that CuFe 2 O 4 magnetic nanoparticles (MNPs) possessed high catalytic performance in the reduction of nitrophenol for the first time. The as-prepared CuFe 2 O 4 MNPs exhibited several advantages such as stability, monodispersity, low-cost, simplicity and rapid separation performance over other catalysts for the reduction of nitrophenol. The CuFe 2 O 4 MNPs showed high efficiency in the catalytic reduction of 4-nitrophenol to 4-aminophenol with the conversion of 95% within 40 s in the presence of NaBH 4 . The pseudo-first-order kinetic equation could describe the reduction of 4-nitrophenol with the excess amount of NaBH 4 .
研究领域:
材料科学
·
环境化学
✓ 已验证
产品关联
DOI
高影响因子
SURFACE REVIEW AND LETTERS
·
2019
·
IF 0.748
XIANGRUI MENG,MEIFENG HAO,YIWEI JIANG,XIANGZHENYUE SUN,YAN WANG,YUQING MIAO
A simple wet-explosion method was employed to synthesize the Ni–Bi–P composite microspheres. The hollow structure was obtained possibly due to the violent evolution of gas bubbles when the reaction reagents were mixed. The hollow microspheres of Ni–Bi–P exhibited outstanding high catalytic activity for the reduction of p -nitrophenol ( p -NP) to form p -aminophenol in the presence of NaBH 4 within only 1 s. Due to the space limitation, the hollow structure of Ni–Bi–P microspheres helps to accommodate and confine the molecules of NaBH 4 and p -NP within the small space where NaBH 4 and p -NP contact closely at Ni–Bi–P catalysts. The synergetic action of Ni, Bi and P elements also contributes the enhanced catalytic activity.
研究领域:
材料科学
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环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
CLAYS AND CLAY MINERALS
·
2024
·Vol. 71
·期 6
·745-759
·
IF 2
Peiping Zhang,Tongtong Liu,Xue Sun,Qing Liang,Wei Zhang,Weikun Ning,Wenqing Li,Xuefa Shi,Shiding Miao
Natural clays are often employed as substrates for heterogeneous catalysts. However, the direct use of raw clays as catalysts has received less research attention. The objective of the present study was to help fill this gap by investigating catalytic properties of raw pelagic clays (PC) collected from the Indian Ocean. The raw PC were discovered to be efficient catalysts in the reduction of 4-nitrophenol (4-NP) in the presence of NaBH4. The effects of parameters including pH values, dosages of PC, and initial concentration of 4-NP and NaBH4 on the conversion or degradation rate of 4-NP have been investigated. The 4-NP was observed to be completely degraded within 480 s under conditions of 0.10 mM 4-NP, 25.0 mM NaBH4, and 0.20 g/L PC at an initial pH value of 7.0. The apparent rate constant was evaluated to be 27.53 × 10–3 s–1. Unlike previous pseudo-first order kinetics experiments, the induction period and degradation stages were observed to occur simultaneously during the PC catalysis. The S-shaped kinetics for 4-NP conversion was found to be perfectly matched by Fermi's function, and the enzyme-like catalysis by PC was appointed to describe the kinetics. Species of Fe(III), Mn(IV), and Mn(III) in PC were found to be essential, and were partly reduced to Fe(0) and Mn(II) by NaBH4 in our reaction, contributing to rapid conversion of 4-NP to 4-aminophenol (4-AP). The raw PC was converted to magnetic PC (m-PC) particles, which made PC particles separate easily for cycling use. This discovery would also have applications in continuous flow-fluid catalysis.
研究领域:
环境科学
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催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2021
·
IF 4.539
Jinming Ma,Huizhen Deng,Zhe Zhang,Lexin Zhang,Zhihui Qin,Yaru Zhang,Lili Gao,Tifeng Jiao
In this study, a series of Ag 3 PO 4 /PPy/PANI ternary composite catalysts were fabricated by adjusting the mixed solution of pyrrole and aniline with different volume ratios of 4:1, 3:2, 1:1, 2:3, and 1:4, and combining with the in-situ synthesis method. The synthesized Ag 3 PO 4 /PPy/PANI nanoparticles were examined by XRD , SEM, TEM and EDX , Raman spectroscopy . When the ratio of pyrrole and aniline is 1:1, the polymerized PPy/PANI acted as the supporting matrix to effectively immobilize and prevent the aggregation of Ag 3 PO 4 nanoparticles. The catalytic performances of the Ag 3 PO 4 /PPy/PANI composites were confirmed for reduction of 2-nitroaniline (2-NA) and 4-nitrophenol (4-NP) in the presence of NaBH 4 at room temperature by UV–vis spectroscopy. Results showed that the catalytic reduction effect of the Ag 3 PO 4 /PPy/PANI (1:1) on 2-NA is obviously better than that on 4-NP, which followed the pseudo-first-order kinetic, and the corresponding rate constants are 0.0053 min −1 and 0.022 min −1 , respectively, indicating that it has potential application in wastewater treatment in industries.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2023
·
IF 3.8
Ahmed M. Senan,Muhammed Tilahun Muhammed,Laila A. Al-Shuraym,Sadeq K. Alhag,Niyazi A.S. Al-Areqi,Senem Akkoç
1-Phenyl ethanol derivatives are well-known classes of drug molecules that play an important role as effective substitute analogs to anticancer and antiviral agents. In this work, phenylacetylene was selected as a simple alkyne in the presence of iron (II) phthalocyanine with NaBH 4 as a catalyst. This reaction has been proven that it is a significantly efficient catalyzed conversion of terminal and internal alkynes to 1-phenyl ethanol derivatives as secondary alcohols followed by the addition and elimination mechanism. However, such drug design by compiling the redox reaction and its sequence essentially requires exact stoichiometry of iron phthalocyanine to alkynes. The products were characterized using flash column chromatography with an eluent ratio of PE: EA (5: 1 / V: V), gas chromatography, 1 H, and 13 C NMR spectroscopy. The potential of the synthesized compounds to bind to protein kinase B was investigated through molecular docking to dig out their probable anticancer activity. Compound 7 (1-(4-bromophenyl) ethan-1-ol) exhibited the highest binding potential. However, the binding potential of all the compounds was less than the standard parent compound. In addition, the density functional theory (DFT) studies of the compounds were also applied which revealed that compound 1 might have the highest chemical stability.
研究领域:
药物化学
·
计算化学
·
癌症研究
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2026
·
IF 7.5
Huaxia Zhou,Chenxi Shang,Tayirjan Taylor Isimjan,Xiulin Yang
High-entropy materials, with their multi-element synergistic effects, offer abundant active sites, holding great promise for designing efficient catalysts for sodium borohydride (NaBH 4 ) hydrolysis. Herein, we for the first time synthesize a metal-rich amorphous high-entropy compound Co 3 B‒HEA via a hydrothermal-chemical reduction method, constructing a novel “high-entropy matrix-boride” composite catalytic system. Experimental results demonstrate that Co 3 B‒HEA achieves a maximum hydrogen generation rate (HGR) of 8539.2 mL min −1 g cat −1 at 25 °C. Systematic characterizations reveal three key structural innovations: uniformly distributed multi-metallic active sites, a unique amorphous structure, and strong electronic interactions between Co 3 B and the HEA matrix. Kinetic studies demonstrate zero-order reaction behavior with respect to NaBH 4 concentration and a low activation energy (47.24 kJ mol −1 ), indicating enhanced reaction efficiency. Based on the Michaelis–Menten model, we propose a novel multi-element synergistic activation mechanism: Ru, Co, Fe, Ni, and Mo collectively activate B H 4 - and H 2 O molecules, fundamentally boosting the NaBH 4 hydrolysis rate. Moreover, hydrogen generated from NaBH 4 hydrolysis by the Co 3 B‒HEA catalyst was used directly to drive a custom H 2 -air fuel cell, successfully lighting up small light bulbs and demonstrating its potential for practical applications. This work offers a novel strategy for designing high-performance catalysts for hydrogen production and their practical energy utilization.
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产品关联
DOI
高影响因子
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