Nano Research
·
2016
·Vol. 10
·期 2
·595-604
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IF 8.893
Cui Liang,Xu Yuanhong,Niu Li,Yang Wenrong,Liu Jingquan
The issues of hydrogen generation and storage have hindered the widespread use and commercialization of hydrogen fuel cell vehicles. It is thus highly attractive, but the design and development of highly active non-noble-metal catalysts for on-demand hydrogen release from alkaline NaBH 4 solution under mild conditions remains a key challenge. Herein, we describe the use of CoP nanowire array integrated on a Ti mesh (CoP NA/Ti) as a three-dimensional (3D) monolithic catalyst for efficient hydrolytic dehydrogenation of NaBH 4 in basic solutions. The CoP NA/Ti works as an on/off switch for on-demand hydrogen generation at a rate of 6,500 mL/(min·g) and a low activation energy of 41 kJ/mol. It is highly robust for repeated usage after recycling, without sacrificing catalytic performance. Remarkably, this catalyst also performs efficiently for the hydrolysis of NH 3 BH 3 .
研究领域:
材料科学
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催化
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能源存储
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氢燃料电池
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DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2025
·
IF 6.9
Yuyang Cao,Shilong Yang,Pu Liu,Qianqian Zhu,Xiucheng Zheng
The cost-effective RuNi nanoalloys are confined by wheat straw-based carbon (marked as WSC) with the adsorption-NaBH 4 reduction method. WSC with N/O co-doping and a unique micropore-predominant porous structure not only favors the homogeneous and tight dispersion of the RuNi alloys but also improves the hydrophilicity of the resulting catalysts. Furthermore, the different electronegativity induces electron transfer between Ru and Ni, favoring the atomic utilization of noble metal Ru. As a result, the bimetallic catalysts present exciting catalytic activity toward the hydrolysis of ammonia borane (abbreviated as AB, NH 3 BH 3 ). Specially, catalyzed by the optimal Ru 0.50 Ni 0.50 @WSC (10 mg), the hydrogen generation rate (HRG) and turnover frequency (TOF) are separately 59100 mL min −1 g-1 Ru and 254.0 min −1 . In addition, the isotope experiments induce a kinetic isotope effect of 2.84, identifying that the O–H bond cleavage is dominant in this reaction. Noteworthy, the controllable hydrolysis of AB over Ru 0.50 Ni 0.50 @WSC can be easily realized by introducing certain amounts of Zn(NO 3 ) 2 and EDTA-2Na, respectively. This work offers an efficient and relatively low-cost catalyst, as well as deep understanding for the controllable hydrogen release from AB hydrolysis.
研究领域:
材料科学
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催化化学
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DOI
高影响因子
iScience
·
2023
·
IF 5.8
Qing Zhang,Chen Fang,Yanlan Wang,Xiang Liu
Summary In the winter months, the temperature in most of the Earth stays below 0°C; the average temperature in winter at the South Pole is about −60°C. Therefore, it is urgent to develop efficient catalytic systems for selective and efficient H 2 evolution upon NH 3 BH 3 hydrolysis at subzero temperatures. For solving the freezing issue of water at below 0°C, herein, we have employed a facile and surfactant-free approach to synthesize M-Pt/C nanocomposites (M = Pd, Rh, Ru, Ni, Cu, or Fe), by the alloying of commercial Pt/C with Pd, Rh, Ru, Cu, Ni, or Fe for selective and efficient H 2 evolution upon NH 3 BH 3 hydrolysis in saline solution at below 0°C, even at −15°C. In addition, NH 3 BH 3 hydrolysis over Pd-Pt/C in the saturated NaCl solution is utilized not only for safe hydrogen production but also for its in situ hydrogenation reduction in organic chemistry, which could avoid using dangerous hydrogen cylinders.
研究领域:
化学
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材料科学
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能源研究
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DOI
PubMed
高影响因子
ChemCatChem
·
2021
·Vol. 13
·期 19
·4142-4150
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IF 5.686
Jiaxin Liu,Peiyun Li,Renfeng Jiang,Xiucheng Zheng,Pu Liu
Graphical Catalytic Hydrolysis : Ruthenium nanoparticles with different dosages are immobilized on a naturally cationic polysaccharide polymer (chitosan, CS) via an adsorption-in situ reduction method for boosting AB hydrolysis. Catalyzed by the optimal Ru/CS catalysts, the turnover frequency is 338.1 min −1 in alkaline solution at 303 K and the apparent activation energy is 41.3 kJ mol −1 , which are superior to many results reported previously. Developing an advanced heterogeneous catalyst is essential for realizing high-performance ammonia borane (AB) hydrolysis, which is a safe and efficient way to generate hydrogen. In this work, a series of ruthenium (Ru) nanoparticles (NPs) immobilized on chitosan (CS) natural polymers are synthesized via an adsorption-in situ reduction method. Various analytical techniques, including XRD, XPS, FT-IR, SEM and TEM, are adopted to explore the structure-catalytic performance relationships of the obtained catalysts for hydrolysis of AB. Benefitting from the possible interaction between Ru NPs and the amino and hydroxyl groups in CS, the as-prepared catalysts exhibit excellent catalytic behavior for hydrogen generation from AB hydrolysis. Catalyzed by the optimal Ru/CS, the turnover frequency reaches up to 331.8 min −1 in NaOH solution at 303 K, and the corresponding apparent activation energy is 41.3 kJ mol −1 , which are superior to many results previously reported. This work demonstrates that the obtained Ru/CS is a promising and efficient catalyst for the hydrolysis of solid hydrogen storage materials.
研究领域:
材料科学
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催化化学
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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Weifeng Chen,Guo Lv,Jinrun Fu,Haiyan Ren,Jialu Shen,Jie Cao,Xiang Liu
Achieving the controlled release of H2 through an effective approach still faces many challenges. Herein, high-quality graphene quantum dots (GQDs) are synthesized from a new precursor, 1,2,4-trihydroxy benzene, and a multifunctional platform of Rh@GQDs is further developed for the controlled H2 evolution upon the hydrolysis of NH3BH3 (AB). More importantly, the designing concepts of multistep and stepless speed controls have been introduced in the domains of both H2 evolution for the first time. Through a novel designing protocol, the rate of H2 evolution can be freely regulated and constantly varied on demand by means of chelation between Zn2+ and ethylene diamine tetraacetic acid (EDTA). The density functional theory calculation indicates that Zn2+ has the priority to be adsorbed onto Rh(100) due to its larger adsorption energy (107.98 kcal·mol–1) than that of AB (36.36 kcal·mol–1). A controlling mechanism is presented such that Zn2+ will cover the active sites of the nanocatalyst to prevent the H2 evolution, and EDTA can chelate Zn2+ to reactivate the nanocatalyst for the production of H2, greatly facilitating use of this strategy in other catalytic reactions. Moreover, it is demonstrated that the protocol is equally valid for diverse hydrogen storage materials. Therefore, this work not only establishes whole new concepts for the controlled production of H2 but also explains their mechanism, thus remarkably advancing the utilization of H2 energy and significantly enlightening the controlled process of catalysis.
研究领域:
材料科学
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催化化学
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能源科学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2024
·
IF 5.8
Jinjin Wu,Renfeng Jiang,Shinuo Liu,Guangping Zheng,Pu Liu,Xiucheng Zheng
The dehydrogenation of liquid-phase chemical hydrogen storage materials (such as ammonia borane, AB, NH 3 BH 3 ) is a promising strategy to develop the promising hydrogen economy. Considering that the self-hydrolysis of AB is nearly impossible at room temperature, it is very worthwhile to search a robust catalyst for this hydrolytic reaction and clarify the catalytic mechanism. In this work, a glucose-derived N/O co-doped and multi-level porous carbon (marked as g-pC, S BET = 1356 m 2 g −1 , V total = 0.762 cm 3 g −1 , S micro = 1079 m 2 g −1 , V micro = 0.427 cm 3 g −1 ) is prepared for confining RuPd alloys. Benefitting from the positive effect of g-pC (such as the particular anchoring and geometric effects on highly and tightly confining RuPd nanoparticles, as well as enhanced hydrophilicity) and the exceptional metal alloy effect, the obtained bimetallic catalysts unveil drastically enhanced catalytic activity in AB hydrolysis compared to the monometallic counterparts. Especially, catalyzed by the optimal Ru 0.25 Pd 0.75 @g-pC with a mean alloy size of 1.5 nm (10 mg), the dehydrogenation of 1.00 mmol AB can be finished within 1 min at 303 K in NaOH solution (1.5 M). The corresponding turnover frequency and hydrogen generation rate are calculated to be 541.09 min −1 and 145,950 mL min −1 g −1 , respectively. Moreover, about 62% of the initial catalytic activity is still retained even in the 18th cyclic experiment, suggesting the extraordinarily long durability. In addition, the isotopic analyses present a kinetic isotope effect (KIE) of 3.38, further confirming that the scission of an O-H bond in H 2 O is the rate-controlling step in this hydrolytic reaction. Our work offers a competitive metal alloy catalyst for generating hydrogen from AB aqueous solution and promote the development and safety utilization of hydrogen energy.
研究领域:
材料科学
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化学工程
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能源科学
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DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Yuyang Cao,Shilong Yang,Yuting Liu,Xingyu Liu,Yue Li,Xiucheng Zheng,Zhikun Peng,Pu Liu
At present, controllable producing hydrogen from the catalytic hydrolysis of ammonia borane (AB, NH 3 BH 3 ) is very meaningful and challenging. Therefore, developing an effective catalyst for the reaction, clarifying its catalytic mechanism, and realizing controllable hydrogen release are extremely indispensable. In this work, RuPd nanoalloys are evenly confined by the agricultural waste wheat straw-derived carbon (denoted as WSC) with a micropore-dominant porous structure and plentiful N/O doping. Attributing to the particular support effect of WSC and the interesting RuPd alloy effect, the as-prepared bimetallic catalysts provide encouraging catalytic performance in AB hydrolysis. Catalyzed by the optimal Ru 0.50 Pd 0.50 @WSC, the turnover frequency (TOF) and hydrogen evolution rate are 214.5 min −1 and 50800 mL min −1 g −1 , respectively, and the apparent activation energy is only 23.2 kJ mol −1 . Moreover, introducing proper NaOH (1.5 M) further accelerates hydrogen release (TOF = 502.8 min −1 , specific rate = 119100 mL min −1 g −1 ). The isotope experiments depict a kinetic isotope effect of 2.85, evidencing the vital role of the hydrogen–oxygen bond scission in this catalytic reaction. More importantly, benefitting from the difference in adsorption energy and strong coordination ability, the “on–off” control for the hydrolysis of AB over Ru 0.50 Pd 0.50 @WSC can be realized with the Zn 2+ /EDTA 2- system. This study provides an attractive metal alloy catalyst and some insights for the controllable hydrolysis of AB.
研究领域:
化学
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材料科学
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催化反应
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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2018
·
IF 4.229
Hailiang Chu,Nianpu Li,Shujun Qiu,Yongjin Zou,Cuili Xiang,Fen Xu,Lixian Sun
In this paper, ruthenium supported on nitrogen-doped porous carbon (Ru/NPC) catalyst is synthesized by a simple method of in situ reduction using ammonia borane (AB) as reducing agent. The composition and structure of Ru/NPC catalyst are systematically characterized. This catalyst can efficiently catalyze the hydrolysis of AB. The hydrogen production reaction is completed within about 90 s at a temperature of 298 K and the maximum rate of hydrogen production is 3276 ml·s −1 ·g −1 with a reduced activation energy of 24.95 kJ·mol −1 . The turnover frequency (TOF) for hydrogen production is about 813 mol H2 ·mol Ru −1 ·min −1 . Moreover, this catalyst can be recycled with a well-maintained performance. After five cycles, the maximum rate of hydrogen generation is maintained at 2206 ml·s −1 ·g −1 , corresponding to 67.3% of the initial catalytic activity . Our results suggest that Ru/NPC prepared by in situ reduction is a highly efficient catalyst for hydrolytic dehydrogenation of AB.
研究领域:
化学
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材料科学
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能源科学
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产品关联
DOI
高影响因子
RSC Advances
·
2020
·Vol. 10
·期 17
·9996-10005
·
IF 3.119
Xueying Qiu,Jiaxi Liu,Pengru Huang,Shujun Qiu,Chaoming Weng,Hailiang Chu,Yongjin Zou,Cuili Xiang,Fen Xu,Lixian Sun
Ammonia borane (AB, NH3BH3) with extremely high hydrogen content (19.6 wt%) is considered to be one of the most promising chemical hydrides for storing hydrogen. According to the starting materials of AB and H2O, a hydrogen capacity of 7.8 wt% is achieved for the AB hydrolytic dehydrogenation system with the presence of a highly efficient catalyst. In this work, ruthenium nanoparticles supported on magnesium–aluminum layered double hydroxides (Ru/MgAl-LDHs) were successfully synthesized via a simple method, i.e., chemical reduction. The effect of Mg/Al molar ratios in MgAl-LDHs on the catalytic performance for AB hydrolytic dehydrogenation was systematically investigated. Catalyzed by the as-synthesized Ru/Mg1Al1-LDHs catalyst, it took about 130 s at room temperature to complete the hydrolysis reaction of AB, which achieved a rate of hydrogen production of about 740 ml s−1 g−1. Furthermore, a relatively high activity (TOF = 137.1 molH2 molRu−1 min−1), low activation energy (Ea = 30.8 kJ mol−1) and fairly good recyclability of the Ru/Mg1Al1-LDHs catalyst in ten cycles were achieved toward AB hydrolysis for hydrogen generation. More importantly, the mechanism of AB hydrolysis catalyzed by Ru/MgAl-LDHs was simulated via density functional theory. The facile preparation and high catalytic performance of Ru/MgAl-LDHs make it an efficient catalyst for hydrolytic dehydrogenation of AB.
研究领域:
化学
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材料科学
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催化
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Zhenluo Yuan,Fei Ya,Yang Shi,Shuyan Guan,Pingping Wang,Pei Liu,Shiqian Zhao,Qiuming Peng,Yanping Fan,Baozhong Liu
Ru/N-Mo 2 C MXene was assembled by hydrothermal and impregnation reduction process. • The introduction of Ru/N-Mo 2 C MXene accelerates the hydrolysis rate of ammonia borane. • Ru/N-Mo 2 C MXene exhibits a high TOF value of 1092 mol H2 ∙mol Ru −1 ∙min −1 . • Dual active sites of Ru and N-Mo 2 C MXene promotes the hydrogen production for NH 3 BH 3 . Ammonia borane (NH 3 BH 3 , AB) is an ideal hydrogen storage medium, but its intrinsic physicochemical properties require efficient catalysts for rapid hydrolytic dehydrogenation at room temperature. Herein, the Ru nanoparticles anchored nitrogen-doped Mo 2 C MXene (Ru/N-Mo 2 C MXene) catalyst was successfully synthesized via a hydrothermal method combined with an impregnation-reduction strategy, using urea as the nitrogen source. When the mass ratio of Mo 2 C MXene to urea was 1:6, the Ru/N-Mo 2 C MXene catalyst exhibited optimal performance. At 298 K, the turnover frequency value of Ru/N-Mo 2 C MXene was 1092 mol H2 ∙mol Ru −1 ∙min −1 , with an activation energy of 51.74 kJ∙mol −1 , and the catalytic activity remained 86.2% after five cycles. Mechanism analysis indicates that the superior hydrogen production performance of AB is attributed to both the generation of 1.59 nm Ru nanoparticles and the modulated local electronic structure induced by N doping originating from Ru/N-Mo 2 C MXene. These features facilitate the generation of dual active sites (electron-rich Ru and electron-deficient N-Mo 2 C MXene), which efficiently promote the cleavage of B H in AB and O H in H 2 O, thereby significantly boosting the catalytic activity of Ru/N-Mo 2 C MXene for AB hydrogen production. This work establishes a feasible strategy for designing high-efficiency catalysts for ammonia borane hydrolysis.
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DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2022
·
IF 7.139
Kexin Liu,Shilong Yang,Yi Chen,Wenlei Zhang,Pu Liu,Xiucheng Zheng
The hydrolysis of ammonia borane (NH 3 BH 3 , AB) is an efficient strategy for high-purify hydrogen evolution . However, it is indispensable to develop a suitable catalyst because this reaction is kinetically infeasible at room temperature . In this work, we prepared a series of nano hexagonal boron nitride (h-BN) supported CuNi bimetallic catalysts through a facile adsorption-chemical reduction procedure. The effects of various molar ratios of Cu to Ni and CuNi loadings on AB hydrolysis were investigated in details. Benefitting from the proper porous structure , the interesting alloy effect of Cu and Ni, as well as the synergistic effect between h-BN and CuNi, 20 wt% Cu 0.5 Ni 0.5 /h-BN displays the highest catalytic activity among the as-prepared catalysts. Apart from satisfactory durability, the corresponding hydrogen generation rate, turnover frequency at 303 K in base solution and apparent activation energy are 2437.0 mL g −1 min −1 , 6.33 min −1 and 23.02 kJ mol −1 , respectively, which are very outstanding compared with many previous results. Our work not only provides a proper non-precious metal catalyst for hydrogen generation from the hydrolysis of chemical hydrogen storage materials but also offers a facile strategy for synthesizing metallic functional materials .
研究领域:
催化材料
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能源化学
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产品关联
DOI
高影响因子
FUEL
·
2025
·
IF 7.5
Yu-Yang Cao,Yi Xiong,Xiao-Li Zhang,Xin-Xin Guan,Xiu-Cheng Zheng
Developing a convenient and environmental-friendly catalyst preparation method is of great significance, while the catalytic hydrolysis of ammonia borane (NH 3 BH 3 , AB) is an effective in-situ hydrogen production strategy but faces many challenges including the absence of practicable catalysts. In this study, Ru nanoparticles are tightly encapsulated into the framework of chitosan (CS)-derived carbon aerogel (CCA) through a facile ice-crystal template method combined with one-step direct calcination without using any additional chemical activators. The exciting coordination between Ru 3+ and the N/O-based functional groups of CS in aqueous solution, the hierarchical porous structure of CCA and the self-doped N/O favor the tight and high dispersion of Ru NPs, facilitate mass transfer, as well as improve the hydrophilicity of the resulting catalysts. Therefore, the resulting catalysts exhibit excellent activity and durability in the hydrolytic dehydrogenation of AB. Activated by the optimal [email protected] , the turnover frequency (TOF) and hydrogen generation rate (HGR) in the absence of any strong base are separately 136.6 min −1 and 30.3 × 10 3 mL min −1 g Ru −1 , and the apparent activation energy is 42.1 kJ mol −1 . Interestingly, the introduction of NaOH (2.0 M) can further significantly accelerate hydrogen release (TOF = 562.9 min −1 , HGR = 124.7 × 10 3 mL min −1 g Ru −1 ). Additionally, the kinetic isotope effect of 2.82 recommends that an O–H bond dissociation in water acts a dominant role in AB hydrolysis over [email protected] . This work develops a facile and environmentally friendly method for preparing supported metal-based nanocatalysts that can be effectively used in many reactions including AB hydrolysis.
研究领域:
材料化学
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纳米催化
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能源化学
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绿色化学
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氢能源
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）