JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Zhenji Li,Zhao Zhang,Jun Guo,Hongwei Jia,Wei Zhao,Lijun Lei,Que Huang,Lang Han,Changcheng Liu,Li Guo
MgH₂ is recognized as a promising material for hydrogen production due to its high hydrogen density, abundant availability, and non-polluting hydrolysis by-products, making it a viable hydrogen source for fuel cells. This study, for the first time, investigates the hydrogen production performance of the MgH₂-MOx-NaH (M = Ti, Zr, Mo, Fe, V, Bi) system, which exhibits remarkable hydrolysis properties in aqueous solutions. A series of MgH₂-MOx-NaH composite powders were synthesized via mechanical ball milling. The results revealed that V₂O₅-NaH and Bi₂O₃-NaH significantly enhanced the hydrolysis performance of MgH₂ for hydrogen production. Specifically, Bi₂O₃-NaH and V₂O₅-NaH effectively refined MgH₂ particles and mitigated agglomeration during the milling process. Hydrolysis tests demonstrated that the conversion rate and the hydrogen generation rate (mHGR) of composites initially increased with ball milling time and then decreased. The maximum hydrolysis hydrogen production yield and conversion rate for MgH₂-Bi₂O₃-NaH and MgH₂-V₂O₅-NaH composites occurred at a ball milling duration of 10 hours, and reached up to 1354.1 mL g⁻¹ (88.5 %) and 1273.5 mL g⁻¹ (81.8 %), respectively, within 8 minutes. Kinetic tests of hydrolysis hydrogen production showed that the reaction rate and hydrogen conversion increased with elevated hydrolysis temperatures. The activation energies for the hydrolysis of MgH₂-MOx-NaH (M = Ti, Zr, Mo, Fe, V, Bi) were calculated from the hydrolysis-hydrogen production curves using the Arrhenius formula, yielding values of 41.32, 37.66, 36.40, 34.60, 30.80, and 27.17 kJ mol⁻¹, respectively. The lower activation energies for hydrolysis indicate improved reaction kinetics, suggesting that the incorporation of transition metal oxides and sodium hydride effectively enhances both the hydrolytic conversion and reaction rate of MgH₂.
研究领域:
材料科学
·
能源工程
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2024
·
IF 3.9
Shijie Wang,Shenghan Zhang,Zhenye Zhang,Xinliang Guo,Yu Tan,Kexin Liang,Xijun Wang
Liquid organic hydrogen carrier (LOHC) has been recognized as a highly promising candidate for hydrogen storage materials in addressing hydrogen utilization issues. However, the hydrogenation and dehydrogenation of LOHC typically require noble metal catalysts and harsh reaction conditions. In this paper, we proposed an efficient reversible electrochemical hydrogen storage system based on a nitrogen heterocyclic organic hydrogen carrier, quinoxaline , in which water was used as the solvent and hydrogen source for quinoxaline hydrogenation, and a self-supporting dendritic P-WO 3 /NF electrode was employed as the electrocatalyst. The catalytic properties of P-WO 3 /NF for electrochemical hydrogenation of quinoxaline and dehydrogenation of 1,2,3,4-tetrahydroquinoxaline were studied in 1 M KOH solution under mild conditions. The results showed that the hydrogenation conversion of quinoxaline was 90%, the selectivity was 99%, and the dehydrogenation conversion of 1,2,3,4-tetrahydroquinoxaline was 100%, the selectivity was 100%. This indicates that the system has high conversion efficiency, outstanding selectivity, and good reversibility. Meanwhile, the P-WO 3 /NF electrode adapted to the system exhibited good catalytic stability. In addition, no pre-prepared external hydrogen was required in the electrochemical hydrogenation reaction involving water, which gave the system an excellent safety profile. The reversible electrochemical hydrogen storage system established by this work broadens the vision of LOHC in hydrogen storage applications.
研究领域:
材料科学
·
能源化学
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2022
·
IF 7.139
Haiguang Gao,Rui Shi,Yuting Shao,Yana Liu,Yunfeng Zhu,Jiguang Zhang,Liquan Li
Herein, a novel flower-like Ni MOF with good thermostability is introduced into MgH 2 for the first time, and which demonstrates excellent catalytic activity on improving hydrogen storage performance of MgH 2 . The peak dehydrogenation temperature of MgH 2 -5 wt.% Ni MOF is 78 °C lower than that of pure MgH 2 . Besides, MgH 2 -5 wt.% Ni MOF shows faster de/hydrogenation kinetics, releasing 6.4 wt% hydrogen at 300 °C within 600 s and restoring about 5.7 wt% hydrogen at 150 °C after dehydrogenation. The apparent activation energy for de/hydrogenation reactions are calculated to be 107.8 and 42.8 kJ/mol H 2 respectively, which are much lower than that of MgH 2 doped with other MOFs. In addition, the catalytic mechanism of flower-like Ni MOF is investigated in depth, through XRD , XPS and TEM methods. The high catalytic activity of flower-like Ni MOF can be attributed to the combining effect of in-situ generated Mg 2 Ni/Mg 2 NiH 4 , MgO nanoparticles , amorphous C and remaining layered Ni MOF. This research extends the knowledge of elaborating efficient catalysts via MOFs in hydrogen storage materials.
研究领域:
材料科学
·
能源化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Menghui Wei,Junchao Han,Qikang Wu,Jingjing Li,Zili Ji,Zhi Li,Jia Liang,Yanhui Guo
High water-source adaptability is meaningful to the popularization of hydrolysis of borohydrides as portable hydrogen generation technique. Herein, the key catalyst that can enable high water-sources adaptive hydrolysis of borohydrides is successfully developed for the first time. The as-prepared monolithic CoMoB based catalyst has outstanding catalytic activity with high hydrogen generation rate of the 3.0 L min −1 g −1 at 25 °C and low activation energy of 38.7 kJ mol −1 toward the hydrolysis of NaBH 4 using deionized water. More importantly, the catalyst exhibits distinguished durability toward hydrolysis of borohydrides in various water, including deionized water, lake water, and even seawater benefiting from its unique structure and gas scouring effect. Furthermore, an efficient NaBH 4 -based H 2 supply system is developed with the catalyst and this system successfully achieves full drive of 100 W fuel cell using different sources of water. This study may provide a new protocol to develop portable H 2 generation system with high water source adaptability in wild environments.
研究领域:
材料科学
·
催化化学
·
能源技术
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Huiling Zhang,Jingnan Yang,Teng Zhao,Fujun Lan,Yixin Luo,Fei Han,Xianliang Qiao,Qingxin Guan,Mo Qiu,Wei Li
Directional activation of oxygen-containing groups is a crucial challenge in the catalytic conversion of renewable biomass to high-value products. Herein, we fabricated uniform dispersed NiCo alloy nanoparticles by direct reduction flower-like layer double hydroxides (LDHs) precursors. The as-obtained Ni 2 Co 1 AlO exhibited outstanding yield (97.6 %) of tetrahydrofurfuryl alcohol (THFOL) in furfural hydrogenation, which is significantly superior to those of monometallic Ni-based (75 %) and Co-based (0 %) LDH catalysts and even higher than the most noble metal catalysts. The Ni 2 Co 1 AlO showed robust stability, e.g., the catalyst can be recycled up to 10 times without loss of its conversion and selectivity, which is attributed to the ultra-dispersed metal cations in layers and the confined effect of metal oxides. Characterizations and theoretical calculations demonstrate that alloying Ni with Co can downshift the d -band center of Ni in NiCo alloys, which facilitates the H* desorption to improve hydrogenation activity. The unique electronic interactions between Ni and Co facilitated the parallel adsorption of furfural while reduced the energy barriers of the furan ring hydrogenation, promoting the production of THFOL. This work provides a promising strategy of tailoring d -band center, which can shed light on the design of heterogeneous catalysts.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Xiao-Dong Zhou,Xue-Long Yin,Lang Liu,Xue-Li Huang,Jing-Mei Liu,Ting Liu,He Lin,Feng-Yun Ma
Understanding hydrogen activation is crucial for improving the performance of direct coal liquefaction (DCL) which is essential for the clean, efficient conversion of coal to fuel oils and aromatic chemicals. Three hydrogen sources are involved in DCL: solvent hydrogen (SH), dissolved hydrogen that reacts directly (DHD), and dissolved hydrogen that reacts through a solvent (DHS). Quantitatively studying DHS is challenging because it is generated through the dehydrogenation of hydrogen-donor solvents produced via the hydrogenation of gas-phase H 2 and solvents. This research establishes for the first time a quantitative method for determining DHS consumption (DHSC) based on protium- and deuterium-nuclear-magnetic-resonance results for solvents after isotope-tracer reactions. Comparative experiments and quantum-chemical calculations were performed to confirm the method’s reliability. The isotope-tracer method showed that DHSC accounts for < 7 % of the total hydrogen consumption under catalysis with ferric stearate, nickel stearate, or molybdenum 2-ethylhexanoate, while DHD consumption accounts for > 50 %. Thus, DHD, rather than DHS, is the primary hydrogen source for catalytic activation. Furthermore, the comparative experiments also showed that hydrogen consumption is greater for one hydrogen source than for the coexistence of the three hydrogen sources, indicating competition among the three sources. The quantum-chemical calculations showed that the competitiveness among the three sources follows the order of DHS < SH < DHD, this agrees with the order of hydrogen consumption in the isotope-tracer experiments. This study quantitatively reveals the mechanism responsible for hydrogen activation by catalysts and provides a scientific basis for optimization and mutual matching of solvents and catalysts.
研究领域:
化学工程
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2017
·
IF 3.133
Dandan Peng,Yuan Li,Yang Liu,Lu Zhang,Hongming Zhang,Zhenmin Ding,Shumin Han
In this paper, a magnesium hydride-carbon composite (MgH 2 @CS) was successfully synthesized by hydrogenation, employing magnesium powder and carbonized-starch (CS) as the raw material. The as-prepared MgH 2 @CS was ball-milled with LiBH 4 to constitute a novel Li–Mg–B–H system (2LiBH 4 –MgH 2 @CS). Compared with the primary 2LiBH 4 –MgH 2 , the 2LiBH 4 –MgH 2 @CS composite showed a significant improvement in hydrogen storage performance. Temperature programmed desorption (TPD) analyses show that the 2LiBH 4 –MgH 2 @CS composite starts to slowly release hydrogen at about 150 °C, which is 245 °C lower than that of the pure 2LiBH 4 –MgH 2 ; the final hydrogen desorption capacity reaches 9.3 wt% (LiBH 4 with a weight loss of 7.0 wt%). In particular, the capacity retention rate of 2LiBH 4 –MgH 2 @CS reaches 80.5% after five reversible de/hydrogenation cycles at 400 °C. Microstructure analyses reveal that the CS with lamellar structure could not only serve as a support for anchoring well-dispersed MgH 2 nanoparticles , but could also effectively prevent the aggregation and growth of Mg and magnesium hydrides during de/hydrogenation. Furthermore, the homogeneous nanosized Mg that is generated from decomposition of MgH 2 @CS has high reactivity, which could accelerate the decomposition of LiBH 4 and meanwhile shorten the incubation period of MgB 2 , thereby greatly enhancing the kinetics of dehydrogenation . These studies provide us with fundamental insights into the design of the Li–Mg–B–H system.
研究领域:
材料科学
·
能源储存与转换
✓ 已验证
DOI
高影响因子
RSC Advances
·
2018
·Vol. 8
·期 17
·9211-9217
·
IF 2.936
Ning Zhao,Jianxin Zou,Xiaoqin Zeng,Wenjiang Ding
A new hydrogen storage composite containing NaBH4 and a 3d transition metal fluoride, 3NaBH4/ScF3, was synthesized via ball milling. The composite shows no reaction during milling and its dehydriding process can be divided into three steps upon heating: (i) partial substitution of H− by F− in NaBH4 to form NaBHxF4−x at the early stage, releasing about 0.19 wt% of hydrogen; (ii) formations of Na3ScF6, NaBF4 and ScB2 through the reaction between NaBH4 and ScF3, with 2.52 wt% of hydrogen release and a dehydriding activation energy of 162.67 kJ mol−1 H2; (iii) further reaction of residual NaBH4 and Na3ScF6 to form NaF, B and ScB2, with a dehydriding activation energy of 169.37 kJ mol−1 H2. The total hydrogen release of the composite reaches 5.54 wt% at 530 °C. The complete dehydrided composite cannot be rehydrogenated while the products after the second dehydriding step can be hydrogenated with an absorption activation energy of 44.58 kJ mol−1 H2. These results demonstrate that by adding 3d transition metal fluorides into NaBH4, a partial reversibility in NaBH4 can be achieved.
研究领域:
材料科学
·
氢存储
·
能源材料
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Yuxin Li,Guolang Zhou,Jingzhou Yin,Jianmei Chen,Chao Tang,Cheng Liu,Qiaoqi Li,Tianshi Wang,Feng Li,Chao Yao,Lili Zhang
The production of hydrogen from sodium borohydride (NaBH 4 ) with a suitable catalyst is a promising route for the hydrogen industry. The exploration of the energy-saving catalysts with visible light response and photothermal effect is necessary for utilizing solar energy in hydrogen utilization from hydrolysis of NaBH 4 . In this study, a series of photo-thermal catalysts of Co x FeAl layered double hydroxides (Co x FeAl-LDHs x = 4, 6, 8) with abundant oxygen vacancy (V o ) are successfully synthesized for photo-thermal synergic catalytic H 2 generation from hydrolysis of NaBH 4 . Co x FeAl-LDHs differ in bandgap, V o concentration, and photo-thermal performance, with Co 6 FeAl-LDH show the highest concentration of V o and most efficient photo-thermal performance under 400–700 nm irradiation. Co 6 FeAl-LDH can significantly lower the activation energy of the hydrolysis of NaBH 4 ( E a = 35.46 kJ mol −1 ) and demonstrates excellent photo-thermal synergic performance with H 2 generation rate of 3.38 mol g −1 h −1 without additional heat source. The mechanism study shows that the h + , ∙OH, and V o in Co x FeAl-LDHs also play essential roles in the hydrolysis of NaBH 4 . This work develops a hydrotalcite-based photo-thermal synergistic catalyst, which provides a new approach for the design of sodium borohydride hydrolysis catalysts for hydrogen production.
研究领域:
材料科学
·
催化化学
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2019
·
IF 4.084
Tianping Huang,Jianxin Zou,Xiaoqin Zeng,Jie Wang,Huabing Liu,Wenjiang Ding
In the present work, NaBH 4 based hydrogen storage materials, 3NaBH 4 -(x)YF 3 -(1-x)GdF 3 composites, were prepared via mechanical ball milling with different values of x (2/3, 1/2, 1/3). The de-/rehydrogenation thermodynamic and kinetic behaviors of 3NaBH 4 -(x)YF 3 -(1-x)GdF 3 composites were systematically investigated. These composites showed a single endothermal peak of hydrogen desorption even though two metal fluorides were added simultaneously into NaBH 4 . All the 3NaBH 4 -(x)YF 3 -(1-x)GdF 3 composites showed reversible hydrogen sorption ability and the best hydrogen absorption kinetics was observed in the 3NaBH 4 -0.5YF 3 -0.5GdF 3 composite, with about 2 wt% hydrogen absorbed at 370 °C under 3.2 MPa H 2 pressure in 1 h. Its hydrogen absorption kinetic behaviors were correlated closely to a First-order reaction model based on experimental results. According to the pressure-composition-temperature (PCT) tests, the reversible hydrogen storage capacity increases, and the hydrogen desorption enthalpy decreases along with more GdF 3 addition. In particular, the desorption enthalpy with regard to the apparent Pauling's electronegativity (χ p ) of added metal cations can be described as Δ H d = −2748.21χ p +3852.99 kJ/mol H 2 , where χ p =(x)∙χ p (Y 3+ )+(1-x)∙χ p (Gd 3+ ). This research helps us to clarify the effect of co-addition of two rare earth metal fluorides on reversible hydrogen sorption in NaBH 4 .
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Jibao Zhang,Yan Li,Zhenyuan Yin,Praveen Linga,Tianbiao He,Xiang Yuan Zheng
Hydrogen (H 2 ) emerges as a promising future clean energy for the low-carbon and sustainable future due to its high energy density and no pollutant or greenhouse gas emissions after combustion. The advantage of H 2 storage in solid-hydrate form is the requirement of only moderate pressure and temperature compared to compressed H 2 storage and the relatively lower energy consumption compared to liquid H 2 storage. However, the slow kinetics of H 2 hydrate formation is one major challenge to breakthrough for the large-scale development of hydrate-based H 2 storage. In this study, we introduced an environmental-benign kinetic promoter ( L -valine, L -Val) and coupled it with a thermodynamic promoter tetrahydrofuran (THF) using stoichiometric concentration (5.56 mol%) to enhance H 2 hydrate formation kinetics. 0.3 wt% L -Val coupled with 5.56 mol% THF yields the optimal kinetic enhancement, and the maximum volumetric H 2 uptake ( V H2 ) is 29.83 ± 1.22 volume of H 2 /volume of H 2 -THF hydrate (v /v). The reusability of L -Val is proved in five consecutive cycles of H 2 -THF hydrate formation and dissociation with consistently superior H 2 uptake. Furthermore, it was identified that cooling rate ( R c ) was an important factor determining the H 2 -THF hydrate formation kinetics. Lower R c (0.05 K/min) shows an optimal promoting effect of V H2 , which was 105.29% higher than that at higher R c (0.3 K/min). A mechanism is proposed to explain the effect of R c on H 2 -THF hydrate formation kinetics. The maximum gravimetric H 2 ( G H2 ) reported in our study reaches 0.26 ± 0.01 wt%, which was superior in current literature below 15.0 MPa. The results provide insights into speeding up H 2 uptake in solid-hydrate form and have potential applications in hydrate-based hydrogen storage.
研究领域:
化学工程
·
能源存储
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2023
·
IF 12.9
Yang Hu,Siyu Kuang,Xuerong Zhou,Xiang Li,Sheng Zhang,Roel Prins,Chenxi Zhang,Sensen Shang,Qiang Sheng
A bulk MoP catalyst and a series of MoP catalysts modified by cerium oxide [Ce–MoP(x), where x represents the Ce/Mo molar ratio] were prepared by coprecipitation followed by in situ H2 temperature-programmed reduction. The addition of cerium oxide did not affect the electronic structure of MoP but decreased the MoP particle size and changed the morphology and the coordination state of MoP particles. The MoP catalyst was an aggregate of heterogeneously distributed pebble-like particles, while the Ce–MoP(x) catalysts were a mixture of pebble-like and rod-like particles. MoP only possessed a small amount of acid sites but showed almost no basicity. More acid sites and a large number of weak basic sites were found in Ce–MoP(0.4). The capacity of H2 adsorption on MoP was significantly enhanced by cerium oxide, which is related to their close proximity. We systematically studied the hydrodenitrogenation (HDN) of quinoline, the hydrodesulfurization (HDS) of dibenzothiophene (DBT), the desulfurization of 2-phenylcyclohexanethiol under both H2 and Ar, and the hydrogen evolution reaction (HER) under acidic conditions over these MoP catalysts to gain in-depth insights into the influences of cerium oxide on the catalytic performances of MoP and the correlations among HER and hydrotreating reactions. The introduction of cerium oxide, on the one hand, inhibited the HER and the hydrogen-related reactions over MoP (i.e., the hydrogenation, hydrogenolysis, and dehydrogenation reactions) but, on the other hand, facilitated the elimination reactions that do not need hydrogen. The results suggest that there is a correlation between the HER and the hydrogen-related reactions in the networks of quinoline HDN and DBT HDS. The correlation is discussed by considering the different H2 adsorption behaviors and the different coordination states of the MoP and Ce–MoP(x) catalysts.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）