JOURNAL OF CATALYSIS
·
2024
·
IF 6.5
Xilun Zhang,Hongliang Liang,Fei Chang
Catalytic hydrogenation of alkynes to alkenes is pivotal in both petrochemical and fine chemical industries. Its implementation relies on the use of transition metals, especially those precious Pd-based catalysts. In this work, we utilize a melt infiltration method to prepare magnesium oxide-supported potassium hydride (KH/MgO), which is illustrated as a transition-metal-free catalyst for selective hydrogenation of alkynes. H 2 -D 2 exchange experiment proves that dihydrogen activation and dissociation on KH/MgO is plausible at room temperature and ambient pressure. KH/MgO catalyzes hydrogenation of diphenylacetylene (DPA) already at 40 ℃, implying its high intrinsic activity at very mild conditions. Under an optimized condition of 80°C, 2 bar H 2 , and 40 h, 75 % conversion of DPA is achieved, affording 82 % selectivity to stilbenes. Mechanistic study suggests that surface hydride on KH/MgO plays an important role toward dihydrogen activation, and involved in the hydrogenation step to form stilbenes. This work shows the promise for using light metal hydrides consisting of earth-abundant elements as alternative hydrogenation catalysts.
研究领域:
化学
·
催化科学
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产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Hailiang Chu,Chengwang Yin,Yongpeng Xia,Yong Shen Chua,Shujun Qiu,Fen Xu,Lixian Sun
While magnesium hydride (MgH 2 ) is widely acknowledged as an encouraging solid-state hydrogen storage material , its practical utility is hampered by the elevated operating temperatures and sluggish kinetic characteristics. To address these limitations, a composite catalyst consisting of Ni nanoparticles (NPs) deposited onto TiO 2 microspheres (Ni/TiO 2 -MS) was developed and employed as a catalytic agent to enhance the hydrogen desorption and absorption properties of MgH 2 . Remarkably, the introduction of Ni/TiO 2 -MS resulted in a significant reduction of the initial dehydrogenation temperature of MgH 2 to 181.4 °C, demonstrating a decrease of 78.2 °C compared to ball-milled MgH 2 (BM-MgH 2 ). The optimal BM-MgH 2 -Ni/TiO 2 -MS facilitated the desorption of 6.3 wt % of hydrogen within 5 min at 300 °C, while at 150 °C, its dehydrogenated product could absorb 5.4 wt % of hydrogen in only 1 minute. Moreover, the BM-MgH 2 -Ni/TiO 2 -MS sample exhibited remarkable cycling stability over 20 cycles. Through the mechanistic analysis, the simultaneous presence of in-situ formation of Mg 2 Ni/Mg 2 NiH 4 and multivalent titanium species engendered a synergistically catalytic effect, significantly enhancing the hydrogen storage capabilities of MgH 2 . This study affords a very potential strategy for the design of active catalysts aimed at enhancing the hydrogen dehydrogenation/absorption kinetics of MgH 2 .
研究领域:
储能
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纳米材料
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催化
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氢能
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材料科学
✓ 已验证
DOI
高影响因子
Carbon Energy
·
2023
·Vol. 5
·期 7
·e294
·
IF 20.5
Ruisong Li,Daoxiong Wu,Peng Rao,Peilin Deng,Jing Li,Junming Luo,Wei Huang,Qi Chen,Zhenye Kang,Yijun Shen,Xinlong Tian
As a carbon-free energy carrier, hydrogen has become the pivot for future clean energy, while efficient hydrogen production and combustion still require precious metal-based catalysts. Single-atom catalysts (SACs) with high atomic utilization open up a desirable perspective for the scale applications of precious metals, but the general and facile preparation of various precious metal-based SACs remains challenging. Herein, a general movable printing method has been developed to synthesize various precious metal-based SACs, such as Pd, Pt, Rh, Ir, and Ru, and the features of highly dispersed single atoms with nitrogen coordination have been identified by comprehensive characterizations. More importantly, the synthesized Pt- and Ru-based SACs exhibit much higher activities than their corresponding nanoparticle counterparts for hydrogen oxidation reaction and hydrogen evolution reaction (HER). In addition, the Pd-based SAC delivers an excellent activity for photocatalytic hydrogen evolution. Especially for the superior mass activity of Ru-based SACs toward HER, density functional theory calculations confirmed that the adsorption of the hydrogen atom has a significant effect on the spin state and electronic structure of the catalysts.
研究领域:
催化
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材料科学
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能源科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
Inorganics
·
2025
·Vol. 13
·期 3
·74
·
IF 3
Yan Chu,Shiwei Fang,Yingjue Chen,Xiaoqi Zhang,Jie Zheng,Zhenglong Li,Wubin Du,Wengang Cui,Jian Miao,Yaxiong Yang,Yongfeng Liu,Mingxia Gao,Hongge Pan
LiAlH4, characterized by high hydrogen capacity and metastable properties, is regarded as a promising hydrogen source under mild conditions. However, its reversible regeneration from dehydrogenated production is hindered thermodynamically and kinetically. Herein, we demonstrate an active Li–Al–Ti nanocrystalline alloy prepared by melt spinning and cryomilling to enable directly synthesizing nano-LiAlH4. Due to the non-equilibrium preparation methods, the grain/particle size of the alloy was reduced, stress defects were introduced, and the dispersion of the Ti catalyst was promoted. The refined Li–Al–Ti nanocrystalline alloy with abundant defects and uniform catalytic sites demonstrated a high reactivity of the particle surface, thereby enhancing hydrogen absorption and desorption kinetics. Nano-LiAlH4was directly obtained by ball milling a 5% Ti containing Li–Al–Ti nanocrystalline alloy with a grain size of 17.4 nm and Al3Ti catalytic phase distributed under 20 bar hydrogen pressure for 16 h. The obtained LiAlH4exhibited room temperature dehydrogenation performance and good reversibility. This finding provides a potential strategy for the non-solvent synthesis and direct hydrogenation of metastable LiAlH4hydrogen storage materials.
研究领域:
材料科学
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氢能技术
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2017
·
IF 3.582
Honghui Cheng,Kang Li,Xiaolu Fan,Haoran Lou,Yanqi Liu,Qi Qi,Jiamin Zhang,Jingjing Liu,Kai Yan,Yao Zhang
In the present work, two-dimension lamellar Ti 3 C 2 was employed as additive of LiNa 2 AlH 6 . Volumetric dehydrogenation results informed that the onset dehydrogenation temperature of the ball milled LiNa 2 AlH 6 + 5 wt% Ti 3 C 2 sample was lowered by 68 K from that of pristine LiNa 2 AlH 6 . Isothermal pressure-composition (P-C-I) curves and van't Hoff plots demonstrated that the dehydrogenation enthalpy value (61 kJ mol H 2 −1 ) of LiNa 2 AlH 6 + 5 wt% Ti 3 C 2 was significantly reduced from the pristine LiNa 2 AlH 6 (68 kJ mol H 2 −1 ). By means of XPS analyses, it can be revealed that the destabilization of LiNa 2 AlH 6 should be resulted from the involvement of Ti and the yield of unidentified Ti 3+ species. Furthermore, it can be concluded that the lowering of dehydrogenation temperature was merely due to the thermal destabilization of LiNa 2 AlH 6 by Ti 3 C 2 , since Ti 3 C 2 hardly improved the dehydrogenation kinetics of LiNa 2 AlH 6 and reduced its activation energy . However, hydrogenation kinetics was slightly enhanced from the released products of LiNa 2 AlH 6 + 5 wt% Ti 3 C 2 .
研究领域:
材料科学
·
能源储存与转换
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2018
·
IF 3.779
Zan Jiang,Jianguang Yuan,Huanqing Han,Ying Wu
As an important member of complex hydrides , Mg(BH 4 ) 2 has a high gravimetric capacity (14.9 wt%). In this study, the Mg(BH 4 ) 2 was synthesized by the ion exchange method. Afterwards, the Mg(BH 4 ) 2 composites with different amounts (2, 5, 10, 25 and 50 wt%) of carbon nanotubes (CNTs) were prepared by mechanical milling. Effects of the CNTs on the microstructural evolution and hydrogen storage properties were investigated. The onset desorption temperature of the Mg(BH 4 ) 2 -5 wt% CNTs is decreased to lower temperature around 120 °C from 275 °C. The desorption plateau of Mg(BH 4 ) 2 -5 wt% CNTs is the highest, which ascribes that CNTs causes the reaction pathway change. Additionally, the Mg(BH 4 ) 2 -5 wt% CNTs shows the best dehydriding kinetics properties, and can desorb 6.04 wt% hydrogen within 2000 s at 300 °C. The dehydrogenation activation energy of the Mg(BH 4 ) 2 -5 wt% CNTs is decreased to 130.2 kJ/mol H 2 , which is much lower than that of pure Mg(BH 4 ) 2 .
研究领域:
材料科学
·
无机化学
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能源材料
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纳米材料
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固态储氢
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2021
·
IF 5.316
Zi Jun Gao,Zhou Peng Li,Bin Hong Liu
In this work, we synthesized La-incorporated Ni-B amorphous composites and investigated their effects on enhancing dehydrogenation/hydrogenation properties of MgH 2 . MgH 2 with 5 wt% 2La-3Ni-B demonstrated significantly improved dehydriding kinetics. About 6.0 wt% hydrogen could be released within 5 min at 300 °C. Moreover, no decrease in deydrogenation rate was observed within ten cycles. XRD , XPS , SEM and HRTEM examinations revealed that the La incorporation into Ni-B resulted in an amorphous La-B-O structure that could keep its disorder state up to 600 °C. The crystallization and growth of Ni dispersed in the La-B-O structure was significantly retarded. Also the alloying of Mg with Ni or La was not observed. As a result, the added La-Ni-B composites showed higher structural and catalytic stability than Ni-B during hydriding/dehydriding cycling of MgH 2 at high temperatures.
研究领域:
材料科学
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能源存储
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2014
·Vol. 2
·期 22
·8557-8570
·
IF 0
Lina Chong,Jianxin Zou,Xiaoqin Zeng,Wenjiang Ding
In the present work, two new reversible hydrogen storage composites, NaBH4 + LaF3 and NaBH4 + LaH2, have been prepared through a mechanical milling method with the aim of comparatively studying the effects of La fluoride and La hydride on the hydrogen sorption behaviors of NaBH4. Experimental investigations have shown that both La fluoride and La hydride enable reversible hydrogen sorption in NaBH4. In particular, LaF3 exhibits a superior promoting effect than LaH2, which agrees well with theoretical predictions. Surprisingly, better hydrogen sorption properties can be achieved in both systems through undergoing de-/rehydriding cycles. The reversible hydrogen storage capacity reaches up to 3.0 wt% at 238 °C and 2.9 wt% at 326 °C in NaBH4 + LaF3 and NaBH4 + LaH2 systems after the 6th dehydrogenation, respectively. In both cases, the formation of La boride plays the major role in the reversible hydrogen sorption in NaBH4. The superior promoting effect of La fluoride than La hydride upon modifications of thermodynamics and kinetics of NaBH4 should be ascribed to the following factors: (i) the formation of a thermodynamically more stable compound NaF instead of NaH reduces the overall enthalpy changes of re/de-hydriding reactions in NaBH4 + LaF3 to −31.8 kJ mol−1 H2 and 72.5 kJ mol−1 H2, respectively; (ii) the ion exchange of F− for H− leads to the reduction of the onset dehydrogenation temperature of NaBH4 to 160 °C in the NaBH4 + LaF3 composite; (iii) the F− anion favors the formation of LaB6 while H− favors the formation of LaB4. The role of functional anions and cations, de-/rehydrogenation mechanisms and nucleation modes in the two reversible hydrogen storage composites have been proposed based on experimental and theoretical analyses. The comparison study carried out in this work helps to design and search for new metal borohydride based composites for reversible hydrogen storage.
研究领域:
材料科学
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能源存储
✓ 已验证
产品关联
DOI
RSC Advances
·
2021
·Vol. 11
·期 60
·37677-37683
·
IF 3.361
Ying Cheng,Shuhua Zhou,Biqing Shi,Bing Dong,Xianbin Ji,Siqi Li,Wei Zhang
The effect of the solid solution Ce0.8Fe0.1Zr0.1O2, successfully prepared by a hydrothermal synthesis method, on the hydrogen sorption properties of MgH2 is systemically investigated. The Ce0.8Fe0.1Zr0.1O2-modified MgH2 composite exhibits remarkable hydrogen kinetics properties and thermodynamics behavior compared to those of as-milled MgH2, with a reduction in the initial desorption temperature of approximately 82 K. With respect to the hydrogen kinetics, the Ce0.8Fe0.1Zr0.1O2-added sample could uptake approximately 5.3 wt% H2 at 473 K in 2500 s, whereas only 1.5 wt% hydrogen could be absorbed by pristine MgH2 in the same conditions. Furthermore, about 4.5 wt% of hydrogen could be desorbed by Ce0.8Fe0.1Zr0.1O2-doped MgH2 composite at 623 K, which was 2 wt% higher than the as-milled MgH2 sample over the same period of time. The decomposition apparent activation energy for MgH2–Ce0.8Fe0.1Zr0.1O2 is reduced to 84.3 kJ mol−1, which is about 77 kJ mol−1 lower than that of pristine MgH2. It is believed that the notable improvement in the hydrogen sorption kinetics is due to the in situ-formed active species of CeH2.51 and MgO as well as the abundant oxygen vacancies, which play a vital role in catalyzing the hydrogen sorption performance of MgH2.
研究领域:
材料科学
·
能源储存与转换
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Progress in Natural Science-Materials International
·
2022
·
IF 4.269
Yaobin Han,Chaoling Wu,Qian Wang,Derui Sun,Wenyu Cheng,Xiangyang Li,Yuchi Zhang,Xingzhong Cao,Yigang Yan,Yao Wang,Yungui Chen
The V 72 Ti 18 Cr 10 alloy was prepared by a co-precipitation-reduction method in order to consume less energy during whole-life alloy manufacturing, and the phase evolution process in hydrogenation/dehydrogenation process was investigated. The structure refinement analysis of the alloy contented with 1 wt% hydrogen after hydrogenation shows that BCC phase, BCC-hydride phase and FCC phase coexisted, but little BCT phase was found. It indicates that the phase evolution process during hydrogenation was BCC→ BCC-hydride→ FCC, nevertheless the formation of BCT phase was restrained. The limited particle sizes of the alloy in the range of 0.1–5 μm and fewer defects than the normal alloy ingot contributed to the suppression of BCT formation. The annealed alloy, which had similar particle sizes with the unannealed alloy, has less unevenness of the compositions than the unannealed alloy, and the annealed alloy showed flatter plateau in the hydrogenation PCT (pressure-composition-temperature) curves. However, the BCT phase in the annealed alloy appeared in its dehydrogenation process owing to the produced defects during the following dehydrogenation and the hydrogenation process. The alloy with the limited particle sizes even in the range from 0.1 μm to 5 μm could not prevent the generation of BCT phase in the dehydrogenation process.
研究领域:
材料科学
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2021
·Vol. 27
·期 35
·9087-9093
·
IF 5.236
Yongyang Zhu,Hao Zhong,Hui Wang,Liuzhang Ouyang,Jiangwen Liu,Zhenguo Huang,Min Zhu
Graphical A cost-effective way to produce NaBH 4 with high yield by ball milling hydrated borax (Na 2 B 4 O 7 ⋅ 10H 2 O) with cheap Al or Al 88 Si 12 at ambient condition is presented. An effective strategy was developed to facilitate mass transfer during the reaction by introducing NaH to enable the formation of loose NaAlO 2 instead of dense Al 2 O 3 on Al surface, and by using Si as a milling additive that prevents agglomeration and also breaks up passivation layers. A significant obstacle in the large-scale applications of sodium borohydride (NaBH 4 ) for hydrogen storage is its high cost. Herein, we report a new method to synthesize NaBH 4 by ball milling hydrated sodium tetraborate (Na 2 B 4 O 7 ⋅ 10H 2 O) with low-cost Al or Al 88 Si 12 , instead of Na, Mg or Ca. An effective strategy is developed to facilitate mass transfer during the reaction by introducing NaH to enable the formation of NaAlO 2 instead of dense Al 2 O 3 on Al surface, and by using Si as a milling additive to prevent agglomeration and also break up passivation layers. Another advantage of this process is that hydrogen in Na 2 B 4 O 7 ⋅ 10H 2 O serves as a hydrogen source for NaBH 4 generation. Considering the low cost of the starting materials and simplicity in operation, our studies demonstrate the potential of producing NaBH 4 in a more economical way than the commercial process.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
PubMed
高影响因子
BMC PLANT BIOLOGY
·
2022
·Vol. 22
·期 1
·1-14
·
IF 5.26
Cheng Pengfei,Feng Liying,Zhang Shuoyu,Li Longna,Guan Rongzhan,Long Weihua,Xian Zhihui,Zhang Jiefu,Shen Wenbiao
Background Cold stress adversely influences rapeseeds ( Brassica napus L.) growth and yield during winter and spring seasons. Hydrogen (H 2 ) is a potential gasotransmitter that is used to enhance tolerance against abiotic stress, including cold stress. However, convenience and stability are two crucial limiting factors upon the application of H 2 in field agriculture. To explore the application of H 2 in field, here we evaluated the role of ammonia borane (AB), a new candidate for a H 2 donor produced by industrial chemical production, in plant cold tolerance. Results The application with AB could obviously alleviate the inhibition of rapeseed seedling growth and reduce the oxidative damage caused by cold stress. The above physiological process was closely related to the increased antioxidant enzyme system and reestablished redox homeostasis. Importantly, cold stress-triggered endogenous H 2 S biosynthesis was further stimulated by AB addition. The removal or inhibition of H 2 S synthesis significantly abolished plant tolerance against cold stress elicited by AB. Further field experiments demonstrated that the phenotypic and physiological performances of rapeseed plants after challenged with cold stress in the winter and early spring seasons were significantly improved by administration with AB. Particularly, the most studied cold-stress response pathway, the ICE1-CBF-COR transcriptional cascade, was significantly up-regulated either. Conclusion Overall, this study clearly observed the evidence that AB-increased tolerance against cold stress could be suitable for using in field agriculture by stimulation of H 2 S signaling.
研究领域:
植物学
·
农业科学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）