Ruthenium supported on MIL-101 as an efficient catalyst for hydrogen generation from hydrolysis of amine boranes

Cao, Nan; Liu, Teng; Su, Jun; Wu, Xiaojun; Luo, Wei; Cheng, Gongzhen

doi:10.1039/c4nj00739e

Cited by 56 publications

(16 citation statements)

References 25 publications

(14 reference statements)

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“…For catalysis of NaBH 4 , the use of finely divided metal catalysts are often emphasized elsewhere, particularly the use of Pd [29][30][31][32], Pt [33][34][35][36] and Ru [37][38][39][40][41]. However, despite their excellent catalytic efficiencies, the use of those metal catalysts is highly cost prohibitive, which makes their usage for fuel-cells applications highly uneconomical.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Fe-Fe2B catalysts via solvothermal route for hydrogen generation by hydrolysis of NaBH4

Baris¹,

Şimşek²,

Taşkaya³

et al. 2018

Journal of Boron

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In this study, iron sulfate (FeSO 4) and sodium borohydride (NaBH 4) were used to synthesize Fe-Fe 2 B nanocrystals via the solvothermal route. Synthesis of Fe-Fe 2 B nanocrystals was carried out under Argon (Ar) gas atmosphere with aqueous solutions of FeSO 4 .7H 2 O and NaBH 4 at various concentrations and reaction time. The phases and microstructures of nanocrystals thus formed were characterized by X-Ray diffraction (XRD) spectroscopy and scanning electron microscopy (SEM). Surface areas of nanocrystals were measured by a surface area and pore-size analyzer using nitrogen adsorption-desorption method together with Brunauer-Emmett-Teller (BET) equation. The vacuum dried nanoparticles were calcined under both Ar and air at 500 ºC. Nano-cylindrical structures of Fe-Fe 2 B were observed when calcinated under Ar atmosphere; whereas more irregular shaped particles were noticed when calcinated under air. The surface areas of Fe-Fe 2 B were determined as 12 m 2 /g, 5.5 m 2 /g and 16.5 m 2 /g, for vacuum dried, Ar-calcined and O 2-calcined products respectively. The catalytic effect of those nano-particles to generate hydrogen was studied by determining reaction rate of decomposition of NaBH 4 in aqueous alkaline solution. The catalytic activity was investigated by systematic variation of three parameters (1) the amount of Fe-Fe 2 B, (2) the concentration of NaBH 4 and (3) the concentration of NaOH. The effect of temperature on the catalytic activity was also studied separately for the most effective composition by varying the temperature from 25 to 70 °C. It was noticed that the catalytic activity of vacuum dried nanocrystals was the highest. The catalytic activity was found to increase with the increase in NaBH 4 concentration and decrease with the increase in NaOH concentration. The influence of temperature studied with 0.01 g of Fe-Fe 2 B in 1 % w/w NaBH 4 solution showed that the rate of hydrogen generation could be increased almost 5 times more by varying the temperature from 25 °C to 70 °C.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Fe-Fe2B catalysts via solvothermal route for hydrogen generation by hydrolysis of NaBH4

Baris¹,

Şimşek²,

Taşkaya³

et al. 2018

Journal of Boron

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“…Due to the ultrahigh porosity and large surface area [2], together with chemical tunability and structural modifiability [3], the area of MOFs has become one of the fastest growing fields in chemistry [4], such as gas absorption and storage [5,6], energy technologies [7], thin film devices [8], chemical sensors [9], and heterogeneous catalysis [10−12]. The tunable pores of MOFs can be employed to control the growth and hinder the aggregation of metal NPs in confined cavities, that markedly improved the catalytic performance and durability [13]. So far, many different kinds of metal NPs@MOFs catalysts have been studied, such as noble metal Pt@MIL-101 [14], non-noble metal Cu-MOF-74 [15], as well as composites, Rh-Ni@MOF-74(Ni) [16], CuCo@MIL-101 [17] and Pd/CeMIL-101 [18], etc.…”

Section: Introductionmentioning

confidence: 99%

Bimetallic RuM (M=Co, Ni) Alloy NPs Supported on MIL-110(Al): Synergetic Catalysis in Hydrolytic Dehydrogenation of Ammonia Borane

Ning

Zhou

et al. 2018

Chinese Journal of Chemical Physics

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By adjusting various Ru/M (M=Co, Ni) molar ratios, a series of highly dispersed bimetallic RuM alloy nanoparticles (NPs) anchored on MIL-110(Al) have been successfully prepared via a conventional impregnation-reduction method. And they are first used as heterogeneous catalysts for the dehydrogenation reaction of AB at room temperature. The results reveal that the as-prepared Ru 1 Co 1 @MIL-110 and Ru 1 Ni 1 @MIL-110 exhibit the highest catalytic activities in different RuCo and RuNi molar ratios, respectively. It is worthy of note that the turnover frequency (TOF) values of Ru 1 Co 1 @MIL-110 and Ru 1 Ni 1 @MIL-110 catalysts reached 488.1 and 417.1 mol H 2 min −1 (mol Ru) −1 and the activation energies (E a) are 31.7 and 36.0 kJ/mol, respectively. The superior catalytic performance is attributed to the bimetallic synergistic action between Ru and M, uniform distribution of metal NPs as well as bi-functional effect between RuM alloy NPs and MIL-110. Moreover, these catalysts exhibit favorable stability after 5 consecutive cycles for the hydrolysis of AB.

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“…Fe 0.1 @BiVO 4 和五次催化循环后的 Ru 1 Fe 0.1 @BiVO 4 的红外光谱图。从图中可以看出, 在约 730 cm -1 处出现的 BiVO 4 Fe 0.1 @BiVO 4 对 AB 的水解活性, 这种较强的协同作用可能是由于 Ru 和 Fe 之间的电子效应引起的 [26] 。 Ru 和 Fe 的电负性分别为 2.2 和 1.83, 其电负性差值较大, 将产生强的电子效应, 因此, 引入 Fe 对提高不同催化剂对 AB 水解产氢速率图 Fig. 6 Plots of n(H 2 )/n(AB) vs. time from the hydrolysis of AB (18.5 mg) (A) Catalysts with the same nanoparticles loadings; (B) Ru 1 Fe x NPs; (C) Ru 1 Fe x @BiVO 4 ; (D) Catalysts with different supporters Fe x @BiVO 4 比相应的纯 Ru 1 Fe x NPs 的产氢速率都高。随着 x 从 0.05 增大到 0.3, 催化反应速率先增加后降低。这是由于随着另一个是通过两个片段 NH 3 BH 2 -和 OH-的还原消除脱氢而形成羟基中间体 NH 3 BH 2 OH。第三步, 一个 H 2 O 分子进攻金属表面的中间体 NH 3 BH 2 OH, 产生 1 个分子 H 2 并形成中间体 NH 3 BH(OH) 2 ; 随后, 另一个 H 2 O 分子通过相同的机制进攻, 也释放 1 个分子 H 2 并得到中间体 E a 为 43.7 kJmol -1 , 而且转化频率(TOF)为 205.4 mol H 2 mol R u min -1 。从表 2 可以看出, 与其他钌基催化剂相比, 实验制备的催化剂 Ru 1 Fe 0.1 @BiVO 4 对 AB 水解产氢具有较低的 E a 和较高的 TOF 值, 优势显著, 具有潜在的应用价值。为了探究催化剂的催化稳定性, 实验测试了催化剂五次循环性能, 如图 8(C)所示, 催化剂经过五次循环后活性有所降低, 这可能与水解过程中溶液的粘度增加或偏硼酸盐浓度增加有关[29] 。…”

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RuFe Nanoparticles Modified Sheet-like BiVO 4: High-efficient Synergistic Catalyst for Ammonia Borane Hydrolytic Dehydrogenation

Zhang

Wan

et al. 2020

Journal of Inorganic Materials

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Developing highly efficient and low-cost catalysts is crucial in the field of clean energy economy, in which ammonia borane (AB) has attracted great attention due to its high hydrogen production through the catalytic hydrolysis. In this work, BiVO 4 nanosheet was firstly synthesized by a facile reflux method. And then bimetallic RuFe@BiVO 4 catalysts with different molar ratios of Ru/Fe were prepared via in situ impregnation-reduction techniques and their catalytic activities were also tested in the hydrogen generation from aqueous solution of AB at room temperature. Compared with the releasing hydrogen rates of catalysts of BiVO 4 , Ru@BiVO 4 , Fe@BiVO 4 , RuFe NPs and RuFe@BiVO 4 , respectively, Ru 1 Fe 0.1 @BiVO 4 exhibits the highest catalytic activity for the dehydrogenation of AB among all catalysts, the activation energy (E a) and turnover frequency (TOF) are 43.7 kJmol-1 and 205.4 mol H2 mol Ru min-1 , respectively. The addition of non-noble Fe can significantly enhance the catalytic activity of Ru counterparts, which is closely related to the strong electronic effect between Ru and Fe NPs, bi-functional effect generated between the RuFe NPs and the support BiVO 4 .

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Ruthenium supported on MIL-101 as an efficient catalyst for hydrogen generation from hydrolysis of amine boranes

Cited by 56 publications

References 25 publications

Synthesis of Fe-Fe2B catalysts via solvothermal route for hydrogen generation by hydrolysis of NaBH4

Synthesis of Fe-Fe2B catalysts via solvothermal route for hydrogen generation by hydrolysis of NaBH4

Bimetallic RuM (M=Co, Ni) Alloy NPs Supported on MIL-110(Al): Synergetic Catalysis in Hydrolytic Dehydrogenation of Ammonia Borane

RuFe Nanoparticles Modified Sheet-like BiVO 4: High-efficient Synergistic Catalyst for Ammonia Borane Hydrolytic Dehydrogenation

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