Nonstoichiometric Yttrium Hydride–Promoted Reversible Hydrogen Storage in a Liquid Organic Hydrogen Carrier

Open AccessCCS ChemistryRESEARCH ARTICLE1 Mar 2021Nonstoichiometric Yttrium Hydride–Promoted Reversible Hydrogen Storage in a Liquid Organic Hydrogen Carrier Yong Wu, Yanru Guo, Hongen Yu, Xiaojing Jiang, Yuxuan Zhang, Yue Qi, Kai Fu, Lei Xie, Guoling Li, Jie Zheng and Xingguo Li Yong Wu Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 , Yanru Guo Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 , Hongen Yu Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 , Xiaojing Jiang Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 , Yuxuan Zhang Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 , Yue Qi Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 , Kai Fu Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 , Lei Xie Sunan Institute for Molecular Engineering, Peking University, Nanjing 215500 , Guoling Li College of Materials Science and Engineering, Qingdao University, Qingdao 266071. , Jie Zheng *Corresponding authors: E-mail Address: email protected E-mail Address: email protected Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 and Xingguo Li *Corresponding authors: E-mail Address: email protected E-mail Address: email protected Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 https://doi.org/10.31635/ccschem.020.202000255 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail N-Ethylcarbazole (NEC) is one of the most promising liquid organic hydrogen carriers (LOHCs), but its application is limited by sluggish kinetics due to lack of high-efficiency, low-cost catalysts. This work reports a cobalt (Co)-based catalyst promoted by nonstoichiometric yttrium hydride (YH3−x) to achieve high-efficiency, reversible hydrogen storage in NEC, with >5.5 wt % reversible hydrogen storage capacity could be achieved below 473 K, and with good kinetics. The YH3−x-promoted Co-based catalyst is the first non-noble metal catalyst with high activity for NEC hydrogenation and 12H-NEC dehydrogenation reactions. A mechanistic study suggests that YH3−x facilitates the reversible hydrogen transfer both in the hydrogenation and the dehydrogenation reactions. The nonstoichiometric YH3−x contained both lattice H and H vacancies with tunable H chemical potential serve as the H donor and H acceptor for reversible hydrogen transfer. Our results support the practical application of LOHCs and inspire new approaches for the utilization of conventional metal hydrides to promote versatile H transfer reactions. Download figure Download PowerPoint Introduction Hydrogen storage and transport are critical enabling technologies that support the widespread application of hydrogen energy. Liquid organic hydrogen carriers (LOHCs) have attracted enormous academic and industrial interest for their promising applications in large scale, long-distance H2 transportation and onboard hydrogen storage due to their high capacity, good reversibility, low cost, highly safe, easy thermal management, and good compatibility with existing gasoline infrastructure.1–7 LOHCs are typically represented in their H lean form. Recently, Benzyltoluene, dibenzyltoluene, biphenyl, diphenylmethane, 2-methylindole, 2-picoline, acridine, and N-ethylcarbazole (NEC) are widely being studied.8–14 Among these LOHCs, NEC and its fully hydrogenated form (dodecahydro-N-ethylcarbazole, 12H-NEC) is one of the most promising LOHC couples due to its high capacity (5.8 wt % and 55 g H2 L−1), moderate operation temperature (dehydrogenation temperature below 473 K), low volatility, and low toxicity.15–20 Almost all the LOHCs, including NEC, suffer from sluggish hydrogenation and dehydrogenation kinetics. Currently, there remains a lack of high-efficiency, low-cost catalysts to achieve efficient hydrogenation and dehydrogenation, which is the major obstacle for the practical application of LOHCs. Moreover, typically, different catalysts are required for NEC hydrogenation and 12H-NEC dehydrogenation. Ruthenium (Ru)-based catalysts show the best hydrogenation performance, while palladium (Pd)-based catalysts exhibit the best dehydrogenation performance.21,22 The requirement of two different catalysts significantly increases the complexity and cost of the system. Undoubtedly, a single non-noble metal catalyst with both hydrogenation and dehydrogenation catalytic performance (two-direction catalyst) is highly desirable for LOHC-based hydrogen storage systems. However, two-direction catalysts for hydrogen storage in NEC are extremely rare. To the best of our knowledge, Pd2email protected was the only reported efficient two-directional catalyst for NEC, which was also based on noble metals.23 There are several non-noble metal, two-direction catalysts for quinoline and its derivatives, including Cu/TiO2,24 single-atom Co catalysts on porous N-doped carbon,25 Ni31Si12/Ni2email protected2,26 email protected,27 and transition metal/carbon dyads.28 However, the gravimetric hydrogen storage capacities of quinoline and its derivatives are too low (99.9%) at 623 K, 4 MPa H2 for 6 h in a Sievert-type reactor and subsequently pulverized by ball milling (Fritsch Pulverisette 5) at 0.4 MPa H2, 250 rpm. The composition was estimated to be YH2.75 based on the hydrogen absorption capacity. YD3−x was prepared by the same method using D2. We prepared the Al2O3-supported cobalt boride (Co-B/Al2O3) catalyst using 100 mg of cetyltrimethylammonium bromide and 47 mg CoCl2·6H2O dissolved in 2.5 mL deionized water with ultrasonication. Then 1.5 mL NaBH4 aqueous solution (0.176 mol L−1) was added until no bubbles were observed, followed by the addition of 220 mg γ-Al2O3 (Beijing Langely Co., Ltd, 99.95%). Subsequently, the mixtures were ultrasonicated for 40 min. The Co-B/Al2O3 was separated by centrifugation (10000 rpm for 10 min) and dried in vacuum at 333 K overnight. Cobalt boride nanoparticles were prepared by the same method but without the addition of Al2O3. The Co/Al2O3 catalyst was obtained by the impregnation reduction method using 94 mg CoCl2·6H2O, 440 mg γ-Al2O3, and 20 mL deionized water. The parameters of the reduction process were programmed, as follows: heating to 393 K (3 K min−1), maintaining at 393 K for 2 h, then heating to 973 K (5 K min−1), and maintaining at 973 K for 2 h (Ar = 70 sccm and H2 = 30 sccm). The Co-B/Al2O3-YH3−x catalyst was obtained by milling 250 mg Co-B/Al2O3 and 250 mg YH3−x in an agate mortar for 5 min in an Ar-filled glove box. The Co-B/Al2O3-YD3−x catalyst was prepared by the same method using YD3−x, and the Co/Al2O3-YH3−x catalyst was prepared by the same method using Co/Al2O3. The prepared catalysts were characterized by powder X-ray diffraction (XRD; PANalytical X'Pert3 Powder, Cu Kα), inductively coupled plasma optical emission spectroscopy (ICP-OES, Prodigy 7, Leeman), X-ray photoelectron spectroscopy (XPS; Axis Ultra, Kratos Analytical Ltd.), field emission high-resolution transmission electron microscope (HRTEM; JEM-2100 F), scanning electron microscopy (SEM; Hitachi S4800), and temperature-programmed desorption (TPD) in Ar flow at temperature ramping rate of 5 K min−1 (Quantachrome Autosorb iQ). Hydrogen storage performance measurement The hydrogen storage performance was measured in an SLM microform high-pressure autoclave (150 mL, Beijing Century Senlang Co., Ltd.) with a high-precision pressure gauge (accuracy 0.01 MPa, L61 K, Hong Kong Huibang Technology Co., Ltd) and a gas flowmeter (50 mL min−1, D07, Beijing Seven Star Flow Co., Ltd.). The setup is illustrated schematically in Supporting Information Figure S1. NEC (1.00 g, Beijing InnoChem Science (b) The hydrogenation and dehydrogenation kinetics on different catalysts; (c) Reversible hydrogen storage in NEC/12H-NEC on the Co-B/Al2O3-YH3−x catalyst. (Hy: hydrogenation; De: Dehydrogenation). Download figure Download PowerPoint Currently, Ru/Al2O3 and Pd/Al2O3 are the best catalysts for NEC hydrogenation and 12H-NEC dehydrogenation, respectively.15,22 Remarkably, the noble-metal-free Co-B/Al2O3-YH3−x catalyst showed a similar hydrogenation and dehydrogenation efficiency when compared with that of the two milestone catalysts (Figure 2b). To the best of our knowledge, Pd2email protected reported by Forberg et al.23 is the only catalyst active for both NEC hydrogenation and 12H-NEC dehydrogenation, which exhibited similar catalytic performance, but their system required much more sophisticated preparation procedure. Indeed, the comparative study displayed in Supporting Information Table S1 shows that almost all the catalysts reported in the literature are noble-metal-based and are only active for either hydrogenation or dehydrogenation reactions.15,23,30,37–42 Favorably, our Co-B/Al2O3-YH3−x catalyst could achieve high catalytic performance for both NEC hydrogenation and 12H-NEC dehydrogenation processes without the use of expensive noble metals. Also, the performances of different catalysts were compared, as shown in Figure 2b, to provide a better understanding of the role of each component of the Co-B/Al2O3-YH3−x catalyst. We observed that Co-B/Al2O3 only showed poor activity for the hydrogenation and dehydrogenation reactions, while YH3−x was completely inactive. Besides, simply blending Co-B with YH3−x also leads to similar activity for hydrogenation and dehydrogenation, but the activity decayed very rapidly due to the agglomeration of Co-B nanoparticles (see Supporting Information Figure S10). Therefore, the catalytic activity originated from the synergism of Co-B and YH3−x, while the Al2O3 component enhanced cyclic stability. The effect of temperature and hydrogenation pressure on the catalytic reactions was investigated. The results demonstrated that the hydrogen uptake rates increased with both the hydrogen pressure (3–10 MPa H2, see Supporting Information Figure S11) and temperature (413–453 K, see Supporting Information Figure S12a), whereas the hydrogen release rates also increase with the increase of temperature (463–483 K), see Supporting Information Figure S12b). The apparent activation energies for the hydrogenation and dehydrogenation reactions obtained from Arrhenius plots were 149 ± 1 kJ mol−1 and 199 ± 7 kJ mol−1, respectively (see Supporting Information Figures S12c and d). Although the kinetics were enhanced, the activation energy value was much higher than that of Ru- and Pd-based catalysts (typically 30–70 kJ mol−1),15,20,43 suggesting a new reaction mechanism of our fabricated catalyst different from conventional surface catalysis. YH3−x-mediated H transfer mechanisms Then we demonstrated that the remarkable catalytic promotion effect of YH3−x is originated from new H transfer mechanisms mediated by YH3−x. We used the isotope labeling method to study the H transfer mechanisms (Figures 3a–3c and Supporting Information Figure S13). The hydrogenation and the dehydrogenation reactions were carried out on the deuterated catalyst Co-B/Al2O3-YD3−x, and the isotope distribution was analyzed after the reaction. The solid catalyst is heated in Ar flow to 1000 K, and the released gas is detected by a mass spectrometer (MS). The gas-phase was measured using a residual gas analyzer, and the liquid phase was analyzed by FT-IR. Figure 3 | (a–c) Analysis of the D content in the liquid, gas, and solid phases after hydrogenation of NEC and dehydrogenation of 12H-NEC on Co-B/Al2O3-YH3−x (De: 473 K, vacuum, 30 min): (a) FT-IR spectra of the hydrogenation products; (b and c) composition of the gas phase and the gas generated from heating the solid catalyst analyzed by mass spectroscopy; (d and e) The kinetic isotope effect (KIE) of NEC hydrogenation (453 K, 3 MPa H2/D2) and 12H-NEC/12D-NEC dehydrogenation (473 K, 0.1 MPa H2/D2) on different catalysts: (d) Co-B/Al2O3-YH3−x, (e) Ru/Al2O3 for hydrogenation and Pd/Al2O3 for dehydrogenation. (12D-NEC is obtained by deuteration of NEC on Ru/Al2O3 catalyst.) Download figure Download PowerPoint We first analyzed the isotope distribution after Co-B/Al2O3-YD3−x catalyzed hydrogenation. Partial deuteration was observed in the liquid product , as evidenced by the C-D stretching peak at 2160 cm−1 in the FT-IR spectrum (Figure 3a). MS analysis suggested that a large amount of H was found in the solid catalyst after hydrogenation, while the gas phase remained H2 (Figures 3b and 3c). This notable redistribution indicated that the lattice D in YD3−x could be transferred to NEC to form 12(H/D)-NEC, and the D vacancies could be replenished by H2. The hydrogen transfer mechanism is schematically illustrated in Figure 4a. Co-B is the other essential component in the composite catalyst. Here, the role of the Co-B was to activate the NEC molecules. Figure 4 | (a) The YH3−x-mediated H transfer mechanisms in NEC hydrogenation and 12H-NEC dehydrogenation reactions of the Co-B/Al2O3-YH3−x catalyst; (b and c) The PCI curve (left) and the corresponding H chemical potential (μH) diagram (right) for the H transfer processes in (b) NEC hydrogenation and (c) 12H-NEC dehydrogenation. Spontaneous H transfer requires a downward change of μH. The filled H bonding sites or bands are represented in green. Download figure Download PowerPoint We then analyzed the isotope distribution after dehydrogenation. H2, HD, and D2 were detected in the generated gas, and the solid catalyst also contained both H and D (Figures 3b and 3c). For comparison, direct H-D exchange of YD3−x with 0.1 MPa H2 at the same temperature results in much less D release. As shown in Supporting Information Figure S14, the gas phase only contained a low fraction of HD but no D2 after 2 h. Therefore, the presence of 12H-NEC facilitated the release of the lattice D from YD3−x. This is quite surprising as the release of the lattice H was only affected by the H2 partial pressure in general circumstances. A reasonable explanation is that H in 12H-NEC could be transferred into the vacancies of the YD3 lattice, which facilitated the release of the lattice D, as schematically illustrated in Figure 4c. Similarly, here, the 12H-NEC molecules needed to be adsorbed and activated by the Co-B catalyst. We further investigated the kinetic isotope effect (KIE) in hydrogenation and dehydrogenation of NEC. For the Co-B/Al2O3-YH3−x catalyst, hydrogenation using H2 is much faster than deuteration using D2, and dehydrogenation of 12H-NEC is much faster than that of 12D-NEC (Figure 3d and Supporting Information Figure S15). The ratios of the initial reaction rates rH/rD for H/D uptake and release were was 2.4 and respectively. For comparison, there was observed for the hydrogenation catalyst Ru/Al2O3 and dehydrogenation catalyst Pd/Al2O3 (Figure In conventional surface hydrogenation and dehydrogenation catalysts typically show no the large of the Co-B/Al2O3-YH3−x catalyst suggested that H transfer a role in both the hydrogenation and dehydrogenation of NEC. The H transfer mechanisms shown in Figure H in the YH3−x lattice, which could the large by the different rate of H and between YH3−x and the transition metal catalyst hydrogenation and dehydrogenation both activation of the LOHC molecules and fast H transfer. conventional surface catalysts, the two processes have to be H or H bonding sites on the catalyst surface have to be the activated LOHC NEC/12H-NEC requires to H As a H transfer is inefficient due to H or H bonding sites the activated NEC/12H-NEC molecules. Indeed, non-noble metal catalysts are active only for hydrogenation and dehydrogenation of while a of could be used for hydrogenation of NEC and dehydrogenation of YH3−x is a large for both H and sites with fast hydrogen absorption and desorption which an H transfer as suggested by the isotope labeling results (Figure the other YH3−x showed activity for both hydrogenation and dehydrogenation, which indicated that YH3−x was to activate the NEC/12H-NEC molecules. Therefore, the synergism is essential for efficient hydrogenation and dehydrogenation (Figure Co-B for activation of the NEC/12H-NEC molecules and YH3−x for fast H transfer. Moreover, H transfer between the activated NEC/12H-NEC molecules requires H the In this work, the the Although quite an catalytic performance effect was the was after 5 hydrogenation and dehydrogenation cycles, which is one major of the performance study on more of the preparation is required to the H transfer To further this we the promotion effect of YH3−x to other Al2O3-supported transition metal catalysts. As shown in Figure the different catalytic performance, YH3−x by simple hand milling leads to performance for all the catalysts which suggests that the synergism is quite general for NEC hydrogenation and 12H-NEC dehydrogenation. In this work, the synergism with the to the mechanistic was on or and the was transferred to the hydride to form which and the hydride reaction with H2. Here, the synergism also a key is used to activate and the hydride as an H donor for the activated Figure 5 | Catalytic performance of different catalysts in reversible hydrogen storage in NEC. The H2 in 2 h is used as a figure of The hydrogenation conditions on and Ni/Al2O3-YH3 are K, 3 MPa The results of dehydrogenation on Ru/Al2O3 and are Download figure Download PowerPoint As shown in Figure the catalytic performance also on of is the of the Co-B/Al2O3-YH3−x exhibited the two-direction catalytic performance all the noble-metal-free catalysts. However, Co/Al2O3-YH3−x prepared by a thermal reduction in H2 only showed very low activity (see Supporting Information Figure The XPS spectra (Figures 1b and electron transfer between Co and which to a more activation effect for both NEC and 12H-NEC on the other was more active for 12H-NEC dehydrogenation but less active for NEC hydrogenation compared to (see Supporting Information Figure Therefore, to the role of B in the further is of the of YH3−x The mechanisms shown in Figure H transfer from YH3−x to NEC in hydrogenation and from 12H-NEC to YH3−x in dehydrogenation. The H transfer between the two phases H2, the H transfer could be by the different H2 pressure in hydrogenation and dehydrogenation. The temperature is also too small to the H transfer In this we show that the of YH3−x is essential for the two-direction H which is to In the YH3 H all the and of the Y The nonstoichiometric YH3−x has The H is by the H2 partial which is by the Yttrium could form two and The H2 pressure for the transition was at 473 K. Therefore, the hexagonal YH3 structure in YH3−x is kept in both hydrogenation MPa and dehydrogenation MPa reactions, which is in agreement with the XRD results (Figure However, the H and H chemical potential of YH3−x were different in hydrogenation and dehydrogenation We obtained a PCI which a of of the H bonding sites in a metal hydride with the bonding when the H2 pressure increases Therefore, the PCI curve could also be as the of states of the H bonding sites in The H2 pressure is to H chemical potential (μH) by the H = 1 2 H 2 = mol−1 is the gas is the temperature in K, and = 0.1 is the pressure. kJ the H bonding to an H Here, the of is the H2 at 0.1 at a in this also