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Design strategies of highly selective nickel catalysts for H2 production via hydrous hydrazine decomposition: a review

Design strategies of highly selective nickel catalysts for H2 production via hydrous hydrazine... Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 National Science Review 5: 356–364, 2018 REVIEW doi: 10.1093/nsr/nwx123 Advance access publication 29 September 2017 CHEMISTRY Design strategies of highly selective nickel catalysts for H production via hydrous hydrazine decomposition: a review 1,† 1,2,† 1,∗ 1,∗ Lei He , Binglian Liang , Yanqiang Huang and Tao Zhang ABSTRACT Hydrazine, a widely used liquid propellant, has the potential to be employed as a hydrogen source in certain instances and has therefore attracted considerable attention; consequently, the complete decomposition of hydrazine with 100% H selectivity under mild conditions has become the current research focus for catalyst design. In this review, the strategies for the design of efficient catalysts are summarized for complete hydrazine decomposition. The first part of this review introduces the mechanism of hydrazine decomposition, while the second part illustrates the key factors influencing the H selectivity of nickel catalysts, including the effects of alloying, alkali promoter addition and strong metal–support interactions. Finally, the critical elements of catalyst design employed in industrial applications are analyzed. Keywords: hydrazine, selectivity, H , catalyst, nickel However, subsequent reactions also need to be INTRODUCTION considered. The produced H can further react with Hydrazine (N H ) is an energy-rich molecule, 2 4 N H according to the following reaction: 2 4 which can decompose into a mixture of N ,H and 2 2 NH [1]. In the presence of efficient catalysts, the State Key Laboratory N H (l) + H (g) → 2NH (g)  H (298) 2 4 2 3 r decomposition rate can be enhanced even at low of Catalysis, Dalian temperatures. During the decomposition process, −1 Institute of Chemical =−142.5kJmol . (3) the chemical energy in N H can be converted into 2 4 Physics, Chinese kinetic energy. One such application of N H de- 2 4 Academy of Sciences, Furthermore, decomposition of the NH compo- composition is in orbiting satellites, which use hy- Dalian 116023, China nent in the produced mixture can form H and N : 2 2 drazine to control their altitude and orbit adjustment and University of Chinese Academy of propulsion. NH (g) → 1/2N (g) + 3/2H (g)  H (298) 3 2 2 r Sciences, Beijing The thermal or catalytic decomposition of hy- 100039, China drazine occurs via two routes according to Eqs. −1 =+45.9kJmol . (4) (1–4) [1,2]: Corresponding Complete: N H (l) → N (g) + 2H (g) 2 4 2 2 During a catalytic decomposition process, the authors. E-mails: above-mentioned parallel reactions during catalytic ◦ −1 ◦ [email protected]; H (298) =−50.6kJmol , G (298) r r decomposition lead to a superimposition of the [email protected] −1 reaction products [1,3]. For each equation men- Equally contributed =−149.4kJmol . (1) to this work. tioned above, more than one elementary step is per- formed during the reaction process, which leads to Incomplete: N H (l) → 4/3NH (g) + 2 4 3 hydrazine decomposition containing many elemen- Received 2 July 1/3N (g) 2016; Revised 10 tary steps, hence the difficulty in describing them. ◦ −1 ◦ September 2016; To simplify the research that has been conducted us- H (298) =−111.9kJmol , G (298) r r Accepted 10 ing various catalytic systems, the above reactions are −1 September 2016 =−171.3kJmol . (2) unified by one equation, where x represents the H The Author(s) 2017. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd. All rights reserved. For permissions, plea se e-mail: [email protected] Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 REVIEW He et al. 357 selectivity: H (g) 6 2 NH (g) N (g) 3N H (l) → 4(1 − x)NH (g) 2 4 3 5 2 N H (g) 2 4 + (1 + 2x)N (g) + 6xH (g). 2 2 (5) Depending on the application, it is desirable to design catalysts with controlled hydrogen selectiv- ity. For example, the specific impulse of a chemi- cal rocket exhibits a maximum in the H selectivity 0 100 200 300 400 range of 30–40% when hydrazine is used as a space Temperature ( ) propellant. The production of CO-free hydrogen is currently Figure 1. Thermodynamic products versus temperature for a hot topic, and the catalytic decomposition of hy- the decomposition of 3 mol hydrazine (0.1 MPa). drazine is proposed for this purpose [4–6]. If com- plete N H decomposition proceeds through equa- 2 4 reducing agent that is used to control corrosion in tion (1), the hydrogen released is calculated to be boilers, reduce noble metal catalysts or graphene ox- 12.5 wt.%. This value is significantly larger than the ide, and to hydrogenate unsaturated bonds in or- target set by the Department of Energy (DOE) for ganic compounds [11]. In the case of handling spent onboard hydrogen systems (5.5 wt.%) [7]. There- hydrazine, complete decomposition of hydrazine fore, N H qualifies as a mobile hydrogen source 2 4 into hydrogen and nitrogen is considered the most meeting the DOE target. Additionally, during the suitable route to circumvent the production of am- complete decomposition of N H , three equivalent 2 4 monia. moles of gaseous products are generated leading to The development of efficient and selective cat- increased volumes of emitted gas, which prevents alysts for H generation from hydrazine is an im- the solubility of ammonia in water, thus providing portant topic considering the applications described a driving force in submarine rescue systems when above. From a thermodynamic perspective, the employing hydrazine for ballast water expulsion. In Gibbs free energy of equation (2) is lower than that such cases, it is critical that catalyst design yields high of the equation (1). That is to say, hydrazine decom- selectivity, especially in mild conditions. position to ammonia is thermodynamically more Another important property of hydrazine is the favorable. As shown in Fig. 1, the major thermo- formation of hydrous hydrazine when hydrazine re- dynamic products of hydrazine decomposition are acts with water, similar to ammonia. The monohy- NH and N at low temperature. Therefore, it is chal- 3 2 drate of hydrazine (N H ·H O) has a much lower 2 4 2 lenging to avoid its undesirable decomposition to freezing point (−51.7 C) compared with N H 2 4 ammonia. (1.4 C), which makes the former a suitable pro- In this review, we briefly introduce the mech- pellant when employed across a wider temperature anism of hydrazine decomposition to demonstrate range. The water molecule may potentially lead to the principles of catalyst design. Thereafter, cat- a partial slowdown of the decomposition rate. Al- alytic systems are presented that focus on the se- though N H ·H O is still considered to be a dan- 2 4 2 lective decomposition of N H or N H ·H Oun- 2 4 2 4 2 gerous chemical, it is far safer to handle compared der mild conditions. To date, multiple strategies to explosive N H and, thus, more suitable for in- 2 4 in catalyst design have been reported, including vestigation in fundamental research. In 2009, Xu and pure metallic nanoparticles and supported catalysts. co-workers proposed the idea of using hydrous hy- These catalytic systems are divided into three types drazine as a potential candidate for chemical hy- according to their influencing factors on H selectiv- drogen storage [8]. Since then, there have been a ity, including alloying effects, alkali promotion and number of reports concerning the decomposition of metal–support interactions. The principal reasons hydrous hydrazine compared with its anhydrous for the tunable selectivity are discussed both experi- counterpart. mentally and theoretically, which may provide guid- Hydrazine, being the simplest diamine, has appli- ance for further catalyst design. In addition to inspir- cations beyond chemical propellants and is widely ing further research on hydrazine decomposition, employed as a precursor in the synthesis of or- we hope that this review will stimulate research on ganic molecules containing N–N bonds, especially other related N-containing reactions, such as NH in the preparation of pesticides and pharmaceu- or NH BH decomposition. 3 3 ticals [9,10]. Additionally, hydrazine is a strong Equilibrium amount (mol) Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 358 Natl Sci Rev, 2018, Vol. 5, No. 3 REVIEW [20,21], Fe (211) [22], Ni [23] and Cu [24] NH surfaces. However, the adsorption conformations of N H H N NH NH H 2 4 2 2 N H 2 4 hydrazine and the intermediates show significant differences in these reports. The hydrazine decom- N=N HN=NH HH 2 NH position mechanism is still contested over different metallic catalysts. Therefore, tailoring of selectivity 2 H N NH H N NH 2 2 through catalyst design is still determined experi- (a) HN=NH N=N HH HH mentally. Essentially, the reaction route is determined by N=N HN=NH the sequence of N–N bond and N–H bond cleav- HH 2 NH age [1]. The N–N bond cleavage energy in gaseous −1 N H N H is 286 kJ mol , and the N–H bond energy 2 4 H 2 4 −1 is 360 kJ mol when the entire bond breaks into (b) N and H atoms. From a thermodynamic viewpoint, N H 2 4 H N NH the first step relating to N–N bond cleavage appears N H 2 2 N H HNNH 2 4 2 4 2 2 2 NH 2 NH 3 3 to be easier, which consequently leads to the pro- H H NN HNNH HN NH HN NH N N 2 2 H H N duction of N and NH . However, the bond en- 2 3 −1 ergy of N–H is lowered to 276 kJ mol if N H 2 4 partially breaks into N H and H adatoms are ob- 2 2 served over a Ni (100) surface [25], which can po- Figure 2. Reaction pathways for hydrazine decomposition. (a) NH ,N and H 3 2 2 formation. (b) NH and N formation. tentially lead to large quantities of H being pro- 3 2 2 duced. In another case, the H–Pt bond is stronger than the N–Pt bond on Pt(111), leading to the bar- MECHANISM CONSIDERATION rier to N–H cleavage being much lower than that to N–N cleavage [15]. As a result, regardless of the Early research focused on mechanistic studies via higher N–H bond energy compared with the N–N adsorption experiments over Ir, Pt and Rh model bond, the first bond to break in hydrazine adsorbed metallic surfaces [12–16]. For example, it has been on platinum is an N–H bond instead of the N–N observed that the initial step of hydrazine decompo- bond. Nitrogen forms and desorbs close to 40 C sition over an Ir surface is the dissociative adsorption through an intramolecular process [15]. Motivated of the N H molecule, which produces the adatoms 2 4 of nitrogen, hydrogen, and NH species [12]. The by these findings, the SiO -supported Ni, Pd and Pt 2 2 adsorbed hydrogen atoms display good mobility and catalysts developed by our group displayed excellent can further react with another hydrogen atom to H selectivity in gas phase hydrazine decomposition, produce molecular hydrogen or with an NH radi- even at room temperature [3]. According to these cal to produce NH . Under mild conditions in the reports, the higher H selectivity on Ni-, Pd- and 3 2 presence of an Ir surface, NH is the main product Pt-based catalysts is because of the lower barrier to because of the ease by which NH combines with N–H cleavage, which may be related to the stronger adsorbed hydrogen. Conversely, the main inter- M–H bond. Furthermore, de Medeiros et al. corre- mediate is NH in the presence of an Rh surface lated H selectivity with the enthalpy of adsorption using temperature-programed surface reaction ex- of hydrazine. Hydrazine decomposition over cata- periments, which generate N and H as the main lysts possessing low enthalpies of adsorption mainly 2 2 products at low N H coverage and N and NH at produces N and H . On catalysts having high en- 2 4 2 3 2 2 −1 high N H coverage [14]. thalpies of adsorption (520 kJ mol ), the reaction 2 4 Isotopic-labeled N H was employed to obtain products are N and NH [26]. To summarize the 2 4 2 3 further information regarding the intermediates dur- most plausible mechanism, general reaction path- ing the decomposition process [17,18]. The ratio of ways for hydrazine decomposition are proposed in 15 14 Fig. 2, showing NH ,N and H formation (Fig. 2a), Nto N in the produced N is small, which il- 2 3 2 2 and NH and N formation (Fig. 2b). Because the lustrates that the produced N–N comes from the 3 2 theory of hydrazine decomposition is not compre- same hydrazine molecule and therefore abrogates hensive enough, catalyst design for H generation the hypothesis of prior N–N cleavage during the from hydrazine is mainly based on experimental ex- N H decomposition process [17]. With the devel- 2 4 ploration. It should be noted that the decomposition opment of computational technologies, theoretical calculations have been performed over noble metal of hydrazine has been studied in the vapor phase as and non-noble metal surfaces. Further detailed re- well as in solution. Although the mechanism is very action pathways have been proposed over various similar in both cases, it is sometimes difficult to ex- modeling surfaces, such as Ir(111) [19], Rh(111) clude solvent and surface interference in the latter Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 REVIEW He et al. 359 In 1979, an Al O -supported Ir–Ni catalyst was case [27]. Therefore, we indicate which phase the re- 2 3 studied for its performance in gas hydrazine decom- action is in hereafter. position at 27 C[31]. Although Ir is considered to be the most active metal for gas hydrazine decom- position, its selectivity for hydrogen is poor at low CATALYTIC SYSTEMS temperatures. Alloying Ni to Ir led to an increase Metallic catalysts are one of the most widely used in H production through complete decomposition catalytic systems in heterogeneous catalysis for via equation (1). The adsorption experiment results industrial applications. These catalysts are often have demonstrated that the surface bonding of NH composed of active metals, supports and other pro- and N adspecies to Ir is weakened by the addition of moters. There are many factors that can influence Ni atoms, which originate from the formation of the catalytic performance, including the choice of metal Ir–Ni alloy. In 2009, Xu and co-workers reported the and support composition, the exposed facet of the excellent performance of Rh–Ni bimetallic nanopar- active metal, the interaction between the metal and ticles in hydrogen production via hydrous hydrazine the support, and the properties of the additional pro- decomposition [32], which inspired the following moters. From a molecular point of view, the surface research on bimetallic catalysts. The catalytic perfor- structure and electronic properties are the main in- mances of various two-component transition metal fluencing factors for heterogeneous catalysts as the catalysts are summarized in Table 1. The Ni-based majority of the reactions occur on the surface. For bimetallic catalysts with or without supports pro- hydrazine decomposition, changes to the sequence vide the highest H selectivity, which stimulated in- of N–N bond and N–H bond cleavage are the ma- terest in investigating the reason for their excellent jor strategy to change selectivity. Among various cat- performance. To date, nanoparticles composed of alytic systems, transition metals (e.g. Ir, Ru and Ni) three types of metals have been reported, includ- are the most efficient candidates for N–H bond ac- ing NiFeCu [33], NiFePd [34] and NiFeMo [35]. tivation and exhibit high activity for hydrazine de- Additionally, other novel materials have been tested composition under mild conditions. However, H in the decomposition of hydrous hydrazine, such selectivity is limited to below 10% over Ru and Ir as Co Se/graphene hybrid nanosheets [36]; Ni– 0.85 catalysts. To date, monometallic catalysts have failed B[37], Co–B [38,39], Fe–B [40] and Rh–Ni–B to achieve the complete catalytic decomposition of [41] materials; Ni–Rh and Ni–Pt nanoparticles im- hydrous hydrazine to H without generating NH . 2 3 mobilized on a metal–organic framework (MOF); Hence, modification of the catalysts is necessary to and MOF-derived carbon dots and nitrogen-doped promote H selectivity. In this section, methods that porous carbon [42–44]. These materials have exhib- have been explored for the promotion of H forma- ited good performance in hydrous hydrazine decom- tion will be introduced, including alloying of a sec- position, although further discussion is not included ond metal, alkali addition and then introduction of in this review. strong metal–support interactions. To study the reasons why the second metal promotes catalytic performance, structural config- uration and surface adsorption experiments were Alloy effect performed. It is well documented that the arrange- ment of the two metals can result in three structure Bimetallic catalysts often exhibit enhanced activity, types: alloy, core-shell, and heterogeneous. For Pt- selectivity and stability compared with their par- promoted Ni catalysts, X-ray diffraction (XRD) re- ent metals because of their distinct electronic and sults illustrate that the main diffraction peaks show chemical properties. Therefore, the development of only the existence of metallic Ni [45]. The diffrac- bimetallic catalysts provides opportunities to obtain tion peaks shift to lower angles after doping with novel catalysts with improved catalytic performance Pt, demonstrating the formation of a Ni–Pt alloy in many industrial applications. To further under- in the bimetallic catalysts. The formation of the stand the origins of their novel properties, bimetallic Ni–Pt alloy has been further confirmed by the co- catalysts have been extensively studied in fundamen- reduction of Ni and the second metal, illustrated by tal research. The geometric and electronic changes H -temperature-programed reduction (TPR) data. of the bimetallic surface have been shown to be the Furthermore, extended X-ray absorption fine struc- reason for their extraordinary properties in many re- ture (EXAFS) experiments have been employed to actions, such as hydrocarbon reforming, as reported previously in the literature [28–30]. In this section of study the Pt oxidation status and its coordination the review, we will focus on summarizing the inves- environment. The results indicate that the majority tigation of bimetallic catalysts for hydrous hydrazine of the Pt species exist in the form of a Ni–Pt al- decomposition to date. loy, which leads to an electronic transfer from Ni to Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 360 Natl Sci Rev, 2018, Vol. 5, No. 3 REVIEW Table 1. Comparison of hydrogen selectivity (%) of hydrous hydrazine decomposition over different bimetallic catalysts. Fe Co Ni Fe 0 [46] 100 [46–48] Co 0 [46]18[46] Ni 100 [46–48]18[46] Ru 99 [49] Rh 30 [32]20[32] 100 [32,50–53] Pd 0 [54]7[54] 100 [55] Ir 0 [56] 100 [57] 100 [56,58] Pt 0 [46]72[59] 100 [45,60–66] Au 80 [58] Cu 0 [46]15[46] 100 [67] Pt. Therefore, the adsorption of H and NH is sig- their catalytic performance. As shown in Fig. 3,the 2 3 nificantly weakened on the bimetallic surface com- low-temperature-reduced catalyst (Ni–Ir/Al O - 2 3 pared with the parent Ni or Pt catalysts, which has 300R) showed >99% H selectivity. In contrast, been proven by H -temperature-programmed des- the analogous high-temperature-reduced catalysts orption (TPD), microcalorimetry and NH -TPD (Ni–Ir/Al O -500R and Ni–Ir/Al O -700R) 3 2 3 2 3 experiments. showed a considerable reduction in H selectivity In addition to the three bimetallic structure [58]. The results of XRD, EXAFS and H -TPR systems, the diverse arrangements of the surface and confirmed alloy formation for all three catalysts. sub-surface metal atoms of the binary system show However, the coordination number of the Ni–Ir a significant influence on the surface adsorption bond increased in the order of Ni–Ir/Al O -300R 2 3 and electronic properties of the alloy catalysts < Ni–Ir/Al O -500R < Ni–Ir/Al O -700R, which 2 3 2 3 [28,30]. Further studies on Ni–Ir catalysts were per- demonstrated the relocation of Ir atoms from the formed to investigate the influence exerted by the surface of the Ni–Ir alloy particle into the core as arrangement of the surface atoms, and revealed that a function of increasing reduction temperature. pretreating temperatures significantly influenced Consequently, the atom arrangement at the surface changed from a Ni–Ir alloy into a Ni-rich surface, leading to a decrease in H selectivity during Ir hydrous hydrazine decomposition. Ni Furthermore, the surface structure was char- acterized for Pt-, Ir- and Au-doped Ni bimetallic catalysts reduced at equivalent temperatures. Corre- lating with their hydrous hydrazine decomposition catalytic performance, it was concluded that the for- mation of a surface alloy is necessary for the purpose Selectivity (%) of obtaining high H selectivity [58]. Provided a ho- -1 Reaction rate (h ) mogeneous alloy is formed, such as a Pt–Ni cata- δ+ lyst, the Ni can be observed because of the partial electron transfer from Ni to a nearby Pt atom. Con- versely, for Au–Ni catalysts, segregation of Au on the 60 8 surface is detected. This structural change greatly in- fluences the surface adsorption properties and cat- alytic performance of the catalyst. The surface struc- ture of the alloy catalyst plays an important role in the generation of H from hydrous hydrazine de- composition and may promote future rational cat- alyst design to obtain good activity and superior selectivity. 0 0 300 500 700 Reduction temperature (ºC) Strong basic promoter Figure 3. Structural model of bimetallic Ni–Ir catalysts for hydrous hydrazine decom- For heterogeneous catalysts, non-active compo- position. Reprinted with permission from [58]. Copyright 2013 Elsevier B.V. nents are typically added as promoters to adjust Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 REVIEW He et al. 361 properties, as shown in the insets of Fig. 4. The ap- parent activation energies were calculated for H (pathway 1) and NH (pathway 2) generation, re- spectively. The results indicated an increase in the activation energy for pathway 2 after the addition of 80 NaOH, which confirmed the inhibition of NH pro- duction with the existence of NaOH. Recently, several supported metal catalysts were shown to catalyze the decomposition of hydrous hy- drazine with nearly 100% H selectivity. This high Magnet (a) (b) selectivity could be attributed to the existence of 0 0.05 0.10 0.25 0.50 1.00 2.50 -1 strong basic sites over the catalysts. In the study of NaOH concentration (mol L ) hydrotalcite-derived Ni/Al O catalysts, H selec- 2 3 2 Figure 4. H selectivity improvement as a function of strong 2 tivity reached 93% at 30 C, which was significantly basic promoter concentration in hydrous hydrazine decom- higher than the impregnated counterpart (67%) position on Raney Ni catalyst. Insets: magnetic separation [70]. The CO –TPD results revealed large concen- property of Raney Ni catalyst after reaction of (a) reactants trations of strong basic sites in the hydrotalcite- with catalyst after reaction and (b) with a magnet to sepa- derived Ni/Al O , which are thought to originate 2 3 rate catalyst. Reprinted with permission from [69]. Copyright 2− from the O species in the Ni–O–Al structure. The 2013 American Institute of Chemical Engineers. strong basic sites inhibit the production of NH and also influence the electronic properties of Ni par- ticles, which consequently improves H selectivity selectivity or enhance activity. For example, the ad- during hydrous hydrazine decomposition in mild dition of alkali promoters is crucial for ammonia syn- conditions. thesis. In the 1970s, strong basic components, e.g. In summary, the promoting effect can be at- NaOH and KOH, were found to improve H selec- tributed to two aspects: i) inhibition of generation of tivity for hydrous hydrazine decomposition over Ir the basic byproduct NH and ii) electronic perturba- catalysts at low temperatures [1]. However, these tion on the surface of the active metal because of the additives could not catalyze this reaction themselves existence of vicinal strong basic sites. However, the and led to a decrease in the reaction rate. Recently, addition of alkalis may not be the best choice to im- the development of non-noble metal catalysts for hy- drous hydrazine decomposition to improve H gen- prove H selectivity via hydrous hydrazine decom- eration has gained significant attention. It is impor- position when taking into account environmental tant to note that strong basic additives are necessary issues. for such catalysts to obtain high H selectivity in mild conditions. These strong basic promoter additives can be divided into two types: i) alkalis (e.g. NaOH) Strong metal–support interaction effect added separately and ii) basic supports combined with the active component during preparation. Widely used industrialized heterogeneous catalysts Xu and co-workers developed the bimetallic often consist of metal nanoparticles supported on Ni–Fe nanocatalyst, which could catalyze the com- large surface area oxides. The importance of these plete decomposition of hydrous hydrazine with oxides has been increasingly recognized over recent the assistance of NaOH [46]. Later, many multi- decades, following the discovery of metal–support component catalysts were found to catalyze this re- interactions. In addition to dispersing metallic par- action with the addition of an alkali, such as Fe– ticles, the oxide support also influences the catalytic B/MWCNT [40] or NiMoB–La(OH) [68]. In our properties of the metal catalysts through geometric research on Raney Ni catalysts [69], the addition or electronic effects. The representative oxides in- of NaOH was precisely controlled. Before the addi- clude CeO ,TiO and Fe O . 2 2 2 3 tion of NaOH to the Raney Ni catalyst, H selec- To investigate the influence of the support for tivity reached only 80% during the decomposition Ni catalysts in hydrous hydrazine decomposition, of hydrous hydrazine. As shown in Fig. 4,asmall two types of Ni/CeO catalysts were prepared us- −1 amount of NaOH (0.05 mol L ) could significantly ing co-precipitation and impregnation methods, de- promote the selectivity to 91%. Further increasing noted as Ni/CeO -CP and Ni/CeO -IMP, respec- 2 2 −1 the concentration of NaOH to above 0.5 mol L , tively [71]. The two Ni/CeO catalysts exhibited the H selectivity reached over 99%. In addition, quite different activity and selectivity toward hy- the Raney Ni catalyst could be easily collected and drous hydrazine decomposition because of their sig- reused after the reaction because of its magnetic nificant structural differences. The Ni particles were H Selectivity (%) 2 Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 362 Natl Sci Rev, 2018, Vol. 5, No. 3 REVIEW ports, as long as a Ni–O–M structure formed. This finding may inspire the future design of more effi- cient catalysts for the decomposition of hydrous hy- drazine using economically viable facile preparation methods. N N H H Ni Ni Ce Ce Ni/CeO Ni/C O -CP CP Ni/CeO -IMP 2 2 O CONCLUSION AND OUTLOOK Different hydrazine usage demands have made hy- Figure 5. Structural models of Ni/CeO -CP and Ni/CeO - 2 2 drazine decomposition selectivity increasingly im- IMP. Reprinted with permission from [71]. Copyright 2015 portant. This focus of this review has been to American Chemical Society. analyze factors that influence improvements to hy- drogen selectivity in mild conditions. As Ni-based catalysts have been proven to be the most active can- highly dispersed in the co-precipitated sample over didates, strategies to further improve their perfor- high Ni loading, which led to improvements in ac- mance have been analyzed, including the choice of tivity for the reaction. In contrast, Ni/CeO -IMP metal composition, alkali promoter addition and the resulted in obvious aggregation of Ni particles be- tailoring of metal–support interactions. Our intent cause of the small surface area of the CeO sup- is to encourage the development of more highly se- port, resulting in significantly lower activity. Fur- lective catalysts for H production via hydrous hy- thermore, H selectivity reached over 99% for the drazine decomposition. Ni/CeO -CP catalyst, considerably higher than for Although many attempts, both experimental and the impregnated counterpart (65%), although the theoretical, have been made to reveal the key factors Ni particle sizes were very similar on both samples. that affect the selectivity of metallic catalysts, the de- Electron microscopy images, H -TPR and Raman tailed mechanism is still not fully understood. There- spectroscopy results indicated that Ni particles fore, studies on hydrazine decomposition are neces- were partially surrounded by amorphous CeO in sary to better understand the reasons for selectivity Ni/CeO -CP (Fig. 5). The co-precipitation method differences. Additionally, such studies may further induced the existence of a Ni–O–Ce structure. How- inspire the exploration of other reactions including ever, for Ni/CeO -IMP, the Ni particles resided on N–N bonds and N–H bonds, such as NH synthesis CeO with little interaction between Ni and CeO 2 2 or decomposition, and provide opportunities for the [71]. This geometric variation of the surface struc- development of novel catalytic systems. ture led to an electronic change of the exposed Ni. Furthermore, the majority of the catalysts re- Using CO as an adsorption probe, Fourier Trans- ported in the literature to date have only been form Infrared Spectroscopy (FT-IR) results illus- successful at the laboratory scale and have shown trated that the exposed Ni species in Ni/CeO -CP limitations in industrial application. As is already differs from metallic Ni. The presence of a weak CO known, this reaction is an exothermal process, and δ+ adsorption band on the Ni site could be observed, the amount of heat released and the distribution of indicating changes to the electronic properties of the gaseous products (N ,H and NH ) depends on 2 2 3 exposed Ni species on Ni/CeO -CP because of the the reactive conditions and the selectivity of the cat- modification of vicinal CeO [71]. In particular, the alysts. Therefore, heat and mass transfer should be CeO support not only played a role in dispersing Ni considered during the design of catalysts. In addi- particles, but also behaved as a promoter or modifier tional, the stabilities of the currently available cata- to improve hydrogen selectivity of Ni in the decom- lysts are not sufficient to meet the demands of indus- position of hydrous hydrazine. trial production. Therefore, many engineering and On the basis of results outlined above, we syn- technological problems need to be investigated and thesized other Ni–O–M structures on varying metal resolved prior to their industrial application. oxide supports. Using the co-precipitation method, a series of supported Ni catalysts were prepared, including Ni/MgO, Ni/La O and Ni/ZrO [71]. 2 3 2 These catalysts had one thing in common: a strong FUNDING metal–support interaction existed between Ni and This work was supported by the National Natural Science Foun- the oxide support. Similar to the Ni/CeO –CP sam- dation of China (21103173 and 21476226), the Strategic Pri- ple, these catalysts all exhibited >80% H selectivity 2 ority Research Program of the Chinese Academy of Sciences for hydrous hydrazine decomposition, which further (XDB17020100), the National Key Projects for Fundamental confirmed the promotion effect of the oxide sup- Research and Development of China (2016YFA0202804) and Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 REVIEW He et al. 363 the Youth Innovation Promotion Association of the Chinese 19. Zhang P, Wang Y and Huang Y et al. Density functional theory Academy of Sciences. investigations on the catalytic mechanisms of hydrazine decom- positions on Ir(111). Catal Today 2011; 165: 80–8. Conflict of interest statement. None declared. 20. Deng Z, Lu X and Wen Z et al. 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Design strategies of highly selective nickel catalysts for H2 production via hydrous hydrazine decomposition: a review

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Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 National Science Review 5: 356–364, 2018 REVIEW doi: 10.1093/nsr/nwx123 Advance access publication 29 September 2017 CHEMISTRY Design strategies of highly selective nickel catalysts for H production via hydrous hydrazine decomposition: a review 1,† 1,2,† 1,∗ 1,∗ Lei He , Binglian Liang , Yanqiang Huang and Tao Zhang ABSTRACT Hydrazine, a widely used liquid propellant, has the potential to be employed as a hydrogen source in certain instances and has therefore attracted considerable attention; consequently, the complete decomposition of hydrazine with 100% H selectivity under mild conditions has become the current research focus for catalyst design. In this review, the strategies for the design of efficient catalysts are summarized for complete hydrazine decomposition. The first part of this review introduces the mechanism of hydrazine decomposition, while the second part illustrates the key factors influencing the H selectivity of nickel catalysts, including the effects of alloying, alkali promoter addition and strong metal–support interactions. Finally, the critical elements of catalyst design employed in industrial applications are analyzed. Keywords: hydrazine, selectivity, H , catalyst, nickel However, subsequent reactions also need to be INTRODUCTION considered. The produced H can further react with Hydrazine (N H ) is an energy-rich molecule, 2 4 N H according to the following reaction: 2 4 which can decompose into a mixture of N ,H and 2 2 NH [1]. In the presence of efficient catalysts, the State Key Laboratory N H (l) + H (g) → 2NH (g)  H (298) 2 4 2 3 r decomposition rate can be enhanced even at low of Catalysis, Dalian temperatures. During the decomposition process, −1 Institute of Chemical =−142.5kJmol . (3) the chemical energy in N H can be converted into 2 4 Physics, Chinese kinetic energy. One such application of N H de- 2 4 Academy of Sciences, Furthermore, decomposition of the NH compo- composition is in orbiting satellites, which use hy- Dalian 116023, China nent in the produced mixture can form H and N : 2 2 drazine to control their altitude and orbit adjustment and University of Chinese Academy of propulsion. NH (g) → 1/2N (g) + 3/2H (g)  H (298) 3 2 2 r Sciences, Beijing The thermal or catalytic decomposition of hy- 100039, China drazine occurs via two routes according to Eqs. −1 =+45.9kJmol . (4) (1–4) [1,2]: Corresponding Complete: N H (l) → N (g) + 2H (g) 2 4 2 2 During a catalytic decomposition process, the authors. E-mails: above-mentioned parallel reactions during catalytic ◦ −1 ◦ [email protected]; H (298) =−50.6kJmol , G (298) r r decomposition lead to a superimposition of the [email protected] −1 reaction products [1,3]. For each equation men- Equally contributed =−149.4kJmol . (1) to this work. tioned above, more than one elementary step is per- formed during the reaction process, which leads to Incomplete: N H (l) → 4/3NH (g) + 2 4 3 hydrazine decomposition containing many elemen- Received 2 July 1/3N (g) 2016; Revised 10 tary steps, hence the difficulty in describing them. ◦ −1 ◦ September 2016; To simplify the research that has been conducted us- H (298) =−111.9kJmol , G (298) r r Accepted 10 ing various catalytic systems, the above reactions are −1 September 2016 =−171.3kJmol . (2) unified by one equation, where x represents the H The Author(s) 2017. Published by Oxford University Press on behalf of China Science Publishing & Media Ltd. All rights reserved. For permissions, plea se e-mail: [email protected] Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 REVIEW He et al. 357 selectivity: H (g) 6 2 NH (g) N (g) 3N H (l) → 4(1 − x)NH (g) 2 4 3 5 2 N H (g) 2 4 + (1 + 2x)N (g) + 6xH (g). 2 2 (5) Depending on the application, it is desirable to design catalysts with controlled hydrogen selectiv- ity. For example, the specific impulse of a chemi- cal rocket exhibits a maximum in the H selectivity 0 100 200 300 400 range of 30–40% when hydrazine is used as a space Temperature ( ) propellant. The production of CO-free hydrogen is currently Figure 1. Thermodynamic products versus temperature for a hot topic, and the catalytic decomposition of hy- the decomposition of 3 mol hydrazine (0.1 MPa). drazine is proposed for this purpose [4–6]. If com- plete N H decomposition proceeds through equa- 2 4 reducing agent that is used to control corrosion in tion (1), the hydrogen released is calculated to be boilers, reduce noble metal catalysts or graphene ox- 12.5 wt.%. This value is significantly larger than the ide, and to hydrogenate unsaturated bonds in or- target set by the Department of Energy (DOE) for ganic compounds [11]. In the case of handling spent onboard hydrogen systems (5.5 wt.%) [7]. There- hydrazine, complete decomposition of hydrazine fore, N H qualifies as a mobile hydrogen source 2 4 into hydrogen and nitrogen is considered the most meeting the DOE target. Additionally, during the suitable route to circumvent the production of am- complete decomposition of N H , three equivalent 2 4 monia. moles of gaseous products are generated leading to The development of efficient and selective cat- increased volumes of emitted gas, which prevents alysts for H generation from hydrazine is an im- the solubility of ammonia in water, thus providing portant topic considering the applications described a driving force in submarine rescue systems when above. From a thermodynamic perspective, the employing hydrazine for ballast water expulsion. In Gibbs free energy of equation (2) is lower than that such cases, it is critical that catalyst design yields high of the equation (1). That is to say, hydrazine decom- selectivity, especially in mild conditions. position to ammonia is thermodynamically more Another important property of hydrazine is the favorable. As shown in Fig. 1, the major thermo- formation of hydrous hydrazine when hydrazine re- dynamic products of hydrazine decomposition are acts with water, similar to ammonia. The monohy- NH and N at low temperature. Therefore, it is chal- 3 2 drate of hydrazine (N H ·H O) has a much lower 2 4 2 lenging to avoid its undesirable decomposition to freezing point (−51.7 C) compared with N H 2 4 ammonia. (1.4 C), which makes the former a suitable pro- In this review, we briefly introduce the mech- pellant when employed across a wider temperature anism of hydrazine decomposition to demonstrate range. The water molecule may potentially lead to the principles of catalyst design. Thereafter, cat- a partial slowdown of the decomposition rate. Al- alytic systems are presented that focus on the se- though N H ·H O is still considered to be a dan- 2 4 2 lective decomposition of N H or N H ·H Oun- 2 4 2 4 2 gerous chemical, it is far safer to handle compared der mild conditions. To date, multiple strategies to explosive N H and, thus, more suitable for in- 2 4 in catalyst design have been reported, including vestigation in fundamental research. In 2009, Xu and pure metallic nanoparticles and supported catalysts. co-workers proposed the idea of using hydrous hy- These catalytic systems are divided into three types drazine as a potential candidate for chemical hy- according to their influencing factors on H selectiv- drogen storage [8]. Since then, there have been a ity, including alloying effects, alkali promotion and number of reports concerning the decomposition of metal–support interactions. The principal reasons hydrous hydrazine compared with its anhydrous for the tunable selectivity are discussed both experi- counterpart. mentally and theoretically, which may provide guid- Hydrazine, being the simplest diamine, has appli- ance for further catalyst design. In addition to inspir- cations beyond chemical propellants and is widely ing further research on hydrazine decomposition, employed as a precursor in the synthesis of or- we hope that this review will stimulate research on ganic molecules containing N–N bonds, especially other related N-containing reactions, such as NH in the preparation of pesticides and pharmaceu- or NH BH decomposition. 3 3 ticals [9,10]. Additionally, hydrazine is a strong Equilibrium amount (mol) Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 358 Natl Sci Rev, 2018, Vol. 5, No. 3 REVIEW [20,21], Fe (211) [22], Ni [23] and Cu [24] NH surfaces. However, the adsorption conformations of N H H N NH NH H 2 4 2 2 N H 2 4 hydrazine and the intermediates show significant differences in these reports. The hydrazine decom- N=N HN=NH HH 2 NH position mechanism is still contested over different metallic catalysts. Therefore, tailoring of selectivity 2 H N NH H N NH 2 2 through catalyst design is still determined experi- (a) HN=NH N=N HH HH mentally. Essentially, the reaction route is determined by N=N HN=NH the sequence of N–N bond and N–H bond cleav- HH 2 NH age [1]. The N–N bond cleavage energy in gaseous −1 N H N H is 286 kJ mol , and the N–H bond energy 2 4 H 2 4 −1 is 360 kJ mol when the entire bond breaks into (b) N and H atoms. From a thermodynamic viewpoint, N H 2 4 H N NH the first step relating to N–N bond cleavage appears N H 2 2 N H HNNH 2 4 2 4 2 2 2 NH 2 NH 3 3 to be easier, which consequently leads to the pro- H H NN HNNH HN NH HN NH N N 2 2 H H N duction of N and NH . However, the bond en- 2 3 −1 ergy of N–H is lowered to 276 kJ mol if N H 2 4 partially breaks into N H and H adatoms are ob- 2 2 served over a Ni (100) surface [25], which can po- Figure 2. Reaction pathways for hydrazine decomposition. (a) NH ,N and H 3 2 2 formation. (b) NH and N formation. tentially lead to large quantities of H being pro- 3 2 2 duced. In another case, the H–Pt bond is stronger than the N–Pt bond on Pt(111), leading to the bar- MECHANISM CONSIDERATION rier to N–H cleavage being much lower than that to N–N cleavage [15]. As a result, regardless of the Early research focused on mechanistic studies via higher N–H bond energy compared with the N–N adsorption experiments over Ir, Pt and Rh model bond, the first bond to break in hydrazine adsorbed metallic surfaces [12–16]. For example, it has been on platinum is an N–H bond instead of the N–N observed that the initial step of hydrazine decompo- bond. Nitrogen forms and desorbs close to 40 C sition over an Ir surface is the dissociative adsorption through an intramolecular process [15]. Motivated of the N H molecule, which produces the adatoms 2 4 of nitrogen, hydrogen, and NH species [12]. The by these findings, the SiO -supported Ni, Pd and Pt 2 2 adsorbed hydrogen atoms display good mobility and catalysts developed by our group displayed excellent can further react with another hydrogen atom to H selectivity in gas phase hydrazine decomposition, produce molecular hydrogen or with an NH radi- even at room temperature [3]. According to these cal to produce NH . Under mild conditions in the reports, the higher H selectivity on Ni-, Pd- and 3 2 presence of an Ir surface, NH is the main product Pt-based catalysts is because of the lower barrier to because of the ease by which NH combines with N–H cleavage, which may be related to the stronger adsorbed hydrogen. Conversely, the main inter- M–H bond. Furthermore, de Medeiros et al. corre- mediate is NH in the presence of an Rh surface lated H selectivity with the enthalpy of adsorption using temperature-programed surface reaction ex- of hydrazine. Hydrazine decomposition over cata- periments, which generate N and H as the main lysts possessing low enthalpies of adsorption mainly 2 2 products at low N H coverage and N and NH at produces N and H . On catalysts having high en- 2 4 2 3 2 2 −1 high N H coverage [14]. thalpies of adsorption (520 kJ mol ), the reaction 2 4 Isotopic-labeled N H was employed to obtain products are N and NH [26]. To summarize the 2 4 2 3 further information regarding the intermediates dur- most plausible mechanism, general reaction path- ing the decomposition process [17,18]. The ratio of ways for hydrazine decomposition are proposed in 15 14 Fig. 2, showing NH ,N and H formation (Fig. 2a), Nto N in the produced N is small, which il- 2 3 2 2 and NH and N formation (Fig. 2b). Because the lustrates that the produced N–N comes from the 3 2 theory of hydrazine decomposition is not compre- same hydrazine molecule and therefore abrogates hensive enough, catalyst design for H generation the hypothesis of prior N–N cleavage during the from hydrazine is mainly based on experimental ex- N H decomposition process [17]. With the devel- 2 4 ploration. It should be noted that the decomposition opment of computational technologies, theoretical calculations have been performed over noble metal of hydrazine has been studied in the vapor phase as and non-noble metal surfaces. Further detailed re- well as in solution. Although the mechanism is very action pathways have been proposed over various similar in both cases, it is sometimes difficult to ex- modeling surfaces, such as Ir(111) [19], Rh(111) clude solvent and surface interference in the latter Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 REVIEW He et al. 359 In 1979, an Al O -supported Ir–Ni catalyst was case [27]. Therefore, we indicate which phase the re- 2 3 studied for its performance in gas hydrazine decom- action is in hereafter. position at 27 C[31]. Although Ir is considered to be the most active metal for gas hydrazine decom- position, its selectivity for hydrogen is poor at low CATALYTIC SYSTEMS temperatures. Alloying Ni to Ir led to an increase Metallic catalysts are one of the most widely used in H production through complete decomposition catalytic systems in heterogeneous catalysis for via equation (1). The adsorption experiment results industrial applications. These catalysts are often have demonstrated that the surface bonding of NH composed of active metals, supports and other pro- and N adspecies to Ir is weakened by the addition of moters. There are many factors that can influence Ni atoms, which originate from the formation of the catalytic performance, including the choice of metal Ir–Ni alloy. In 2009, Xu and co-workers reported the and support composition, the exposed facet of the excellent performance of Rh–Ni bimetallic nanopar- active metal, the interaction between the metal and ticles in hydrogen production via hydrous hydrazine the support, and the properties of the additional pro- decomposition [32], which inspired the following moters. From a molecular point of view, the surface research on bimetallic catalysts. The catalytic perfor- structure and electronic properties are the main in- mances of various two-component transition metal fluencing factors for heterogeneous catalysts as the catalysts are summarized in Table 1. The Ni-based majority of the reactions occur on the surface. For bimetallic catalysts with or without supports pro- hydrazine decomposition, changes to the sequence vide the highest H selectivity, which stimulated in- of N–N bond and N–H bond cleavage are the ma- terest in investigating the reason for their excellent jor strategy to change selectivity. Among various cat- performance. To date, nanoparticles composed of alytic systems, transition metals (e.g. Ir, Ru and Ni) three types of metals have been reported, includ- are the most efficient candidates for N–H bond ac- ing NiFeCu [33], NiFePd [34] and NiFeMo [35]. tivation and exhibit high activity for hydrazine de- Additionally, other novel materials have been tested composition under mild conditions. However, H in the decomposition of hydrous hydrazine, such selectivity is limited to below 10% over Ru and Ir as Co Se/graphene hybrid nanosheets [36]; Ni– 0.85 catalysts. To date, monometallic catalysts have failed B[37], Co–B [38,39], Fe–B [40] and Rh–Ni–B to achieve the complete catalytic decomposition of [41] materials; Ni–Rh and Ni–Pt nanoparticles im- hydrous hydrazine to H without generating NH . 2 3 mobilized on a metal–organic framework (MOF); Hence, modification of the catalysts is necessary to and MOF-derived carbon dots and nitrogen-doped promote H selectivity. In this section, methods that porous carbon [42–44]. These materials have exhib- have been explored for the promotion of H forma- ited good performance in hydrous hydrazine decom- tion will be introduced, including alloying of a sec- position, although further discussion is not included ond metal, alkali addition and then introduction of in this review. strong metal–support interactions. To study the reasons why the second metal promotes catalytic performance, structural config- uration and surface adsorption experiments were Alloy effect performed. It is well documented that the arrange- ment of the two metals can result in three structure Bimetallic catalysts often exhibit enhanced activity, types: alloy, core-shell, and heterogeneous. For Pt- selectivity and stability compared with their par- promoted Ni catalysts, X-ray diffraction (XRD) re- ent metals because of their distinct electronic and sults illustrate that the main diffraction peaks show chemical properties. Therefore, the development of only the existence of metallic Ni [45]. The diffrac- bimetallic catalysts provides opportunities to obtain tion peaks shift to lower angles after doping with novel catalysts with improved catalytic performance Pt, demonstrating the formation of a Ni–Pt alloy in many industrial applications. To further under- in the bimetallic catalysts. The formation of the stand the origins of their novel properties, bimetallic Ni–Pt alloy has been further confirmed by the co- catalysts have been extensively studied in fundamen- reduction of Ni and the second metal, illustrated by tal research. The geometric and electronic changes H -temperature-programed reduction (TPR) data. of the bimetallic surface have been shown to be the Furthermore, extended X-ray absorption fine struc- reason for their extraordinary properties in many re- ture (EXAFS) experiments have been employed to actions, such as hydrocarbon reforming, as reported previously in the literature [28–30]. In this section of study the Pt oxidation status and its coordination the review, we will focus on summarizing the inves- environment. The results indicate that the majority tigation of bimetallic catalysts for hydrous hydrazine of the Pt species exist in the form of a Ni–Pt al- decomposition to date. loy, which leads to an electronic transfer from Ni to Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 360 Natl Sci Rev, 2018, Vol. 5, No. 3 REVIEW Table 1. Comparison of hydrogen selectivity (%) of hydrous hydrazine decomposition over different bimetallic catalysts. Fe Co Ni Fe 0 [46] 100 [46–48] Co 0 [46]18[46] Ni 100 [46–48]18[46] Ru 99 [49] Rh 30 [32]20[32] 100 [32,50–53] Pd 0 [54]7[54] 100 [55] Ir 0 [56] 100 [57] 100 [56,58] Pt 0 [46]72[59] 100 [45,60–66] Au 80 [58] Cu 0 [46]15[46] 100 [67] Pt. Therefore, the adsorption of H and NH is sig- their catalytic performance. As shown in Fig. 3,the 2 3 nificantly weakened on the bimetallic surface com- low-temperature-reduced catalyst (Ni–Ir/Al O - 2 3 pared with the parent Ni or Pt catalysts, which has 300R) showed >99% H selectivity. In contrast, been proven by H -temperature-programmed des- the analogous high-temperature-reduced catalysts orption (TPD), microcalorimetry and NH -TPD (Ni–Ir/Al O -500R and Ni–Ir/Al O -700R) 3 2 3 2 3 experiments. showed a considerable reduction in H selectivity In addition to the three bimetallic structure [58]. The results of XRD, EXAFS and H -TPR systems, the diverse arrangements of the surface and confirmed alloy formation for all three catalysts. sub-surface metal atoms of the binary system show However, the coordination number of the Ni–Ir a significant influence on the surface adsorption bond increased in the order of Ni–Ir/Al O -300R 2 3 and electronic properties of the alloy catalysts < Ni–Ir/Al O -500R < Ni–Ir/Al O -700R, which 2 3 2 3 [28,30]. Further studies on Ni–Ir catalysts were per- demonstrated the relocation of Ir atoms from the formed to investigate the influence exerted by the surface of the Ni–Ir alloy particle into the core as arrangement of the surface atoms, and revealed that a function of increasing reduction temperature. pretreating temperatures significantly influenced Consequently, the atom arrangement at the surface changed from a Ni–Ir alloy into a Ni-rich surface, leading to a decrease in H selectivity during Ir hydrous hydrazine decomposition. Ni Furthermore, the surface structure was char- acterized for Pt-, Ir- and Au-doped Ni bimetallic catalysts reduced at equivalent temperatures. Corre- lating with their hydrous hydrazine decomposition catalytic performance, it was concluded that the for- mation of a surface alloy is necessary for the purpose Selectivity (%) of obtaining high H selectivity [58]. Provided a ho- -1 Reaction rate (h ) mogeneous alloy is formed, such as a Pt–Ni cata- δ+ lyst, the Ni can be observed because of the partial electron transfer from Ni to a nearby Pt atom. Con- versely, for Au–Ni catalysts, segregation of Au on the 60 8 surface is detected. This structural change greatly in- fluences the surface adsorption properties and cat- alytic performance of the catalyst. The surface struc- ture of the alloy catalyst plays an important role in the generation of H from hydrous hydrazine de- composition and may promote future rational cat- alyst design to obtain good activity and superior selectivity. 0 0 300 500 700 Reduction temperature (ºC) Strong basic promoter Figure 3. Structural model of bimetallic Ni–Ir catalysts for hydrous hydrazine decom- For heterogeneous catalysts, non-active compo- position. Reprinted with permission from [58]. Copyright 2013 Elsevier B.V. nents are typically added as promoters to adjust Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 REVIEW He et al. 361 properties, as shown in the insets of Fig. 4. The ap- parent activation energies were calculated for H (pathway 1) and NH (pathway 2) generation, re- spectively. The results indicated an increase in the activation energy for pathway 2 after the addition of 80 NaOH, which confirmed the inhibition of NH pro- duction with the existence of NaOH. Recently, several supported metal catalysts were shown to catalyze the decomposition of hydrous hy- drazine with nearly 100% H selectivity. This high Magnet (a) (b) selectivity could be attributed to the existence of 0 0.05 0.10 0.25 0.50 1.00 2.50 -1 strong basic sites over the catalysts. In the study of NaOH concentration (mol L ) hydrotalcite-derived Ni/Al O catalysts, H selec- 2 3 2 Figure 4. H selectivity improvement as a function of strong 2 tivity reached 93% at 30 C, which was significantly basic promoter concentration in hydrous hydrazine decom- higher than the impregnated counterpart (67%) position on Raney Ni catalyst. Insets: magnetic separation [70]. The CO –TPD results revealed large concen- property of Raney Ni catalyst after reaction of (a) reactants trations of strong basic sites in the hydrotalcite- with catalyst after reaction and (b) with a magnet to sepa- derived Ni/Al O , which are thought to originate 2 3 rate catalyst. Reprinted with permission from [69]. Copyright 2− from the O species in the Ni–O–Al structure. The 2013 American Institute of Chemical Engineers. strong basic sites inhibit the production of NH and also influence the electronic properties of Ni par- ticles, which consequently improves H selectivity selectivity or enhance activity. For example, the ad- during hydrous hydrazine decomposition in mild dition of alkali promoters is crucial for ammonia syn- conditions. thesis. In the 1970s, strong basic components, e.g. In summary, the promoting effect can be at- NaOH and KOH, were found to improve H selec- tributed to two aspects: i) inhibition of generation of tivity for hydrous hydrazine decomposition over Ir the basic byproduct NH and ii) electronic perturba- catalysts at low temperatures [1]. However, these tion on the surface of the active metal because of the additives could not catalyze this reaction themselves existence of vicinal strong basic sites. However, the and led to a decrease in the reaction rate. Recently, addition of alkalis may not be the best choice to im- the development of non-noble metal catalysts for hy- drous hydrazine decomposition to improve H gen- prove H selectivity via hydrous hydrazine decom- eration has gained significant attention. It is impor- position when taking into account environmental tant to note that strong basic additives are necessary issues. for such catalysts to obtain high H selectivity in mild conditions. These strong basic promoter additives can be divided into two types: i) alkalis (e.g. NaOH) Strong metal–support interaction effect added separately and ii) basic supports combined with the active component during preparation. Widely used industrialized heterogeneous catalysts Xu and co-workers developed the bimetallic often consist of metal nanoparticles supported on Ni–Fe nanocatalyst, which could catalyze the com- large surface area oxides. The importance of these plete decomposition of hydrous hydrazine with oxides has been increasingly recognized over recent the assistance of NaOH [46]. Later, many multi- decades, following the discovery of metal–support component catalysts were found to catalyze this re- interactions. In addition to dispersing metallic par- action with the addition of an alkali, such as Fe– ticles, the oxide support also influences the catalytic B/MWCNT [40] or NiMoB–La(OH) [68]. In our properties of the metal catalysts through geometric research on Raney Ni catalysts [69], the addition or electronic effects. The representative oxides in- of NaOH was precisely controlled. Before the addi- clude CeO ,TiO and Fe O . 2 2 2 3 tion of NaOH to the Raney Ni catalyst, H selec- To investigate the influence of the support for tivity reached only 80% during the decomposition Ni catalysts in hydrous hydrazine decomposition, of hydrous hydrazine. As shown in Fig. 4,asmall two types of Ni/CeO catalysts were prepared us- −1 amount of NaOH (0.05 mol L ) could significantly ing co-precipitation and impregnation methods, de- promote the selectivity to 91%. Further increasing noted as Ni/CeO -CP and Ni/CeO -IMP, respec- 2 2 −1 the concentration of NaOH to above 0.5 mol L , tively [71]. The two Ni/CeO catalysts exhibited the H selectivity reached over 99%. In addition, quite different activity and selectivity toward hy- the Raney Ni catalyst could be easily collected and drous hydrazine decomposition because of their sig- reused after the reaction because of its magnetic nificant structural differences. The Ni particles were H Selectivity (%) 2 Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 362 Natl Sci Rev, 2018, Vol. 5, No. 3 REVIEW ports, as long as a Ni–O–M structure formed. This finding may inspire the future design of more effi- cient catalysts for the decomposition of hydrous hy- drazine using economically viable facile preparation methods. N N H H Ni Ni Ce Ce Ni/CeO Ni/C O -CP CP Ni/CeO -IMP 2 2 O CONCLUSION AND OUTLOOK Different hydrazine usage demands have made hy- Figure 5. Structural models of Ni/CeO -CP and Ni/CeO - 2 2 drazine decomposition selectivity increasingly im- IMP. Reprinted with permission from [71]. Copyright 2015 portant. This focus of this review has been to American Chemical Society. analyze factors that influence improvements to hy- drogen selectivity in mild conditions. As Ni-based catalysts have been proven to be the most active can- highly dispersed in the co-precipitated sample over didates, strategies to further improve their perfor- high Ni loading, which led to improvements in ac- mance have been analyzed, including the choice of tivity for the reaction. In contrast, Ni/CeO -IMP metal composition, alkali promoter addition and the resulted in obvious aggregation of Ni particles be- tailoring of metal–support interactions. Our intent cause of the small surface area of the CeO sup- is to encourage the development of more highly se- port, resulting in significantly lower activity. Fur- lective catalysts for H production via hydrous hy- thermore, H selectivity reached over 99% for the drazine decomposition. Ni/CeO -CP catalyst, considerably higher than for Although many attempts, both experimental and the impregnated counterpart (65%), although the theoretical, have been made to reveal the key factors Ni particle sizes were very similar on both samples. that affect the selectivity of metallic catalysts, the de- Electron microscopy images, H -TPR and Raman tailed mechanism is still not fully understood. There- spectroscopy results indicated that Ni particles fore, studies on hydrazine decomposition are neces- were partially surrounded by amorphous CeO in sary to better understand the reasons for selectivity Ni/CeO -CP (Fig. 5). The co-precipitation method differences. Additionally, such studies may further induced the existence of a Ni–O–Ce structure. How- inspire the exploration of other reactions including ever, for Ni/CeO -IMP, the Ni particles resided on N–N bonds and N–H bonds, such as NH synthesis CeO with little interaction between Ni and CeO 2 2 or decomposition, and provide opportunities for the [71]. This geometric variation of the surface struc- development of novel catalytic systems. ture led to an electronic change of the exposed Ni. Furthermore, the majority of the catalysts re- Using CO as an adsorption probe, Fourier Trans- ported in the literature to date have only been form Infrared Spectroscopy (FT-IR) results illus- successful at the laboratory scale and have shown trated that the exposed Ni species in Ni/CeO -CP limitations in industrial application. As is already differs from metallic Ni. The presence of a weak CO known, this reaction is an exothermal process, and δ+ adsorption band on the Ni site could be observed, the amount of heat released and the distribution of indicating changes to the electronic properties of the gaseous products (N ,H and NH ) depends on 2 2 3 exposed Ni species on Ni/CeO -CP because of the the reactive conditions and the selectivity of the cat- modification of vicinal CeO [71]. In particular, the alysts. Therefore, heat and mass transfer should be CeO support not only played a role in dispersing Ni considered during the design of catalysts. In addi- particles, but also behaved as a promoter or modifier tional, the stabilities of the currently available cata- to improve hydrogen selectivity of Ni in the decom- lysts are not sufficient to meet the demands of indus- position of hydrous hydrazine. trial production. Therefore, many engineering and On the basis of results outlined above, we syn- technological problems need to be investigated and thesized other Ni–O–M structures on varying metal resolved prior to their industrial application. oxide supports. Using the co-precipitation method, a series of supported Ni catalysts were prepared, including Ni/MgO, Ni/La O and Ni/ZrO [71]. 2 3 2 These catalysts had one thing in common: a strong FUNDING metal–support interaction existed between Ni and This work was supported by the National Natural Science Foun- the oxide support. Similar to the Ni/CeO –CP sam- dation of China (21103173 and 21476226), the Strategic Pri- ple, these catalysts all exhibited >80% H selectivity 2 ority Research Program of the Chinese Academy of Sciences for hydrous hydrazine decomposition, which further (XDB17020100), the National Key Projects for Fundamental confirmed the promotion effect of the oxide sup- Research and Development of China (2016YFA0202804) and Downloaded from https://academic.oup.com/nsr/article/5/3/356/4282588 by DeepDyve user on 16 July 2022 REVIEW He et al. 363 the Youth Innovation Promotion Association of the Chinese 19. Zhang P, Wang Y and Huang Y et al. Density functional theory Academy of Sciences. investigations on the catalytic mechanisms of hydrazine decom- positions on Ir(111). Catal Today 2011; 165: 80–8. Conflict of interest statement. None declared. 20. Deng Z, Lu X and Wen Z et al. 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Published: May 1, 2018

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