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Topics in Catalysis

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Open Access 17.07.2023 | Original Paper

A Highly Active and Reusable Multicomponent high Entropy Metal Oxide Catalyst for Nitroarenes Hydrogenation

verfasst von: Nayereh Soltani, Jamil Ur Rahman, Patricia Almeida Carvalho, Terje G. Finstad

Erschienen in: Topics in Catalysis | Ausgabe 5-8/2024

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Abstract

It is well known that multicomponent catalysts can improve catalytic performance, however their rational design and precise control of catalytic activities by varying the composition of the elements is challenging. Herein, we present a facile and scalable synthetic strategy for production of senary and septenary metal oxide nanoparticles with a chemical composition of MSbO_x and MSb₂O_x (M: Fe, Ni, Co, Cu, and Zn). All samples were formed in a tetragonal crystal structure with space group 136 and crystallographic symmetry P42/mnm while the details of their constituent unit cells are different, belonging to rutile or trirutile structures. These nanocomposites have an oxygen vacancy-rich construction with uniform elemental distributions that produce various surface functionalities. They showed instantaneous hydrogenation catalytic performance for reduction of 4-nitrophenol to 4-aminophenol at room temperature. Among our samples, the senary catalyst with MSbO_x chemical composition showed better durability and reusability owning to its morphological and microstructural properties. It showed 100% conversion of 4-nitrophenol to 4-aminophenol within 4 min at the 18th run without any by-products.

Supplementary Material 1

Supplementary Information

The online version contains supplementary material available at https://doi.org/10.1007/s11244-023-01846-z.

The original online version of this article was revised: In this article the author’s name Jamil Ur Rahman was incorrectly written as Jamal Ur Rahman.

A correction to this article is available online at https://doi.org/10.1007/s11244-023-01852-1.

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Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

1 Introduction

Metal oxide nanoparticles (NPs), with their countless compositions, structures and bonding, constitute a class of inorganic materials that exhibit a very diverse range of properties. They have found a variety of potential applications in different fields including as catalysts, sensors, batteries, fuel cells, solar cells, magnetic storage media, etc. [1‐6].

Recently, researchers focus on the synthesis of a new class of oxide systems containing multiple metal cations (typically ≥ 5) stabilized in a single-phase crystal structure. These materials are based on stabilization by entropy and known as high-entropy oxides (HEO) [6, 7]. The stabilization concept was first discovered in high entropy metallic alloys. Due to the electronic interaction between the various cations in the oxide, they can show remarkable properties and unexpected behavior [7]. The random distribution of cations increases the configurational entropy and contributes to phase stability. Simultaneously, it will influence the distribution of lattice site energies and lattice distortions, leading to a nonlinear synergetic response [6]. The vast variety of metal compositions offers a flexible design and potential to develop customized properties [8]. The enthalpy of mixing and configurational entropy are the main design parameters for the formation of a stable phase. Moreover, the size and valency of cations are important to accommodate the oxygen sub-lattice, and maintain the charge balance [7].

In the field of catalysis, metal oxides play a critical role in petrochemical and refining processes, chemical synthesis and environmental improvements [5]. However, multi-metal oxide NPs developed much slower compared to multicomponent metal-based catalysts and there are plenty of room to discover and develop. The major reason is that multi-metal oxide catalysts are more complex due to the possible presence of multiple oxidation states and different surface termination functionalities [9]. The synthesis method can widely change the characteristics and control the properties of the obtained oxide NPs [6]. It is important to develop new strategies for facile, green and scalable synthesis of multi-metal oxide NPs based on earth abundant elements with the desired physical properties.

Amongst multi-metal oxide compounds, one of the most important class of catalysts attaining commercial status are those based on antimonates. They mostly belong to the rutile and trirutile crystal structure families, but some of them have more complex structures [10]. Antimony-based oxide catalysts have good oxygen binding energetics and strong phase stability, and they were found to efficiently catalyze a wide variety of reactions [11‐14].

The present work is derived from an interesting part of our previously published work [15], where we obtained senary and septenary transition metal antimony-based oxide NPs as an intermediate product through a simple and scalable thermal treatment method. These nanocomposites have chemical composition of MSbO_x (M: Fe, Ni, Co, Cu, and Zn) and show an oxygen vacancy-rich structure which is favorable in catalytic applications. Herein, we tried to synthesize senary and septenary versions of well-known transition metal antimonate catalysts with the chemical composition of MSb₂O_x through the same method, and compare their catalytic performance. To investigate the efficiency of these nanocomposite as a heterogeneous catalyst, the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of NaBH₄ in an aqueous medium at room temperature were used as a model reaction [16‐18]. This reaction is a convenient model reaction as has been characterized by many and there is essentially no reaction at room temperature without catalyst. This heterogeneous catalytic reduction is environmentally and industrially important because 4-NP is an organic pollutant in industrial wastewaters and 4-AP is an important industrial intermediate used for the preparation of analgesics, antipyretic drugs, and photographic developers [3, 19‐22]. Oxygen-deficient metal oxides can easily adsorb and activate nitroarenes through the adsorption of the oxygen ends of 4-NPs by oxygen vacancies [23]. The catalytic capability of different samples is compared and discussed in terms of reduction time, rate constant, and catalyst reusability.

2 Experimental

2.1 Materials and Methods

The metal salts of antimony chloride (SbCl₃), iron chloride (FeCl₃), nickel chloride (NiCl₂·6H₂O), cobalt chloride (CoCl₂·6H₂O), copper chloride (CuCl₂), and zinc chloride (ZnCl₂) with purities more than 97%, were used as metal precursors. Polyvinyl pyrrolidone (PVP10) and ethanol (≥ 99.9%) were used as stabilizer and solvent, respectively. All chemicals were purchased from Sigma-Aldrich and VWR chemicals and used without further purification.

A facile thermal treatment method has been applied for the synthesis of multi-component metal oxide NPs [15]. In the synthesis process for each case, the appropriate amount of PVP was dissolved in ethanol under vigorously stirring at a temperature of 60 °C followed by the addition of metal chlorides according to the stoichiometry, and ultra-sonication. The final solution was air-dried at 60 °C for 24 h in a petri dish. The resulting green solid was crushed and ground into powder and calcined in air at 600 °C for 2 h. The molar ratio of PVP (in terms of its repeating unit) to metal chlorides was kept at 1.2 and the equimolar of transition metal elements was used for all of samples. The nominal compositions of samples are Fe_0.25Ni_0.25Co_0.25Cu_0.25SbO_x, Fe_0.2Ni_0.2Co_0.2Cu_0.2Zn_0.2SbO_x, Fe_0.25Ni_0.25Co_0.25Cu_0.25Sb₂O_x, and Fe_0.2Ni_0.2Co_0.2Cu_0.2Zn_0.2Sb₂O_x which is referred to as (FeNiCoCu)SbO_x, (FeNiCoCuZn)SbO_x, (FeNiCoCu)Sb₂O_x and (FeNiCoCuZn)Sb₂O_x respectively in the remainder of the text. The nominal composition is the only difference in the synthesis of the samples. The nominal composition is given by the relative amount of Sb atoms and transition metal atoms in the precursors which is given by their weight and composition. The experimental determination of the actual composition of the samples is described in Sect. 2.2.

2.2 Characterization

The structural characterization of the samples was done by X-ray diffraction (XRD), using the Bruker AXS D8 discover system by Cu Kα (λ = 1.5406 Å) as X-ray source. Diffrac.EVA6, and Diffrac.Topas6 programs were used for analysis of XRD patterns. Morphology, particle size and compositional analysis of products was carried out by scanning electron microscopy (FEI Quanta 200 FEG SEM) and energy-dispersive X-rays (EDX) spectroscopy (an attachment to SEM instrument), and also using high-resolution transmission electron microscopy (HR-TEM, 0.8 Å resolution), and energy-dispersive X-rays (EDX) with a FEI Titan G2 60–300 microscope operated at 300 kV. A fully-automatic gas adsorption measurement device (BELSORP-Minix) was used for evaluated of specific surface area of samples according to the Brunauer–Emmett–Teller (BET) theory [20]. Samples were degassed at 250 °C for 2 h under vacuum before the measurement and nitrogen gas was used as absorbate at 77 K. The catalytic reaction of samples was monitored by absorption spectra recorded using UV-visible spectrophotometry (Specord 200 Plus, Analytik Jena, Germany) in the wavelength range of 250–550 nm.

2.3 Catalytic Reaction

The powder samples were dispersed ultrasonically in deionized water followed by the addition of freshly prepared aqueous solutions of 4-NP (10^− 4 M) and NaBH₄ (6 × 10^− 2 M) with the volume ratio of 1:1:1. The reaction for all samples is instantaneous and cannot be monitored even with minimizing the amount of catalyst. Therefore, to compare the catalytic performance of the samples, an experiment consisting of several runs was performed for each sample. After completing the reduction in each run, fresh 4-NP solution (10^− 3 M) was added to the used mixture with the volume ratio of 0.1:3 relative to the volume of the mixture in the first run. The reduction of 4-NP was monitored using UV–vis absorption spectroscopy by analyzing of the suspension at different time intervals.

3 Results and Discussion

The proposed mechanism for the synthesis of multi-component metal oxide NPs using the thermal treatment method is described elsewhere [15]. In summary, by dissolving of metallic salts in the PVP solution, the stable complexes are formed by ionic bonds between the metallic ions and amide group of polymeric chains. These bonds cause the uniform stabilization of metallic ions with local stoichiometry in the cavities of the polymer chains in the drying step and formation of multi-component metal oxide NPs in the calcination process [15, 25‐28]. A key development in this method is keeping the metals well mixed and preventing phase separation.

The formation of MSbO_x and MSb₂O_x NPs was confirmed by powder X-ray diffraction studies (Fig. 1). The XRD patterns of all samples are similar and high crystallinity of products is evident from the sharp peaks. They are all consistent with the tetragonal structure with space group 136 and crystallographic symmetry P42/mnm. However, the arrangement of atoms and lattice parameters are somehow different and influencing the diffraction patterns. For (FeNiCoCu)SbO_x, the dominant diffraction peaks match those listed for the tetragonal rutile-type compound of Fe_0.5Sb_0.5O₂ (COD 9,009,425). The metal sites in this structure are occupied by Sb and Fe with no ordering and forms a pseudo-solid-solution of FeO₂ and SbO₂ with rutile structure. All the transition metals used here can be introduced into oxide solid solutions with this structure.

The peaks observed in the XRD patterns of (FeNiCoCuZn)SbO_x match perfectly with the crystalline planes of the Fe_0.5Sb_0.5O₂ (COD 9,009,428), which has larger unit cell than that of rutile type (inset in Fig. 1) and two different atomic sites for metal cations (trirutile-type). The metal sites in this structure are occupied by Sb and Fe without ordering, so all the transition metals can be placed on any of these sites randomly.

The dominating diffraction peaks in the XRD profiles of (FeNiCoCu)Sb₂O_x can be indexed as the tetragonal trirutile-type compound of CoSb₂O₆ (COD 1,530,639). In this structure there are two different sites for Co and Sb cations in the lattice. It is expected that all transition metals occupy the cobalt site.

The XRD pattern of (FeNiCoCuZn)Sb₂O_x shows a series of sharp and well-defined peaks matching that from a single-phase tetragonal structure of the trirutile-type such as the compound ZnSb₂O₆ (COD 9,012,739). The zinc site in this structure can probably be occupied by all the transition metals in the samples. The positions of atoms and vacancies in the crystal structure of the samples were checked using XRD patterns in the EVA-, VESTA- and Topas-programs after having obtained quantitative EDX results.

The average crystallite size and lattice parameters of samples were estimated by Rietvald refinement of the XRD patterns using Diffrac.Topas6 program (Table 1).

Table 1

Microstructural parameters, particle sizes and BET surface area for different samples

Sample	Microstrain (×10^− 4)	Crystallite size (nm)	Lattice parameters (Å)		Particle size (nm)	Surface area (m² g^− 1)
Sample	Rietveld	Rietveld	ɑ	c	SEM	BET
(FeNiCoCu)SbO_x	3.9	19.5	4.64	3.08	53.0	11.33
(FeNiCoCu)Sb₂O_x	3.6	26.7	4.65	9.27	59.4	10.93
(FeNiCoCuZn)SbO_x	3.4	25.9	4.63	9.21	60.0	10.36
(FeNiCoCuZn)Sb₂O_x	3.4	33.6	4.66	9.24	121.0	7.48

The morphology and particle size distribution of samples were analyzed using TEM and SEM images (Fig. 2). The images reveal that all samples consist of particles with a quasi-polyhedron (angular) morphology. The average size and size distribution of the particles were evaluated from at least 200 particles for each sample. The senary samples contain particles with a narrower size distribution compared to the septenary samples. The (FeNiCoCu)SbO_x, particles have relatively uniform size ranging from 25 to 75 nm, while (FeNiCoCuZn)SbO_x contain particles with a wider range of sizes from 20 to 120 nm. The particle sizes in the (FeNiCoCu)Sb₂O_x have a size from 25 to 100 nm whereas (FeNiCoCuZn)Sb₂O_x are fairly inhomogeneous, containing a mixture of small and large particles ranging from 50 to 200. The average particle sizes of the samples were listed in Table 1. The results show that the average particle sizes are larger than the estimated crystallite sizes from the XRD peak broadening, indicating that each particle can be composed of several crystallites and is polycrystalline in nature.

The specific surface area of samples was evaluated by N₂ adsorption-desorption isotherms and BET analysis. A reversible type II isotherm (IUPAC classification [29]) was obtained for all samples, which reflects the physisorption of gases on nonporous adsorbents. The results (Table 1) show that the BET-specific surface area of samples is consistent with the size distribution and average particle size of samples and the senary sample of (FeNiCoCu)SbO_x shows the highest active surface area. An increase in the active surface area indicates an increase in the number of active sites that leads to improved catalytic performance [30].

The compositions of samples were investigated by EDX attachment to the SEM instrument. The EDX analysis confirmed that all the elements are homogeneously distributed across each sample, however they showed some deviation from the target composition. The average atomic fractions of the elements (Table 2) indicate that the synthesis process left behind some lattice vacancies in the crystals, probably antimony and oxygen vacancies. The non-stoichiometric phenomena on metal oxides containing the transition metals originate from the unfilled 3d electron shell [1]. To explore the type and the concentration of vacancies, the crystal structures were modeled using VESTA program first by considering no vacancies on the transition metal sites, and then by considering no vacancies in the metal sites. In the latter case, it was assumed that the Sb sites are occupied partially with the transition metals. Then, the calculated XRD patterns of samples were compared with the experimental results by Diffrac.Topas6 program. The calculated XRD patterns were in better agreement with the experimental results when no vacancies were considered on the metal sites. The percentage of oxygen lattice vacancies in this case are listed in Table 2.

Table 2

The quantitative EDX-SEM analysis of different samples and the oxygen vacancy concentration in agreement with EDX and XRD by considering no vacancy in metal sites

Sample	Sb (at%)	Fe (at%)	Ni (at%)	Co (at%)	Cu (at%)	Zn (at%)	O (at%)	Oxygen vacancies (%)
(FeNiCoCu)SbO_x	22.63	7.10	6.95	6.61	4.90	-----	51.81	37.1
(FeNiCoCu)Sb₂O_x	26.00	4.29	7.72	6.79	4.60	-----	50.60	48.8
(FeNiCoCuZn)SbO_x	20.77	4.61	5.20	4.93	3.86	4.16	56.47	35.1
(FeNiCoCuZn)Sb₂O_x	25.77	3.39	3.85	4.53	3.51	4.99	53.96	41.4

Further information on the elemental composition of samples were obtained by atomic EDX map and line scan in STEM-mode HR-TEM images (Fig. 3). The atomic EDX maps reveal that all the NPs contain all elements and the atomic EDX line scan confirmed that all the transition metal elements are evenly distributed through the crystals but the composition of Sb and O shows a small variation in some regions. This suggest that the deficiency of Sb and O atom is somewhat different from particle to particle.

The catalytic activities of the as-synthesized samples were evaluated for the reduction of 4-NP to 4-AP with NaBH₄ as reducing agent in an aqueous medium and room temperature. Nano multi-metal oxide compounds can catalyze the reduction by facilitating electron transfer from the hydrate ion (BH₄⁻) to the nitro group of 4-NP. The adsorption-desorption reaction of the substrate molecules occurs at the active site of the catalyst i.e. oxygen-deficient sites, and transition metal sites. Where, oxygen vacancies act as adsorption centers to absorb the oxygen end of 4-NP [23] and transition metals on the surface can bind with BH₄⁻ to form metal-hydride complex [31]. Then 4-NP is hydrogenated by coupling surface hydrogen species and electron transfer to nitro group. Simultaneously, the BH4- ions contribute to regenerating oxygen vacancies in the lattice by releasing oxygen atoms from the lattice sites [23].

All the adsorption-desorption steps occur quickly, and the rate-determining step is the reduction of adsorbed 4-NP on the surface by surface-hydrogen species [18, 32]. The catalytic process was monitored using UV–vis spectrophotometer. 4-NP shows strong absorption at 317 nm in aqueous medium, which shifted to 400 nm by addition of NaBH₄ due to the formation of 4-nitrophenolate ions. With a complete reduction in the presence of the catalyst, the characteristic peak of 4-NP disappears, and a new peak appears at 300 nm, consistent with the formation of 4-AP, and the color of the reaction mixture changes from yellow to colorless. The experiments showed that all samples have strong reducing capacity and give a sharp color change instantaneously. The reactions are very fast and their rate values cannot be determined even by minimizing the amount of catalyst (a quarter of the initial amount). The high catalytic activity of samples can be explained by the oxygen deficiency sites and the cocktail effect [33] in the multicomponent compounds that can alter the energy levels of bound intermediates and reduce the energy barrier for molecular adsorption, activation, and conversion [34].

To compare the catalytic performance of the samples, after the completion of reduction, fresh 4-NP solution was added to the used mixtures and the catalytic reaction was monitored in the repeated runs, where a run is defined as the time to complete the reduction. Figure 4 shows the time-dependent concentration changes of 4-NP and 4-AP during the catalytic reaction in the presence of (FeNiCoCu)SbO_x for 18 runs. The reduction in the second run is completed within 1 min. The conversion time for complete reduction increases in subsequent runs, reaching 4 min after 18 runs. Reconstruction of the surface during catalysis processes can be the main reason for the increase in the reduction time, especially in the first few runs. Evidence of this is the relative decrease in reflection intensity for the crystal planes (101) and (200) of the tetragonal structure in the XRD patterns of the recovered catalysts after the reaction (Fig. 5). The relative decrease in these peaks corresponds to the reduction of the oxygen vacancies on the surface of the samples according to the comprehensive structural analyses via Rietveld refinement done by Diffrac.Topas6 program. Moreover, termination of catalyst surfaces by oxygen anions reduces accessibility of reactant molecules to metal cations on the surface [5]. The continuous use of the mixture with the addition of fresh 4-NP solution reduces the concentration of catalyst and NaBH₄, and causes the formation of excess products in the reaction mixture. All these, together with the accumulation and precipitation of the catalyst over time, leads to an increase in the reaction time.

The kinetics of the catalytic reactions were evaluated using the pseudo first-order correlation [21, 22, 35]:

$$ln\frac{C}{{C}_{0}}=-kt$$

Where, C₀ and C are the absorbance intensities of 4-NP at reaction time of 0 and t, respectively and k is the apparent first-order rate constant. The plot of ln(C/C₀) as a function of reaction time showing a linear correlation and the rate constant can be calculated from the slope of the linear fit.

The ln(C/C0) plots for (FeNiCoCu)SbO_x by considering complete reduction of 4-NP to 4-AP are shown in Fig. 6. The calculated rate constant for different samples is calculated for 10 runs and the results are summarized in Table 3. The rate constants for FeNiCoCu)SbO_x, (FeNiCoCu)Sb₂O_x, (FeNiCoCuZn)SbO_x and (FeNiCoCuZn)Sb₂O_x samples in the tenth run reached to 22%, 27%, 25% and 14% of their values in the second run, respectively.

Table 3

The rate constant in each run for different catalysts is calculated by considering a complete reduction of 4-NP to 4-AP (×10^− 3 s^− 1)

Sample	Second	Third	Fourth	Fifth	Sixth	Seventh	Eighth	Ninth	Tenth
(FeNiCoCu)SbO_x	69.2	33.8	25.4	22.4	18.0	17.5	17.3	15.6	15.4
(FeNiCoCu)Sb₂O_x	6.6	2.8	2.5	2.5	2.4	2.3	2.2	2.0	1.8
(FeNiCoCuZn)SbO_x	16.7	9.8	8.7	6.4	6.3	6.0	5.5	4.8	4.2
(FeNiCoCuZn)Sb₂O_x	17.3	9.0	6.3	5.0	3.9	3.7	2.9	2.5	2.4

Among the as-synthesized samples, (FeNiCoCu)SbO_x showed the highest catalytic efficiency, having a k value about 10-times larger than that of (FeNiCoCu)Sb₂O_x and 4-times higher than that for the septenary samples in the second run. Furthermore, this sample showed the reusability by 100% conversion of 4-NP to 4-AP in the eighteenth run after only 4 min. The most important difference between this sample and the others is its simpler crystal structure from rutile family, while the others belong to the trirutile family. It has also a narrow size distribution and largest active surface area among the samples, which results in a considerable improvement in the catalysis performance.

4 Conclusion

The multi-metal oxide NPs with a chemical composition of MSbO_x and MSb₂O_x (M: Ni, Co, Fe, Cu, and Zn) and tetragonal structure (P42/mnm) were successfully synthesized using a simple thermal treatment technique and were screened for the catalytic performance toward the hydrogenation of 4-NP to 4-AP using NaBH₄. The oxygen vacancy-rich structure of these samples causes an instantaneous catalytic reaction in the first run. They showed reusability and relatively strong catalyst activity in the repeated runs despite of the surface reconstruction and reduction of surface oxygen vacancies in the catalytic process. Among our samples, (FeNiCoCu)SbO_x displays superior catalytic performance. The difference between this sample and others are its simple crystal structure, narrow size distribution, and large surface area. The kinetic rate constant for this sample is about ten times higher than that of (FeNiCoCu)Sb₂O_x and four times higher than that for the septenary samples in the second run.

We believe that the facile thermal treatment synthesis technique is a powerful strategy for large-scale production of multicomponent metal oxide NPs with oxygen vacancy-rich structure, while the surface and structural properties can be tuned via modification of initial composition. This method enables the rational design of multicomponent metal oxide NPs for catalytic applications, and the development of environmental remediation and modern technologies.

Acknowledgements

The authors acknowledge the Research Council of Norway for financial support through the.

NEAT Project No. 262339, ANSWER Project No. 280545, and NORTEM Project No.197405. This work made use of instruments in the Structure Physics and Electrochemistry Lab at Oslo Science Park.

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Vorheriger Artikel Chemo-Enzymatic Synthesis of Enantiopure β-Blocker (S)-Metoprolol and Derivatives

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Titel: A Highly Active and Reusable Multicomponent high Entropy Metal Oxide Catalyst for Nitroarenes Hydrogenation
verfasst von: Nayereh Soltani
Jamil Ur Rahman
Patricia Almeida Carvalho
Terje G. Finstad
Publikationsdatum: 17.07.2023
Verlag: Springer US
Erschienen in: Topics in Catalysis / Ausgabe 5-8/2024
Print ISSN: 1022-5528
Elektronische ISSN: 1572-9028
DOI: https://doi.org/10.1007/s11244-023-01846-z

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Abstract

Supplementary Information

Publisher’s Note

1 Introduction

2 Experimental

2.1 Materials and Methods

2.2 Characterization

2.3 Catalytic Reaction

3 Results and Discussion

4 Conclusion

Acknowledgements

Publisher’s Note

Electronic Supplementary Material

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