Benjamin
Mockenhaupt‡
ab,
Jan Konrad
Wied‡
c,
Sebastian
Mangelsen
b,
Ulrich
Schürmann
d,
Lorenz
Kienle
d,
Jörn
Schmedt auf der Günne
*c and
Malte
Behrens
*ab
aInstitute of Inorganic Chemistry, University of Duisburg-Essen, Universitätsstr. 7, 45141 Essen, Germany. E-mail: mbehrens@ac.uni-kiel.de
bInstitute of Inorganic Chemistry, Kiel University, Max-Eyth-Str. 2, 24118 Kiel, Germany
cDepartment of Chemistry and Biology, Inorganic Materials Chemistry, University of Siegen, Adolf-Reichwein-Straße 2, 57076 Siegen, Germany. E-mail: gunnej@chemie.uni-siegen.de
dDepartment of Materials Science, Kiel University, Kaiserstraße 2, 24143 Kiel, Germany
First published on 14th March 2023
The preparation of Al-doped ZnO via thermal decomposition of crystalline precursors, with a particular emphasis on kinetic effects on the solubility limits, was studied. The promoting effect of Al3+ on the catalyst system is discussed for methanol synthesis where ZnO:Al is employed as a support material for copper nanoparticles. The synthesis of the Al-doped zinc oxides in this study was inspired by the industrial synthesis of the methanol synthesis catalyst via a co-precipitated crystalline precursor, here: hydrozincite Zn5(OH)6(CO3)2. To determine the aluminium speciation and the solubility limit of the aluminium cation on zinc positions, a series of zinc oxides with varying aluminium contents was synthesized by calcination of the precursors. Short precipitate ageing time, low ageing temperature and aluminium contents below 3 mol% metal were advantageous to suppress crystalline side-phases in the precursor, which caused an aluminium segregation and non-uniform aluminium distribution in the solid. Even if zinc oxide was the only crystalline phase, TEM revealed such segregation in samples calcined at 320 °C. Only at very low aluminium contents, the dopant was found preferably on the zinc sites of the zinc oxide structure based on the signal dominating the 27Al NMR spectra. The solubility limit regarding this species was determined to be approximately xAl = 0.013 or 1.3% of all metal cations. Annealing experiments showed that aluminium was kinetically trapped on the
site and segregated into ZnAl2O4 upon further heating. This shows that lower calcination temperatures such as applied in catalyst synthesis conserve a higher aluminium doping concentration on that specific site than is expected thermodynamically.
Hence, the electronic conductivity of such a doped zinc oxide increases by the increased Fermi level and the facilitated excitation of the additional electron to the conducting band, which should be associated with a lowered band gap energy.7–10 Such improvement of the electronic properties of zinc oxide is not only of interest in the field of semiconductor applications, but also in the field of catalysis.
Typically, a copper/zinc oxide catalyst contains around 10% aluminium oxide for industrial methanol synthesis from COx/H2 mixtures (synthesis gas). It has been demonstrated that aluminium promotes the catalytic activity by improving and stabilizing the nano-structuring of the catalyst (structural promoter) as well as the strong metal–support interactions between zinc oxide and the copper nanoparticles (electronic promoter). Small amounts of this trivalent cation also increase catalyst lifetime and reduce copper sintering.11–13 The doping effect of bivalent (Mg2+) and trivalent cations (Al3+, Ga3+) in zinc oxide supports on the activity in methanol synthesis was further investigated,14 and it was found that a lower band gap energy of the doped zinc oxide is correlated with a higher catalytic activity after impregnating it with copper. Such a lowered band gap was discussed as a result of aluminium incorporation similar to semiconductor research. Contrarily, a bivalent cation does not lower the band gap nor improve the catalytic activity significantly.14 This finding is in line with studies, which found a correlation in conductivity increase by trivalent cationic-doped zinc oxides and a decrease for cationic dopants of lower valency.15,16 These results led to the hypothesis that beside the structural impact also electronic properties affect the catalysis in a positive way, which can be introduced by the incorporation of the Al3+ cation and could be related to the reducibility of doped zinc oxide under the hydrogenation conditions in methanol synthesis.14
In both fields, semiconductors and catalysis, the efficiency of the promoting effect depends on the maximum incorporation of aluminium ions in zinc oxide and on their lattice site substituting zinc ions () in the zinc oxide lattice.17 Contrarily, a segregated aluminium oxide side-phase in a doped zinc oxide sample could suppress the electronic promotion by its insulating properties.18,19 Thus, the determination of the maximum substitution limit of aluminium atoms in the zinc oxide lattice is of high importance. This can be a quite difficult task because of various side phases which can be formed. The solubility limit depends on the synthesis route and was estimated to be between 0.1 at% and 5.2 at% aluminium in zinc oxide.19–24 The determination of the substitution was performed with several techniques, like optical measurements,19 the reduction of dichromate,20 scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) analysis,21 Raman-spectroscopy,22 resistivity measurements23 and 27Al solid state nuclear magnetic resonance (NMR) spectroscopy.24 With the help of 27Al NMR different aluminium environments can be resolved and assigned to the different coordination numbers of aluminium.24–28 In this regard, the 27Al NMR signal at δiso = 82.6 ppm could unambiguously be assigned to aluminium on a zinc position in the ZnO crystal structure
,27 and Knight shifted signal gave evidence of the targeted n-doping leading to an electronic conductivity.25
With that method, the solubility limit is determined in a closer range of 0.3 at% to <2 at% aluminium in ZnO depending on the synthesis procedure and the synthesis temperature.24,26–29 The inconsistencies with regard to the solubility limit are subject of this contribution. The hypothesis of a solubility limit is consistent with quantum-chemical investigations that suggested a solubility limitation by the formation of the spinel ZnAl2O4, which acts as “thermodynamic sink” and inhibits formation of highly doped ZnO variants.30 This is in agreement with earlier experimental work, where for a ZnO/Al2O3 mixture at temperatures lower than 1250 °C a solubility limit of ≤0.2% was suggested by X-ray diffraction.31 To the best of our knowledge, the solubility limit has not been investigated to that level of details in the context of catalyst synthesis with different occurring side-phases which impose a thermodynamic limit as suggested by theory.30 Clearly, such an investigation requires an analytical technique which can identify and quantify the different chemical environments of the Al atoms and a low-temperature synthesis approach to stabilize high Al substitution levels.
In the field of catalysis, the calcination temperatures are typically lower than the annealing temperatures of semiconductors. At lower temperatures such as 300–400 °C the NMR signal was observed to have a high intensity.28,29 Furthermore it was found that the metallic character of ZnO:Al depends on the atmosphere, i.e. a reductive atmosphere may increase the metallicity of ZnO:Al as indicated from the formation of a Knight shifted 27Al NMR signal.27,32 For methanol synthesis, which inspired this work, the zinc oxide catalyst support is calcined in an oxidative atmosphere at a comparable temperature around 350 °C.33 It is the goal of this work to investigate the solubility limit of Al-doped zinc oxide for materials that represent the catalyst support formed by this method.
To determine the maximum amount of aluminium substituted zinc sites, a series of zinc oxides with varying aluminium content was synthesized using co-precipitation of crystalline hydroxycarbonate precursors, which is the established method for synthesizing Cu/ZnO:Al catalysts. In this case, the copper component was omitted to focus on the support.34 This has the advantage that the aluminium and zinc components are well distributed. In addition, no organic molecules are involved, which could interfere optical measurements. However, this procedure opens another question, namely that of the substitution chemistry in the hydroxy-carbonate precursor. The aluminium doping of a specific precursor phase, like the hydrozincite phase used here, should facilitate the formation of doped oxides upon thermal decomposition of the precursor and increase the inter-dispersion of both elements after calcination. Within our study, the question towards maximum substitution limit of Al3+ ions on the zinc sites in the hydrozincite precursor phase as well as in the zinc oxide structure will be addressed. We further aim at studying the aluminium dopant also under hydrogenation conditions that are relevant for methanol synthesis in forthcoming work. Finally, copper can be deposited on these supports with the aim to relate the catalytic properties to detailed knowledge of the aluminium species and amount. Here, we report on the as-prepared state of the catalyst support.
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Here, ni is the molar amount of element i (i = Zn, Al). Nominal values refer to the amount utilized during synthesis, which was found to match satisfactorily to the experimental values determined by ICP optical emission spectroscopy as discussed below in detail.
For a time-resolved ageing experiment, a synthesis as described above was carried out with aluminium content of 2% (xAl = 0.02). After the finish of co-precipitation, the first sample (t = 0 min) was taken out of the reactor before precipitate ageing. At ageing times of 10 min, 30 min, 60 min and 120 min, additional samples were collected. The total amount of the slurry removed was around 30 ml. After 120 min, the remaining suspension was aged for additional 12 hours in a Teflon-lined steel autoclave (275 ml) under solvothermal conditions at 130 °C. The Teflon-lined steel autoclave was maximum filled by 2/3 of its total volume. The samples were centrifuged and three times washed with deionized water to get rid of excess ions, and afterwards dried at 80 °C for minimum 14 h.
A brief description of the hydrozincite crystal structure is provided as ESI and visualized in Fig. S1.†
X-ray diffraction analysis of the time resolved ageing samples and of the calcined samples was performed on a Bruker D8 advance with Cu-Kα radiation and a LYNXEYE XE-T detector. The diffractograms were recorded in Bragg–Brentano geometry at room temperature between 5° and 90°2θ. Phase analysis was performed by comparing the recorded pattern with structural data from ICSD and COD databases.
Pawley fits were carried out using TOPAS Academic version 6.0.36 Instrumental line broadening was described using the fundamental parameter approach37 as implemented in TOPAS and cross-checked against a measurement of LaB6 (NIST SRM 660c).
The morphology of the samples was investigated by SEM and the micrographs of the samples obtained at different ageing times are shown in Fig. 2. The morphology was similar up to an ageing time of 30 minutes. Aggregated platelets were intergrown to spheres and other larger aggregates, as they are shown in the ESI (Fig. S4 and S11†). After 60 minutes of ageing, the platelet size seemed to decrease and additional larger thin platelets are observed after 120 min of ageing. These larger platelets have grown even thicker and show well defined facets after the solvothermal treatment as shown in Fig. 2. In combination with the temporal evolution of the crystalline phases known from the PXRD results, the immediately formed aggregated spheres are assigned to the hydrozincite phase and the larger platelets formed between 60 and 120 min of ageing, which grow under solvothermal conditions to a crystal habitus well-known for hydrotalcite-like materials,44 are assigned to zaccagnaite.
The investigation of the ageing time series at 2% aluminium demonstrated that aluminium will thermodynamically favour an incorporation into the zaccagnaite phase, which evolved after 120 minutes ageing time and further grows by solvothermal treatment. This results in an aluminium segregation and in an inhomogeneous aluminium distribution in the solid. To suppress this untargeted phase and to receive a more homogeneously doped hydrozincite, the ageing time was set to 10 min for the aluminium concentration variation series. With that shortened ageing time, a kinetically controlled aluminium incorporation into the hydrozincite phase should be favoured.
An increase in the BET surface area of the precursor after 120 minutes ageing time gives an additional indirect hint for a homogeneous aluminium distribution at short ageing times (Fig. S5†). The surface area of the precursor samples aged up to 60 minutes varied around 12 m2 g−1 and found to grow to 28 m2 g−1 after solvothermal treatment despite the newly grown phase clearly exhibiting larger particles. This might be explained by the effect of the aluminium ex-solution on the hydrozincite material leaving a more porous morphology. More evidence for an incorporation of aluminium into this phase is presented below for the aluminium concentration series.
The weak reflections present as shoulders to the first hydrozincite peak indicate that the zaccagnaite structure is present in low concentration (marked with stars). Given that this reflection is hardly discernible and broadened, i.e. on the level of detection, it may account to ∼1–2 wt%. However, the relative intensity of the zaccagnaite reflections does not increase linearly with the aluminium content after their first appearance, which excludes a simple aluminium saturation of the hydrozincite phase with all excess aluminium being segregated into zaccagnaite.
The diffraction pattern of the hydrozincite shows noticeable changes with increasing incorporation of Al: there are slight shifts in the position of the reflections, which become noticeable in particular at higher diffraction angles. The cell volume of the samples was extracted via a Pawley fit and the results are summarized in Fig. 4.
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Fig. 4 Cell volume and volume weighted average domain size estimated from the h00 reflections of the hydrozincite samples versus cation-based molar aluminium fraction xAl. |
The cell shrinks by ∼2 Å3 for the hydrozincite containing 10 at% Al compared to the unsubstituted compound, which can be expected from the lower ionic radius of Al3+ (54 pm) compared to Zn2+ (74 pm).45 For xAl = 0.1 the error becomes fairly large, which is expected due to the overall broadening of the reflections. This in turn hampers a precise determination of the lattice parameters. The line broadening was modelled assuming the effect to be caused by finite crystallite size, which can be justified by the information from electron microscopy. The crystallite size was found to be anisotropic, not unexpected for a layered material.
Furthermore, reflections of type h00, 0k0 and 00l are fairly sharp, where the first one describes the stacking of the layers while the latter two are related to the layer constitution. The cross plane reflections (e.g. 201, 301, 311) show stronger broadening, i.e. there is a loss of coherence among the layers, which is commonly observed for stacking faults in layered materials46,47 and was described earlier for synthetic hydrozincites.48 For an estimation of the crystallite size, the value for the h00 reflections is reported, which varies with a similar non-monotonous dependence on xAl as the cell volume does.
Aside of the zaccagnaite side phase, there are two prominent reflections located at 19.5 and 26.8°2θ appearing with increasing amount of Al3+ in the sample. They could not be assigned to any phase after extensive search in the COD and ICSD databases. Interestingly, the one located at 19.5°2θ has a d-spacing in excellent agreement with the a parameter and may be indexed as 300 reflection, which is forbidden in the space group C2/m that hydrozincite crystallizes in. For the second reflection, no such coincidence could be identified.
To further investigate the origin of these additional reflections, temperature resolved PXRD analysis of the sample with the highest aluminium content (xAl = 0.1) was performed (Fig. 5).
At 215 °C the decomposition starts, which is evidenced by the most intense reflections of the hydrozincite phase (e.g. at 2θ = 12.9°) losing intensity. Complete decomposition is achieved at 250 °C. Simultaneously, the zinc oxide reflections evolved and further increase in intensity as the temperature was elevated, at 300 °C already well-defined reflections of ZnO are visible. This prompt crystallization is markedly different from the case of zaccagnaite (Fig. S8†), where even at 600 °C only very broad reflections of ZnO can be observed. This may be related to the presence of amorphous alumina, hampering the diffusion and crystallite growth of ZnO. Interestingly, the additional reflections at 2θ = 19.5° and 26.8° behaved like those assigned to the hydrozincite regarding the thermal decomposition, which further indicates that they do belong to a disordered hydrozincite phase and not to any side-phase like disordered aluminium hydroxides, although the presence of such phase cannot be ruled out completely based on the experimental evidence.
The potentially high degree of substitution of Zn2+ by Al3+ is likely to cause significant changes in the structure of hydrozincite. This raises the question of how the additional positive charge is compensated. Three possible scenarios, illustrated in Fig. 6, affecting the cation- or anion lattice shall be outlined: the surplus positive charge may be compensated by additional anions (OH− or CO32−) that may be introduced in the interlayer space and lead to a chemical formula (Zn5−5xAl5x(OH)6+5x(CO3)2) or (Zn5−5xAl5x(OH)6(CO3)2+2,5x). Also, deprotonation of hydroxyl groups could compensate the extra charge according to a chemical formula (Zn5−5xAl5x(OH)6−5x(O)5x(CO3)2). Alternatively, for any two Al3+ cations one Zn2+ cation might become a vacancy, which could affect in particular the Zn2+ in tetrahedral coordination since the layer made up of Zn–O octahedra already contains vacancies in the neighbourhood of the tetrahedrally coordinated Zn2+, which could be filled with Al3+: (Zn5−7,5xAl5x(OH)6(CO3)2). A loss of those tetrahedral sites would also disrupt the link between the layers facilitated by the carbonate anions, which would allow for an increased number of stacking faults. This in turn would be a viable explanation for the increasing line width and change of relative intensities in the diffraction patterns with increasing Al content. However, the full structure determination of the potentially modified hydrozincite phase is beyond the scope of the present work.
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Fig. 6 Schematic depiction of potential defects in hydrozincite for balancing the surplus positive charge resulting from substitution of Zn2+ by Al3+: 1. Additional anions occupy the interlayer space. 2. Deprotonation of OH− to form O2− anions. 3. Vacancies on Zn2+ sites. The hydrogen atoms were placed at 0.9 Å distance and are not part of the crystal structure.43,48 |
SEM analysis of the concentration series shown in Fig. 7 revealed that the sample with an aluminium amount xAl = 0.01 contained aggregates of platelets, which formed spherical structures, as already observed in the ageing time series. Based on the assignment introduced above for the ageing time series, first additional larger platelets (highlighted by the arrows), which are encountered in the precursor with xAl = 0.03 aluminium content, are assigned to the zaccagnaite side-phase. Selected SEM-EDX spectra of these larger platelets are shown in the ESI in Fig. S12† and the results are listed in Table S2.† The median cationic ratio of Zn2+:
Al3+ = 3 agreed well with the expected composition of zaccagnaite.44 TEM analysis of the precursors was complicated due to high beam sensitivity and is described as ESI (Fig. S7†).
In order to characterize the aluminium environment in the hydrozincite precursors, a 27Al MAS NMR spectrum of the hydrozincite sample containing 3% aluminium (xAl = 0.03) was recorded (Fig. 8). The single peak at δobs = 14 ppm is indicative of aluminium occupying an octahedrally coordinated site, i.e. substituting a Zn atom in the hydrozincite structure.4027Al NMR peaks corresponding to a different coordination number are not observed. In comparison, the 27Al NMR spectrum of zaccagnaite Zn4Al2(OH)12(CO3)·3H2O exhibits two different signals at δobs = 15 ppm and δobs = 13 ppm. A 27Al 5QMAS NMR spectrum (Fig. S28†) does not resolve any further peaks and shows fairly broad signals, which is fully consistent with the published disordered crystal structure.42
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Fig. 8 Stack plot of 27Al MAS NMR spectra of a coprecipitated hydrozincite precursor with xAl = 3% aluminium incorporation and zaccagnaite. Spinning side bands are labelled with a star (*). |
To further investigate the precursor samples, infrared and Raman spectroscopy have been applied. In the infrared spectra shown in Fig. 9, bands typical for hydrozincite were found.49 For a better comparison between hydrozincite and side-phases, a phase-pure zaccagnaite sample was synthesized as described in the ESI (Fig. S6†) and used as reference for the analysis of vibrational spectroscopy data. The infrared spectra (Fig. 9) show a rather gradual evolution with increasing aluminium content and a clear difference to the zaccagnaite reference pattern demonstrating that the observed bands can be assigned to the hydrozincite phase. The strongest changes are observed for the two antisymmetric carbonate stretching modes (ν3, 1502–1396 cm−1)50 when the aluminium content exceeds xAl = 0.03, i.e. in the same compositional range where the unassigned reflections in PXRD at 2θ = 19.5° and 2θ = 26.8° arise. At the same time, the band at 948 cm−1 disappears, which – in analogy to the hydrotalcite-like materials – is related to hydrogen bonds between hydroxyls and carbonate.51,52 Such hydrogen bonds are also present in hydrozincite48 and thus the vanishing of this band indicates breaking of these bonds. These gradual changes support the defective hydrozincite structure by aluminium incorporation in agreement with the observed additional reflections in PXRD (Fig. 3). An infrared band at 621 cm−1 appeared for xAl > 0.01 and increased with the aluminium content. For hydrotalcites, this band was assigned to hydroxyl groups between the sheets.53 These observations suggest that the anions of hydrozincite are affected by the charge compensating mechanism when zinc is substituted by aluminium through coordination changes of carbonate and hydroxyl. A similar gradual evolution with increasing aluminium content was also found by Raman spectroscopy (Fig. S17†). The Raman modes at 564 cm−1 (Zn-OH) and 494 cm−1 (Me-OH) were present in the samples with xAl = 0.06 and xAl = 0.1 and represent the side-phase54–56 zaccagnaite in agreement with the PXRD results.
Nitrogen physisorption measurements revealed a surface area enlargement after calcination as a result of the decomposition of the hydroxycarbonate by simultaneous pore formation due to water and carbon dioxide emission. There is a clear trend towards larger surface areas for increasing aluminium content with a local maximum at xAl = 0.005 ranging from 31 m2 g−1 (xAl = 0, Fig. S19†) to 106 m2 g−1 (xAl = 0.1, Fig. S19†). The main pore fraction are 10 nm mesopores for the samples up to xAl = 0.02. With an increase in the aluminium content, this fraction increased. For a higher amount than xAl = 0.03, the pore fraction of the 20–30 nm pores starts to increase with further increase in the total pore volume (Fig. S20†).
The larger dimension of this platelet particle suggests that it originates from the zaccagnaite precursor side-phase. Indeed, EDX measurements were performed at several sample positions in the scanning TEM (STEM) mode and, hereby, a wide range of Al contents can be found that are all larger than the nominal 3% and span from 4.5% up to 38.6% (Fig. S22†). The highest aluminium concentrations were found where this thin ex-zaccagnaite platelet is not decorated by the nano-scaled ex-hydrozincite material indicated by the dark contrast in the high-angle annular dark field (HAADF)-STEM image. It is intriguing that it is at these aluminium-rich positions where the FFT has shown zinc oxide as only crystalline component. This suggests that the zinc and aluminium fractions of zaccagnaite have segregated upon decomposition into crystalline zinc oxide and amorphous alumina or nano-scale ZnAl2O4 spinel at a very small scale.
In summary, the electron microscopy investigation revealed the co-existence of two material systems in the sample with 3% aluminium. The major fraction of the material is ex-hydrozincite, i.e. crystalline zinc oxide with an aluminium content close to the nominal value. A minor, but increasing fraction, starting at xAl = 0.03 according to (precursor) PXRD, is ex-zaccagnaite and thus aluminium-richer and nano-structured in a complex manner containing crystalline zinc oxide and amorphous alumina segregated probably at the platelet surface.
After the decomposition of the hydrozincite, there are two different signals observable: δobs = 82 ppm and δobs = 12 ppm. The sharp signal at δobs = 82 ppm has unambiguously been assigned to Al3+ on a zinc position inside the ZnO crystal structure, .27 This small linewidth reflects the low quadrupolar coupling constant and an ordered environment of the
defect. In contrast, zaccagnaite has a disordered crystal structure42 and even without Al substitution hydrozincite has been reported to have a strong tendency for stacking disorder.48 The second signal at δobs = 12 ppm can result from unreacted hydrozincite, but also from a disordered sixfold coordinated aluminium environment at the surface of ZnO particles.25 With increasing temperatures up to 320 °C, a growth of the
signal is observed at the expense of the signal assigned to Al in unreacted hydrozincite (or in sixfold coordination). Here, the greatest build-up occurs between 200 and 240 °C, which is consistent with the formation of ZnO described by variable temperature PXRD (Fig. 5) and the decomposition of hydrozincite. The presence of a zaccagnaite side phase could not be observed by 27Al MAS NMR during the decomposition of the hydrozincite.
In order to find out whether the in-literature-postulated solubility limit of Al3+ in ZnO25–30 is an explanation for the occurrence of extra peaks, a series of samples with different aluminium concentrations was investigated (Fig. 13).
With increasing aluminium concentration, two further signals are observed: δobs = 75 ppm and δobs = 47 ppm. Their chemical shift indicates that δobs = 75 ppm corresponds to a fourfold coordinated aluminium environment, while δobs = 47 ppm corresponds to a fivefold coordinated aluminium environment. Due to their broad line shape and their continuous growth with increasing aluminium concentrations δobs = 75 ppm, δobs = 47 ppm and δobs = 12 ppm, can be assigned to disordered aluminium environments not situated within the crystal structure of ZnO. This is consistent with the observation that with increasing aluminium concentration a steady particle growth is observed for xAl ≥ 0.02 (see previous section Fig. 2). This interpretation is consistent with the areas of high Al concentration in the TEM experiments (Fig. S22†), which is expected when the Al concentration is low within ZnO and the surplus of Al is found segregated from ZnO in form of side phases. TEM experiments provide information from local projections along the electron beam and are thus not expected to return the (lower) average bulk value.
To obtain a better estimate for the maximum degree of Al substitution that can be achieved under these conditions, the amount of signal at δobs = 82 ppm is determined as a function of the degree of substitution xAl (Fig. 14). What can clearly be seen is that the signal/mass ratio increases only up to values of 2%. By interpolation with two linear functions, the “saturation limit” can be determined to xAl = 0.013. This agrees with the reported rough estimates of <2 mol% aluminium content in zinc oxide from other NMR studies.25,27
The band gap determination was performed at room temperature and at −185 °C to exclude heat effects. Afterwards, the measurement was repeated upon temperature increase back to 27 °C to check for thermally induced changes. The similar band gap energies before (25 °C) and after (27 °C) cooling demonstrate good reversibility within an error of around 6 meV. A band gap near 3.30 eV was found for pure zinc oxide at room temperature, which is in alignment with reported values around 3.3 eV.1–4 No clear trend was observed at low doping level, while a slight increase in band gap energy was determined for aluminium contents above 1%. This might be caused to the segregation of aluminium in ex-zaccagnaite regions as it was suggested by the TEM results. Because of the wide band gap of aluminium oxide (ca. 5.6 eV), the presence of disordered alumina could shift the band gap energy of the material to higher values.59 Generally, the band gap can be affected by defects, free excitons, impurities and by the lattice site occupied by the dopant.17,60–65 To exclude free excitons, the band gap energies were recorded at −185 °C. Compared to the room temperature spectra, the absolute energies shifted to higher values. The band gap energy of the undoped ZnO was increased to 3.37 eV at −185 °C. However, the relative trend between the samples was mostly maintained with the exception that the lowest band gap was determined for the sample with xAl = 0.01 in the cryogenic measurements (3.36 eV), which is in the range of the highest occupancy of the site. This finding is in agreement with the model of the band gap renormalisation, which predicts an optimal band gap for zinc oxide, if aluminium substitutes a zinc site.17
The behaviour of the zinc oxide sample with xAl = 0.005 aluminium with its wider band gap than xAl = 0 and xAl = 0.01, however, cannot be explained easily so far. This observation might be related to the Burnstein–Moss effect, which predicts a band gap widening if the lowest conduction band states are occupied by electrons introduced by the dopant and the next free lower level is at higher energies compared to the undoped sample.66,67 Altogether, the band gap trend is complex and likely caused by several effects such as the Burnstein–Moss effect, proper doping and the segregation of alumina when the solubility limit is exceeded.
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Fig. 17 Morphology evolution depending on the calcination temperature of the undoped zinc oxide. Calcination was performed with 2 °C min−1 heating ramp and 4 h holding time in static air. |
In order to obtain insight into the effect of thermal annealing on the presence of the different aluminium species, 27Al MAS NMR was performed (Fig. 18). Up to 620 °C, the presence of the aforementioned four different aluminium species is observed. During this process, a decrease in the signal is observed (Fig. S22†). In thermodynamic equilibrium, the Al substitution limit is expected to be determined by the formation of spinel ZnAl2O4 side phase,30 which under low-temperature conditions amounts to a concentration limit far below the observed values.31 The expected higher substitution levels of the low-temperature route can be explained by the higher chemical potential of Al in the amorphous surface layers formed, which are less favourable to Al then that of the spinel phase. The formation of the spinel phase as seen by 27Al NMR (Fig. 18) begins at annealing temperature of 720 °C upwards and drastically reduces the amount of Al in all phases but not in the spinel phase ZnAl2O4. This is shown by the presence of an additional signal at δobs = 15 ppm corresponding to ZnAl2O4.68
At temperatures of 820 °C, the signal in ZnO has dropped below the detection limit of xAl = 0.0005, which is consistent with the low equilibrium values determined in a previous study.24 We note that all (NMR visible) Al is consumed by the formed spinel ZnAl2O4 phase. At these high annealing temperatures, only two 27Al MAS NMR signals are observed: δobs = 15 ppm, which corresponds to the octahedral coordinated aluminium environment in the ZnAl2O4 crystal structure, and δobs = 75 ppm, which likely results from a cation inversion defect of the zinc and aluminium.68,69
What can be concluded is that the low-temperature approach achieves a much higher Al3+ substitution of the Zn2+ ions in ZnO than the equilibrium concentration would permit. Furthermore, this high substitution level can be maintained up to a temperature of about 720 °C when the activation energy for the formation of spinel crystallite is overcome and low thermodynamic substitution levels in ZnO are observed. It can be concluded that n-doping of ZnO by Al is thus stable under the conditions relevant for the catalytic process.
Together with the results from the composition series, where the increased up to xAl = 0.01 after the calcination of an aluminium-doped hydrozincite, the observation made for the temperature series indicates that the substitution on a zinc site is rather a kinetic effect and can be facilitated by a proper formed precursor acting as a kinetic trap. A further increase in the aluminium content does not result in an increased number of substituted sites but increases the side-phase amount in the precursors phase which has a negative effect on the opto-electrochemical properties. A calcination temperature above 320 °C minimizes the number of substituted sites and is therefore disadvantageous. The results clearly demonstrate that the presence of aluminium-doped zinc oxide containing the
species has to be considered as component of a typical methanol catalyst support.11
Footnotes |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3dt00253e |
‡ These authors contributed equally. |
This journal is © The Royal Society of Chemistry 2023 |