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The adaption of the sol–gel autocombustion method to the Cu/ZrO2 system opens new pathways for the specific optimisation of the activity, long-term stability and CO2 selectivity of methanol steam reforming (MSR) catalysts. Calcination of the same post-combustion precursor at 400 °C, 600 °C or 800 °C allows accessing Cu/ZrO2 interfaces of metallic Cu with either amorphous, tetragonal or monoclinic ZrO2, influencing the CO2 selectivity and the MSR activity distinctly different. While the CO2 selectivity is less affected, the impact of the post-combustion calcination temperature on the Cu and ZrO2 catalyst morphology is more pronounced. A porous and largely amorphous ZrO2 structure in the sample, characteristic for sol–gel autocombustion processes, is obtained at 400 °C. This directly translates into superior activity and long-term stability in MSR compared to Cu/tetragonal ZrO2 and Cu/monoclinic ZrO2 obtained by calcination at 600 °C and 800 °C. The morphology of the latter Cu/ZrO2 catalysts consists of much larger, agglomerated and non-porous crystalline particles. Based on aberration-corrected electron microscopy, we attribute the beneficial catalytic properties of the Cu/amorphous ZrO2 material partially to the enhanced sintering resistance of copper particles provided by the porous support morphology., The adaption of the sol–gel autocombustion method to the Cu/ZrO2 system opens new pathways for the specific optimisation of the activity, long-term stability and CO2 selectivity of methanol steam reforming (MSR) catalysts.

To identify the synergistic action of differently prepared Ni-ZrO2 phase boundaries in methane dry reforming, we compared an “inverse” near-surface intermetallic NiZr catalyst precursor with the respective bulk-intermetallic NixZry material and a supported Ni-ZrO2 catalyst. In all three cases, stable and high methane dry reforming activity with enhanced anticoking properties can be assigned to the presence of extended Ni-ZrO2 phase boundaries, which result from in situ activation of the intermetallic Ni-Zr model catalyst systems under DRM conditions. All three catalysts operate bifunctionally; methane is essentially decomposed to carbon at the metallic Ni0 surface sites, whereas CO2 reacts to CO at reduced Zr centers induced by a spillover of carbon to the phase boundaries. On pure bulk Ni0, dissolved carbon accumulates in surface-near regions, leading to a sufficiently supersaturated state for completely surface-blocking graphitic carbon segregation. In strong contrast, surface-ZrO2 modified bulk Ni0 exhibits virtually the best decoking and carbon conversion conditions due to the presence of highly dispersed ZrO2 islands with a particularly large contribution of interfacial Ni0-ZrO2 sites and short C-diffusion pathways to the latter.

To compare the inherent methanol steam reforming properties of intermetallic compounds and a corresponding intermetallic compound-oxide interface, we selected the Cu-In system as a model to correlate the stability limits, self-activation and redox activation properties with the catalytic performance. Three distinct intermetallic Cu-In compounds - Cu7In3, Cu2In and Cu11In9 - were studied both in an untreated and redox-activated state resulting from alternating oxidation-reduction cycles. The stability of all studied intermetallic compounds during methanol steam reforming (MSR) operation is essentially independent of the initial stoichiometry and all accordingly resist substantial structural changes. The inherent activity under batch MSR conditions is highest for Cu2In, corroborating the results of a Cu2In/In2O3 sample accessed through reactive metal-support interaction. Under flow MSR operation, Cu7In3 displays considerable deactivation, while Cu2In and Cu11In9 feature stable performance at simultaneously high CO2 selectivity. The missing significant self-activation is most evident in the operando thermogravimetric experiments, where no oxidation is detected for any of the intermetallic compounds. In situ X-ray diffraction allowed us to monitor the partial decomposition and redox activation of the Cu-In intermetallic compounds into Cu0.9In0.1/In2O3 (from Cu7In3), Cu7In3/In2O3 (from Cu2In) and Cu7In3/Cu0.9In0.1/In2O3 (from Cu11In9) interfaces with superior MSR performance compared to the untreated samples. Although the catalytic profiles appear surprisingly similar, the latter interface with the highest indium content exhibits the least deactivation, which we explain by formation of stabilizing In2O3 patches under MSR conditions.

The active chemical state of zinc (Zn) in a zinc-copper (Zn-Cu) catalyst during carbon dioxide/carbon monoxide (CO 2 /CO) hydrogenation has been debated to be Zn oxide (ZnO) nanoparticles, metallic Zn, or a Zn-Cu surface alloy. We used x-ray photoelectron spectroscopy at 180 to 500 millibar to probe the nature of Zn and reaction intermediates during CO 2 /CO hydrogenation over Zn/ZnO/Cu(211), where the temperature is sufficiently high for the reaction to rapidly turn over, thus creating an almost adsorbate-free surface. Tuning of the grazing incidence angle makes it possible to achieve either surface or bulk sensitivity. Hydrogenation of CO 2 gives preference to ZnO in the form of clusters or nanoparticles, whereas in pure CO a surface Zn-Cu alloy becomes more prominent. The results reveal a specific role of CO in the formation of the Zn-Cu surface alloy as an active phase that facilitates efficient CO 2 methanol synthesis.

Catalytic properties of In-Pt intermetallic compounds in methanol steam reforming have been investigated. In2Pt has been proven to be mandatory for a high activity and selectivity. Only small amounts of In2O3 have been found to be beneficial for catalytic performance. Heterogeneous catalysts are often complex materials containing different compounds. While this can lead to highly beneficial interfaces, it is difficult to identify the role of single components. In methanol steam reforming (MSR), the interplay between intermetallic compounds, supporting oxides and redox reactions leads to highly active and CO2-selective materials. Herein, the intrinsic catalytic properties of unsupported In3Pt2, In2Pt, and In7Pt3 as model systems for Pt/In2O3-based catalytic materials in MSR are addressed. In2Pt was identified as the essential compound responsible for the reported excellent CO2-selectivity of 99.5 % at 300 °C in supported systems, showing a CO2-selectivity above 99 % even at 400 °C. Additionally, the partial oxidation of In7Pt3 revealed that too much In2O3 is detrimental for the catalytic properties. The study highlights the crucial role of intermetallic In−Pt compounds in Pt/In2O3 materials with excellent CO2-selectivity.

Following the need for an innovative catalyst and material design in catalysis, we provide a comparative approach using pure and Pd-doped LaCu

We assessed the catalytic properties of the Cu/ZrO2 interface in methanol and formaldehyde steam reforming (MSR and FSR) on powder catalysts by using a comparative approach with respect to the influence of the ZrO2 polymorph support structure (monoclinic (m-)ZrO2 vs. tetragonal (t-)ZrO2), its synthesis routine and the choice of the precursor material on the CO2 selectivity. Our studies reveal that ZrO2 exhibits a pronounced versatility as a support material and its catalytic properties depend most strongly on its surface properties governed by its synthesis, especially by the choice of the Zr precursor. The way of combining the support with copper introduces an additional layer of complexity, but its influence on the MSR performance is limited to a modification of the conditions provided by the ZrO2 support. Exploiting the comparative approach regarding the Cu-ZrO2 catalysts in FSR and MSR – including the pure support materials – in combination with in situ Fourier transform infrared (FT-IR) spectroscopy shows that the CO observed in MSR on Cu/m-ZrO2 can be attributed to a spillover of formaldehyde to the support. Side reactions of m-ZrO2 are suppressed at lower temperatures due to its lack of highly reactive sites, resulting in a CO2-selective MSR performance. In Cu/t-ZrO2, however, the amount of CO is higher and a combination of a formaldehyde spillover to the support and a Cu-ZrO2 phase boundary yielding CO leads to the lower CO2 selectivity of these samples. An elevated number of defects and reactive Lewis acidic and Bronsted basic centers of t-ZrO2 explains this increased activity towards side reactions in contrast to Cu/m-ZrO2 catalysts.

A series of novel melilite-type structured compounds of the general formula Sr2Mg1−xMnxGe2−ySiyO7+δ (0 ≤ x ≤ 1; 0 ≤ y ≤ 2) was produced by conventional solid-state syntheses and subsequently characterized by X-ray powder diffraction (XRPD) and Rietveld analysis. All prepared compounds crystallize in the tetragonal space group P21m with the unit cell dimensions varying dependent on the elements contained in the structure. The diffuse reflectance spectra of the obtained powders were recorded, and the color properties were determined by means of the CIE 1976 L*a*b* color coordinates. With the aim of developing new, non-toxic inorganic blue materials that might be of interest for industrial applications, the expensive element Ge was substituted with Si, while the Mg to Mn ratio was simultaneously varied for color optimization. XPS measurements provided evidence that the blue color displayed by some of the candidates in the melilite-type structure is attributable to the presence of the manganese in a mixed oxidation state of 2+/3+. Finally, the highest blue color value was achieved for Sr2Mg0.2Mn0.8Si2O7+δ with b* = −31.3, a remarkable value for an environmentally safe inorganic blue pigment.

Author(s): Ploner, K; Delir Kheyrollahi Nezhad, P; Watschinger, M; Schlicker, L; Bekheet, MF; Gurlo, A; Gili, A; Doran, A; Schwarz, S; Stoger-Pollach, M; Bernardi, J; Armbruster, M; Klotzer, B; Penner, S | Abstract: On Cu/ZrO2 catalysts, variation of the Cu loading from 0.2 wt% to 80 wt% allows assessing the influence of the Cu-ZrO2 interface on the methanol steam reforming (MSR) performance by steering Cu particle size and morphology, revealing the contribution of potential active sites at the interface and the intrinsic relative contributions of the support and Cu surface fraction. As ZrO2 influences both CO2-selective and selectivity-spoiling MSR reaction channels, disentangling support-specific effects from the special phase-boundary reactivity and the intrinsic Cu° reactivity is possible by our approach. By choosing a broad range of Cu loadings, a comparison of the most extreme cases of strong predominance of bulk-like Cu sites (80 wt% Cu) vs. highly dispersed Cu (0.2 wt%), dominated by interfacial and support reactivity, becomes accessible. Cu (80 wt%)/ZrO2 evolves as the best MSR catalyst by avoiding adverse support effects and providing a high number of support-wetting bulk-like Cu sites.

To evaluate the structural and spectroscopic steering factors of noble metal promotion in the catalytic reduction of NO by CO, a series of La(Cu0.7Mn0.3)0.98M0.02O3−δ (M = Pd, Pt, Ru, Rh) perovskite catalysts is investigated. The materials are synthesized by a sol-gel method and characterized by X-ray powder diffraction (XRD), electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). All metal-promoted perovskites exhibit a comparatively higher activity for catalytic reduction of NO by CO with respect to pure La(Cu0.7Mn0.3)O3−δ . Among all catalysts tested, the La(Cu0.7Mn0.3)0.98Pd0.02O3−δ perovskite shows the highest catalytic activity, which is tentatively related to a combined synergistic effect of improved oxygen vacancy activity and noble metals. Additionally, the redox chemistry of the catalysts in different reducing (H2) and oxidizing (NO, O2) atmospheres is tested. An enhanced kinetic reducibility, especially with Pd, was observed. All the H2-reduced catalysts are capable of reducing NO. At low and intermediate temperatures, the formation of N2O is observed, but at higher temperatures NO is exclusively converted to N2. The introduction of noble metals leads to new adsorption sites for NO. As XPS suggests a tendency for depletion of noble metals in the surface-near regions, while the catalytic activity in NO reduction at the same time appears much improved, directed noble metal promotion with modest amounts especially in surface-near regions during synthesis appears as an encouraging method to economize the use of the latter. This work was performed within the framework of the funding programme IMPULSE Iran Austria, financed by funds of the OeAD fonds and of the Ministry of Science, Research and Technology of the Islamic Republic of Iran. We also thank the SFB F45-N16 special research program for financial support. This work was performed within the framework of the research platform ‘‘Materials and Nanoscience” and the special PhD program ‘‘Reactivity and Catalysis”, both at the University of Innsbruck.

The reactive metal-support interaction in the Cu-In2O3 system and its implications on the CO2 selectivity in methanol steam reforming (MSR) have been assessed using nanosized Cu particles on a powdered cubic In2O3 support. Reduction in hydrogen at 300 °C resulted in the formation of metallic Cu particles on In2O3. This system already represents a highly CO2-selective MSR catalyst with ~93% selectivity, but only 56% methanol conversion and a maximum H2 formation rate of 1.3 µmol gCu−1 s−1. After reduction at 400 °C, the system enters an In2O3-supported intermetallic compound state with Cu2In as the majority phase. Cu2In exhibits markedly different self-activating properties at equally pronounced CO2 selectivities between 92% and 94%. A methanol conversion improvement from roughly 64% to 84% accompanied by an increase in the maximum hydrogen formation rate from 1.8 to 3.8 µmol gCu−1 s−1 has been observed from the first to the fourth consecutive runs. The presented results directly show the prospective properties of a new class of Cu-based intermetallic materials, beneficially combining the MSR properties of the catalyst’s constituents Cu and In2O3. In essence, the results also open up the pathway to in-depth development of potentially CO2-selective bulk intermetallic Cu-In compounds with well-defined stoichiometry in MSR., Graphical abstract

To compare the inherent methanol steam reforming properties of intermetallic compounds and a corresponding intermetallic compound–oxide interface, we selected the Cu–In system as a model to correlate the stability limits, self-activation and redox activation properties with the catalytic performance. Three distinct intermetallic Cu–In compounds – Cu7In3, Cu2In and Cu11In9 – were studied both in an untreated and redox-activated state resulting from alternating oxidation–reduction cycles. The stability of all studied intermetallic compounds during methanol steam reforming (MSR) operation is essentially independent of the initial stoichiometry and all accordingly resist substantial structural changes. The inherent activity under batch MSR conditions is highest for Cu2In, corroborating the results of a Cu2In/In2O3 sample accessed through reactive metal–support interaction. Under flow MSR operation, Cu7In3 displays considerable deactivation, while Cu2In and Cu11In9 feature stable performance at simultaneously high CO2 selectivity. The missing significant self-activation is most evident in the operando thermogravimetric experiments, where no oxidation is detected for any of the intermetallic compounds. In situ X-ray diffraction allowed us to monitor the partial decomposition and redox activation of the Cu–In intermetallic compounds into Cu0.9In0.1/In2O3 (from Cu7In3), Cu7In3/In2O3 (from Cu2In) and Cu7In3/Cu0.9In0.1/In2O3 (from Cu11In9) interfaces with superior MSR performance compared to the untreated samples. Although the catalytic profiles appear surprisingly similar, the latter interface with the highest indium content exhibits the least deactivation, which we explain by formation of stabilizing In2O3 patches under MSR conditions., To compare the properties of intermetallic compounds and intermetallic compound–oxide interfaces, Cu–In was used as a model to correlate stability limits, self-activation and redox activation with the inherent methanol steam reforming performance.

We describe a new type of operando Fourier transform infrared (FTIR)–mass spectrometry setup for surface-chemical and reactivity characterization of heterogeneous catalysts. On the basis of a sophisticated all-quartz FTIR reactor cell, capable of operating between room temperature and 1000 °C in reactive gas atmospheres, the setup offers a unique opportunity to simultaneously collect and accordingly correlate FTIR surface-chemical adsorption data of the active catalyst state and FTIR gas phase data with complementary reactivity data obtained via mass spectrometry in situ. The full set of catalytic operation modes (recirculating static and flow reactor conditions) is accessible and can be complemented with a variety of temperature-programmed reaction modes or thermal desorption. Due to the unique transfer process involving a home-built portable glovebox to avoid air exposure, a variety of complementary quasi in situ characterization methods for the pre- and post-reaction catalyst states become accessible. We exemplify the capabilities for additional x-ray photoelectron spectroscopy characterization of surface-chemical states, highlighting the unique strength of combining adsorption, electronic structure, and reactivity data to gain detailed insight into the reactive state of a Cu/ZrO2 heterogeneous catalyst during methanol steam reforming operation.

Structural and chemical consequences of reactive metal-support interaction (RMSI) effects occurring under hydrogen reduction in a metastable metal-oxide system have been exemplified for small PdO particles loaded onto rhombohedral In2O3 (PdO/rh-In2O3) using synchrotron-based in situ X-ray diffraction experiments at temperatures up to 500 °C. rh-In2O3 is a meta-stable In2O3 polymorph that is prone to gas-phase dependent phase transformation to cubic In2O3 (c-In2O3). Cross-influence of metal-support interaction and phase transformation can therefore be expected in similar temperature regimes. To separate both effects, comparable experiments have also been conducted on pure rh-In2O3. Phase transformation of pure rh-In2O3 to cubic In2O3 in hydrogen occurs between 415 °C and 450 °C. On Pd/rh-In2O3, a sequence of PdO reduction to Pd metal, followed by PdH0.706 hydride formation and subsequently, InPd and In3Pd2 intermetallic compound formation have been observed between 30 °C and 500 °C. After the intermetallic compound formation is finished at around 400 °C, the phase transformation to c-In2O3 sets in at exactly the same temperature as on pure rh-In2O3 and extends over the same temperature range. This proves that the phase transformation of rh-In2O3 to c-In2O3 is not influenced by the reduction and the intermetallic compound formation. In contrast to Pd on c-In2O3, In-Pd compound formation from rh-In2O3 occurs at much lower temperatures (230 °C vs. 300 °C), despite finally approaching the same compound stoichiometries (InPd and In3Pd2). This points to a high structural stability of reduced rh-In2O3/stability of oxygen vacancies (compared to c-In2O3) as well as to facilitated diffusion of reduced In(-O) species at low temperatures.

To focus on the influence of the intermetallic compound—oxide interface of Pd-based intermetallic phases in methanol steam reforming (MSR), a co-precipitation pathway has been followed to prepare and subsequently structurally and catalytically characterize a set of nanoparticulate Ga2O3- and In2O3-supported GaPd2 and InPd catalysts, respectively. To study the possible promoting effect of In2O3, an In2O3-doped Ga2O3-supported GaPd2 catalyst has also been examined. While, upon reduction, the same intermetallic compounds are formed, the structure of especially the Ga2O3 support is strikingly different: rhombohedral and spinel-like Ga2O3 phases, as well as hexagonal GaInO3 and rhombohedral In2O3 phases are observed locally on the materials prior to methanol steam reforming by high-resolution transmission electron microscopy. Overall, the structure, phase composition and morphology of the co-precipitated catalysts are much more complex as compared to the respective impregnated counterparts. However, this induces a beneficial effect in activity and CO2 selectivity in MSR. Both Ga2O3 and In2O3 catalysts show a much higher activity, and in the case of GaPd2–Ga2O3, a much higher CO2 selectivity. The promoting effect of In2O3 is also directly detectable, as the CO2 selectivity of the co-precipitated supported Ga2O3–In2O3 catalyst is much higher and comparable to the purely In2O3-supported material, despite the more complex structure and morphology. In all studied cases, no deactivation effects have been observed even after prolonged time-on-stream for 12 h, confirming the stability of the systems.

The catalytic performance of Ag- and Co3O4-impregnated strontium titanium ferrite (SrTi0.7Fe0.3O3-δ, STF) has been assessed in methanol steam reforming as a test reaction and accordingly correlated with spectroscopic and structural characterization after each step of a catalytic cycle including pre-oxidation and pre-reduction. After pre-reduction in hydrogen at 400 °C, metallic silver and oxidized Co in the form of Co3O4 are present. As for catalysis, it was observed that both Ag and Co3O4 are strongly promoting the methanol chemistry with respect to pure STF already at low temperatures (230 °C for both materials). As a consequence, the selectivity towards carbon monoxide is strongly enhanced in comparison to pure STF. On Co3O4-STF, the catalytic profile is basically dominated by a temperature-dependent complex interplay between methanol steam reforming, methanol dehydrogenation and the water-gas shift equilibrium. The results also prove that despite the obvious inadequacy of H2-prereduced Ag-STF to act a...

Starting from subsurface Zr0-doped “inverse” Pd and bulk-intermetallic Pd0Zr0 model catalyst precursors, we investigated the dry reforming reaction of methane (DRM) using synchrotron-based near ambient pressure in-situ X-ray photoelectron spectroscopy (NAP-XPS), in-situ X-ray diffraction and catalytic testing in an ultrahigh-vacuum-compatible recirculating batch reactor cell. Both intermetallic precursors develop a Pd0–ZrO2 phase boundary under realistic DRM conditions, whereby the oxidative segregation of ZrO2 from bulk intermetallic PdxZry leads to a highly active composite layer of carbide-modified Pd0 metal nanoparticles in contact with tetragonal ZrO2. This active state exhibits reaction rates exceeding those of a conventional supported Pd–ZrO2 reference catalyst and its high activity is unambiguously linked to the fast conversion of the highly reactive carbidic/dissolved C-species inside Pd0 toward CO at the Pd/ZrO2 phase boundary, which serves the role of providing efficient CO2 activation sites. In contrast, the near-surface intermetallic precursor decomposes toward ZrO2 islands at the surface of a quasi-infinite Pd0 metal bulk. Strongly delayed Pd carbide accumulation and thus carbon resegregation under reaction conditions leads to a much less active interfacial ZrO2–Pd0 state.