Understanding the internal structure and bonding of lead halide perovskite nanocrystals (NCs) is crucial to designing stable materials for various applications. In this work, we probe the extent of alloying and phase segregations in mixed halide perovskites at three length scales using a combination of optical spectroscopy, X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), and Raman spectroscopy. We observe domain-free mixed halide solid solutions with randomly distributed halide ions about the Pb center with several distinct but dynamically changing [PbCl (x) Br6-x ](4-) environments with only Pb-Cl and Pb-Br bonds. They are also sensitive to the changes in the unit cell dimensions resulting from the substitution of Br by Cl, obeying Vegard's law. Further, we reveal that weak octahedral bonding drives the consistent alteration of the halide environment. These studies provide insights into the chemical bonding driving the improved stability and performance pivotal for designing advanced optoelectronic devices.

Bifunctional Fe–Pt ammonia slip catalysts were studied by operando quick-scanning extended X-ray absorption fine structure spectroscopy (QEXAFS) under conditions mimicking rapid temperature variations that occur in an automotive exhaust gas aftertreatment system during real driving. Two catalysts, Pt/Al2O3 and Fe-ZSM-5, were tested individually, as mixtures and in dual bed arrangements. Applying QEXAFS allowed to track changes of active metal state with high time resolution. It uncovered a strong dependence of the active metal state on reaction conditions and catalyst bed layout. For example, proximity to platinum stabilized iron species in their more active oxidized state and led to higher Fe-ZSM-5 activity. On the contrary, isolated iron species were more susceptible to overreduction by ammonia which led to deactivation and low selectivity. The use of transient conditions uncovered the influence of non-equilibrium phenomena on catalytic performance under industrially relevant conditions. Specifically, the effect of ammonia storage on the increase of activity was shown. This was also accompanied by elevated N2O production not observed during tests with gradual heating. Additionally, unusually high NOx selectivity was detected for Fe-ZSM-5 under these conditions. Lastly, tracking catalyst state under dynamic reaction conditions disclosed that Fe-ZSM-5 activity did not grow directly with temperature increase but rather depended on the oxidation state of Fe and surface concentration of ammonia.

Cation doping is an effective method to alter the local structure and electronic state of V2O5. While it remains a great challenge to experimentally understand whether the doping cations prefer to replace the V ions or reside between the V2O5 layers, namely, substitutional or interstitial positions. In this work, cation-doped V2O5 with different elements M (M = Mn, Ni, and Fe) were synthesized via a hydrothermal method since V and M ions can uniformly distribute in the solution to obtain a homogeneous target material. The impact of doping cations on the local structure of V2O5 is revealed. Multitechniques demonstrate the existence of a small portion of V4+ in the doped samples resulting from the electronic structure change of V. Although the results do not directly certify where the doping cations lie in the V2O5 structure, all information together provide a hint that the doping cations may prefer to reside on the interstitial positions rather than the substitutional positions.

Magnesite has been used to produce struvite from nutrient rich wastewater in the presence of Cu2+ and Zn2+, and the effects of this fertilizer material on soil microflora have been reported.

Reductive treatments with pulses of CO-rich atmosphere have been used to increase and maintain the low temperature activity of a Pt/CeO2-based oxidation catalyst. A combination of operando infrared thermography and spatiotemporal-resolved quick scanning extended X-ray absorption fine structure spectroscopy on a fixed bed microreactor unraveled that, apart from the pulse length, the reaction atmosphere, and the reactor temperature, also the emerging reaction heat during such activating pulses has a strong influence on the structure and catalytic performance of CO and propylene conversion in the axial direction of a fixed-bed and a monolithic reactor. The reductive pulse activation led to an increase of the integral catalyst activity as well as to the generation of zones of different particle sizes along the catalyst bed. In the case of an activation temperature between 250 and 350 degrees C and pulse lengths between 5 and 30 s, a hotspot of more than 80 K was observed at the beginning of the catalyst bed. Spatially resolved X-ray absorption spectroscopy indicates that larger and more reduced Pt particles are formed particularly at the beginning of the catalyst bed, whereas its subsequent part is less affected. Both the length of the reductive pulses and activation temperature have a distinct influence on the noble metal particle size. On the basis of these results, a Pt/CeO2 based honeycomb shaped substrate was activated in a similar manner. Spatially resolved gas phase profiling showed different reaction rates at the beginning of the reactor, which indicates that the concept can be transferred also to industrially relevant catalysts. In the future, such an activation procedure might open up the door to a new class of operation strategies, by which individual zones generated in the catalyst bed could be assigned for removal of specific pollutants in the exhaust stream.

AbstractElectronic metal–support interactions (EMSI) describe the electron flow between metal sites and a metal oxide support. It is generally used to follow the mechanism of redox reactions. In this study of CuO‐CeO2 redox, an additional flow of electrons from metallic Cu to surface carbon species is observed via a combination of operando X‐ray absorption spectroscopy, synchrotron X‐ray powder diffraction, near ambient pressure near edge X‐ray absorption fine structure spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy. An electronic metal–support–carbon interaction (EMSCI) is proposed to explain the reaction pathway of CO oxidation. The EMSCI provides a complete picture of the mass and electron flow, which will help predict and improve the catalytic performance in the selective activation of CO2, carbonate, or carbonyl species in C1 chemistry.

Many processes and materials in heterogeneous catalysis undergo dynamic structural changes depending on their chemical environment. Monitoring such dynamic changes can be challenging using conventional spectroscopic characterization tools, due to the high time resolution required. Here, a high-resolution 2D X-ray camera operating at 50 Hz full-frame rate was synchronized with a QEXAFS monochromator, enabling rapid spectro-microscopic imaging with chemical contrast over individual pixels. This was used to monitor chemical gradients within a model Pt/Al2O3 catalyst during catalytic partial oxidation of methane to synthesis gas. The transition from methane combustion (partly oxidized Pt) to combustion-reforming and partial oxidation (fully reduced Pt) was observed by a characteristic reduction front, which progressed from the end of the catalyst bed towards its beginning on the second time scale. The full-field QEXAFS imaging method applied here allows acquisition of entire XANES spectra `on the fly' in a rapid and spatially resolved manner. The combination of high spatial and temporal resolution with spectroscopic data offers new opportunities for observing dynamic processes in catalysts and other functional materials at work. The methodology is flexible and can be applied at beamlines equipped with a QEXAFS or other fast-scanning monochromators and a suitable sample environment for gas phase analytics to allow for catalytic studies at the same time.

A series of Mn-Co mixed oxides with a gradual variation of the Mn/Co molar ratio were prepared by coprecipitation of cobalt and manganese nitrates. The structure, chemistry, and reducibility of the oxides were studied by X-ray diffraction (XRD), X-ray absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction (TPR). It was found that at concentrations of Mn below 37 atom %, a solid solution with a cubic spinel structure is formed. At concentrations above 63 atom %, a solid solution is formed on the basis of a tetragonal spinel, while at concentrations in a range of 37-63 atom %, a two-phase system, which contains tetragonal and cubic oxides, is formed. To elucidate the reduction route of mixed oxides, two approaches were used. The first was based on a gradual change in the chemical composition of Mn-Co oxides, illustrating slow changes in the TPR profiles. The second approach consisted in a combination of in situ XRD and pseudo-in situ XPS techniques, which made it possible to directly determine the structure and chemistry of the oxides under reductive conditions. It was shown that the reduction of Mn-Co mixed oxides proceeds via two stages. During the first stage, (Mn, Co)3O4 is reduced to (Mn, Co)O. During the second stage, the solid solution (Mn, Co)O is transformed into metallic cobalt and MnO. The introduction of manganese cations into the structure of cobalt oxide leads to a decrease in the rate of both reduction stages. However, the influence of additional cations on the second reduction stage is more noticeable. This is due to crystallographic peculiarities of the compounds: the conversion from the initial oxide (Mn, Co)3O4 into the intermediate oxide (Mn, Co)O requires only a small displacement of cations, whereas the formation of metallic cobalt from (Mn, Co)O requires a rearrangement of the entire structure.

A series of Pt/TiO2 photocatalysts was prepared by impregnation of fresh and thermal-activated titania (commercial Evonik Aeroxide P25 TiO2) with an aqueous solution of H2PtCl6 followed by reduction in an aqueous solution of NaBH4. The thermal activation was performed by annealing in air. The photocatalytic activity of the Pt/TiO2 catalysts was measured for the hydrogen production from a mixture of glycerol under UV radiation. It was found that the activation at 300–600 °C provides an increase in the photoreactivity of resulting Pt/TiO2 photocatalysts in the production of hydrogen while its structural and textural properties do not change. This effect is due to formation of cationic vacancies that limits fast electron–hole recombination.

NaxMn1/3Fe1/3Ni1/3O2 (x = 2/3 and 1) layered oxides are synthesized and applied as positive electrode materials for sodium batteries. The crystal structure of the material changes from the O-3 single phase to P2/O3 mixed phases as the Na content decreases from 1 to 2/3. The mixed-phases Na2/3Mn1/3Fe1/3Ni1/3O2 shows superior cycling performance compared to the single-phase NaMn1/3Fe1/3Ni1/3O2 due to different redox process and structural change that are demonstrated by operando X-ray absorption spectroscopy (XAS). The Na2/3Mn1/3Fe1/3Ni1/3O2 experiences redox reactions of Ni3+vertical bar Ni4+ and Fe3+vertical bar Fe4+ with inactive Mn ions during the charge/discharge processes, while the NaMn1/3Fe1/3Ni1/3O2 undergoes deeper redox reactions from Ni2+vertical bar Ni3+vertical bar Ni4+ and Fe3+vertical bar Fe4+ that Mn ions are irreversibly oxidized to Mn4+ in the 1st charge process. In addition, the mixed-phases material has smaller changes in the transition metal oxygen bond lengths during cycling, corresponding to less distortions of TMO6 units in the crystal structure. The better reversibility of the redox reactions and the occurrence of less structural changes are both responsible for the enhanced cycling performance obtained from the mixed-phases material compared to the single-phase material. These results strengthen the understanding of interactions of transition metals in the layered cathode and provide guidelines for designing positive electrode materials for sodium batteries. interactions of transition metals in the layered cathode and provide guidelines for designing positive electrode materials for sodium batteries.

Nutrient nitrogen (N) and phosphorus (P) recovery from wastewater is an important challenge for enhanced environmental sustainability. Herein we report the synthesis and properties of mesoporous MgO nanoparticles doped with copper (Cu), iron (Fe), and zinc (Zn) as an alternative low-solubility high-abundance magnesium (Mg) source for crystalline struvite precipitation from nutrient-laden wastewater. Undoped MgO was shown to have the fastest phosphate (PO43-) adsorption kinetics with a k(2) value of 0.9 g g(-1) min(-1) at room temperature. The corresponding rate constant decreased for Cu-MgO (0.175 g g(-1) min(-1)), Zn-MgO (0.145 g g(-1) min(-1)), and Fe-MgO (0.02 g g(-1) min(-1)). Undoped MgO resulted in the highest PO43- removal at 94%, while Cu-MgO, Fe-MgO, and Zn-MgO resulted in 90%, 66% and 66%, respectively, under equivalent reaction conditions. All dopants resulted in the production of struvite as the main product with the incorporation of the transition metals into the struvite crystal lattice. X-ray absorption spectroscopy (XAS) showed that the majority of the Cu, Fe, and Zn were primarily in the +2, +3, and +2 oxidation states, respectively. XAS also showed that the Cu atoms exist in elongated octahedral coordination, while Fe was shown to be in octahedral coordination. Zn was shown to be in a complex disordered environment with octahedral sites coexisting with the majority of the tetrahedral sites. Finally, X-ray photoelectron spectroscopy data suggest a two-fold struvite surface enrichment with dopant metals, with Cu exhibiting an interesting new local binding structure. The dopant concentrations utilized were consistent with those found in natural Mg minerals, suggesting that (a) utilizing natural mineral periclase as the Mg source for struvite production can result in struvite formation, albeit at the expense of the reaction kinetics and overall yields, while also (b) supplying essential micronutrients, such as Zn and Cu, necessary for balanced nutrient uptake.

An atomistic understanding of the photoinduced spin-state switching (PSS) within polynuclear systems of d(4)-d(7) transition metal ion complexes is required for their rational integration into light-driven reactions of chemical and biological interest. However, in contrast to mononuclear systems, the multidimensional dynamics of the PSS in solvated molecular arrays have not yet been elucidated due to the expected complications associated with the connectivity between the metal centers and the strong interactions with the surroundings. In this work, the PSS in a solvated triiron(II) metallogrid complex is characterized using transient optical absorption and X-ray emission spectroscopies on the femtosecond time scale. The complementary measurements reveal the photoinduced creation of energy-rich (hot) and long-lived quintet states, whose dynamics differ critically from their mononuclear congeners. This finding opens major prospects for developing novel schemes in solution-phase spin chemistry that are driven by the dynamic PSS process in compact oligometallic arrays.

Phosphorus (P) fertilizers from secondary resources became increasingly important in the last years. However, these novel P-fertilizers can also contain toxic pollutants such as chromium in its hexavalent state (Cr(VI)). This hazardous form of chromium is therefore regulated with low limit values for agricultural products even though the correct determination of Cr(VI) in these fertilizers may be hampered by redox processes, leading to false results. Thus, we applied the novel diffusive gradients in thin-films (DGT) technique for Cr(VI) in fertilizers and compared the results with the standard wet chemical extraction method (German norm DIN EN 15192) and Cr K-edge X-ray absorption near-edge structure (XANES) spectroscopy. We determined an overall good correlation between the wet chemical extraction and the DGT method. DGT was very sensitive and for most tested materials selective for the analysis of Cr(VI) in P-fertilizers. However, hardly soluble Cr(VI) compounds cannot be detected with the DGT method since only mobile Cr(VI) is analyzed. Furthermore, Cr K-edge XANES spectroscopy showed that the DGT binding layer also adsorbs small amounts of mobile Cr(III) so that Cr(VI) values are overestimated. Since certain types of the P-fertilizers contain mobile Cr(III) or partly immobile Cr(VI), it is necessary to optimize the DGT binding layers to avoid aforementioned over- or underestimation. Furthermore, our investigations showed that the Cr K-edge XANES spectroscopy technique is unsuitable to determine small amounts of Cr(VI) in fertilizers (below approx. 1% of Cr(VI) in relation to total Cr).

Na‐ion batteries have experienced rapid development over the past decade and received significant attention from the academic and industrial communities. Although a large amount of effort has been made on material innovations, accessible design strategies on peculiar structural chemistry remain elusive. An approach to in situ construction of new Na‐based cathode materials by substitution in alkali sites is proposed to realize long‐term cycling stability and high‐energy density in low‐cost Na‐ion cathodes. A new compound, [K0.444(1)Na1.414(1)][Mn3/4Fe5/4](CN)6, is obtained through a rational control of K+ content from electrochemical reaction. Results demonstrate that the remaining K+ (≈0.444 mol per unit) in the host matrix can stabilize the intrinsic K‐based structure during reversible Na+ extraction/insertion process without the structural evolution to the Na‐based structure after cycles. Thereby, the as‐prepared cathode shows the remarkably enhanced structural stability with the capacity retention of >78% after 1800 cycles, and a higher average operation voltage of ≈3.65 V versus Na+/Na, directly contrasting the non‐alkali‐site‐substitution cathode materials. This provides new insights into alkali‐site‐substitution constructing advanced Na‐ion cathode materials.

An ≈4 nm FeCrNi film, deposited on a Ru/B 4 C multilayer (ML), is used to study cathodic hydrogen charging in electrolyte. A thin film on a ML allows obtaining precise quantitative information on surface metal composition and oxidation state using the X‐ray standing wave technique combined with near‐edge X‐ray absorption spectroscopy. The metal composition is found being close to the composition of stainless steel (SS) 304, and, as for bulk steel, the outer 2 nm passive layer, consisting of oxidized iron and chromium, is depleted of nickel. Overall, it is found that the film represented a useful replica of the surface of bulk steel. Following exposure to 0.1 m KCl electrolyte at −0.6 V versus Ag/AgCl, 11.3 (±3)% swelling of the film by hydrogen absorption is observed. The estimated absorbed amount is exceeding reported bulk absorption under similar conditions by more than an order of magnitude. Strong hydrogen absorption appears to be enabled by the 2D character of the thin film, i.e., a significantly lower associated strain energy compared with bulk absorption. The strong surface swelling is suggested to be related to the lowering of the pitting corrosion resistance of SS surfaces reported following hydrogen exposure.

A series of Na(0.6)(7)Ni(0.33)Mr(0.67-x)Sn(x)O(2) (x = 0, 0.01, 0.03, 0.05) materials with mixed P2/P3 phases are synthesized with a conventional solid-state reaction method and investigated as cathode materials for sodium ion batteries. The effects of Sn substitution on the structure and electrochemical performance of the Na0.67Ni0.33Mn0.67O2 are systematically investigated. The substituted samples show smaller particle sizes compared to the pristine one and the P2:P3 phase ratio highly depends on the substitution amount. The best electrochemical performance is obtained by Na0.67Ni0.33Mn0.66Sn0.01O2, and it delivers a discharge capacity of 245 mA h g(-1) in 1.5-4.5 V (vs. Na vertical bar Na+), which is the highest result for Na0.67Ni0.33Mn0.67O2 materials reported so far. The ex situ X-ray absorption spectroscopy and X-ray photoelectron spectroscopy measurements reveal that the oxygen ions participate in the redox reactions within the wide voltage range of 1.5-4.5 V. The increased capacity can be attributed to the smaller particle size, which results in more oxygen activity and then higher capacity.

P2-type Fe- and Mn-based layered sodium transition metal oxides are promising positive electrode materials for sodium batteries due to their high energy density and low costs of the constituting transition metals. However, poor structural reversibility and fast capacity decay have prevented their breakthrough so far. Herein, the real-time dynamic phase transitions and capacity fading mechanism of the P2 Na0.67Fe0.5Mn0.5O2 positive electrode are revealed by operando X-ray diffraction, operando/ex situ X-ray absorption spectroscopy, neutron powder diffraction, and neutron pair distribution functions. Upon the desodiation process, a layered OP4 phase with long-range order is found as an intermediate state. With further deep desodiation, the formation of a Na-depleted ramsdellite phase with a short coherent length of 30 Å is observed for the first time. However, the transition from OP4 to ramsdellite is considered to be irreversible due to the breakdown of the layered structural characteristics, resulting in poor cycling performance in a variety of Fe-based layered sodium transition metal oxides. This work suggests that stabilizing the crystal structure by substitution or chemical modification can be a favorable strategy to avoid the degradation of positive electrodes and thus to improve the cycling performance.

Efficient oxygen evolution reaction (OER) electrocatalysts are pivotal for sustainable fuel production, where the Ni-Fe oxyhydroxide (OOH) is among the most active catalysts for alkaline OER. Electrolyte alkali metal cations have been shown to modify the activity and reaction intermediates, however, the exact mechanism is at question due to unexplained deviations from the cation size trend. Our X-ray absorption spectroelectrochemical results show that bigger cations shift the Ni2+/(3+δ)+ redox peak and OER activity to lower potentials (however, with typical discrepancies), following the order CsOH > NaOH ≈ KOH > RbOH > LiOH. Here, we find that the OER activity follows the variations in electrolyte pH rather than a specific cation, which accounts for differences both in basicity of the alkali hydroxides and other contributing anomalies. Our density functional theory-derived reactivity descriptors confirm that cations impose negligible effect on the Lewis acidity of Ni, Fe, and O lattice sites, thus strengthening the conclusions of an indirect pH effect.

We studied powder samples of europium titanates Eu1−x2+Eux3+TiO3+x/2 prepared by sol-gel and coprecipitation methods with subsequent thermal treatment of precursors at different conditions (reducing or oxidizing atmosphere, temperature, exposure time). We have revealed a radical rearrangement in the local, electronic and crystal structure of europium titanates depending on synthesis conditions. The combination of synchrotron X-ray diffraction (s-XRD), X-ray absorption (XANES and EXAFS), infrared and Raman spectroscopies supplemented by photoluminescence and simultaneous thermal analysis was used in our study. It is shown that the combined XANES and thermogravimetric analysis gives clear evidence of a change in the oxidation state of europium cations from Eu2+ to Eu3+. The comparison of s-XRD, XANES, and EXAFS data allowed us to explain the local structure rearrangement during the phase transition from cubic perovskite Eu2+TiO3 (space group Pm3¯m) to pyrochlore phase Eu23+Ti2O7 (space group Fd3¯m) through intermediate layered perovskite Eu23+Ti2O7 with monoclinic structure (space group P21) under annealing in oxidizing atmosphere. The Raman spectroscopy study pointed to significant changes in the local structure of the anionic sublattice upon the observed phase transitions. The analysis of luminescence spectra has shown that Eu3+ cations occupy positions with low local site symmetry in all synthesized compounds regardless of the type of the crystal structure.