We review the structural chemistry and reactivity of copper-exchanged molecular sieves with chabazite (CHA) topology, as an industrially applied catalyst in ammonia mediated reduction of harmful ...nitrogen oxides (NH
3
-SCR) and as a general model system for red-ox active materials (also the recent results in the direct conversion of methane to methanol are considered). Notwithstanding the apparent structural simplicity of the material, a crystalline zeolite with only one crystallographically independent T site, the Cu-SSZ-13 catalyst reveals a high degree of complexity that has been decrypted by state of the art characterization tools. From the reviewed data, the following important aspects in the understanding of the Cu-SSZ-13 catalyst clearly emerged: (i) the structural dynamics of the Cu-species require precise control of the environmental conditions during activation and characterization; (ii) the availability of a large library of well-defined catalysts with different Si/Al and Cu/Al compositional ratios is key in unravelling the red-ox properties of the active Cu sites; (iii) a multi-technique approach is required, combining complementary techniques able to provide independent structural, electronic and vibrational information; (iv) synchrotron radiation based techniques (EXAFS, XANES, XES and time-resolved powder XRD) played a relevant role; (v)
operando
methodology (possibly supported by advanced chemometric approaches) is essential in obtaining structure-reactivity relations; (vi) the support of theoretical studies has been indispensable for the interpretation of the experimental output from characterization and for a critical assessment of mechanistic models. The old literature that classified Cu-exchanged zeolites in the category of single-site catalysts has been partially disproved by the recent advanced studies where it has been shown that the active site in the low temperature NH
3
-SCR catalyst is a mobile Cu-molecular entity that "lives in symbiosis" with an inorganic solid framework. Only in the high temperature NH
3
-SCR regime do the mobile Cu-species lose their ligands and find docking sites at the internal walls of the zeolite framework, thus reflecting the idea of a single-site catalyst. After a brief introduction, the review is divided into three main parts devoted to characterization (Section 2), reactivity (Section 3), and industrial applications (Section 4), followed by some concluding remarks and providing a perspective of the field.
We review the structural chemistry and reactivity of copper-exchanged molecular sieves with chabazite (CHA) topology, as an industrially applied catalyst in ammonia mediated reduction of harmful nitrogen oxides (NH
3
-SCR) and as a general model system for red-ox active materials (also the recent results in the direct conversion of methane to methanol are considered).
During the last two decades, remarkable and often spectacular progress has been made in the methodological and instrumental aspects of x–ray absorption and emission spectroscopy. This progress ...includes considerable technological improvements in the design and production of detectors especially with the development and expansion of large-scale synchrotron reactors All this has resulted in improved analytical performance and new applications, as well as in the perspective of a dramatic enhancement in the potential of x–ray based analysis techniques for the near future. This comprehensive two-volume treatise features articles that explain the phenomena and describe examples of X–ray absorption and emission applications in several fields, including chemistry, biochemistry, catalysis, amorphous and liquid systems, synchrotron radiation, and surface phenomena. Contributors explain the underlying theory, how to set up X–ray absorption experiments, and how to analyze the details of the resulting spectra. X-Ray Absorption and X-ray Emission Spectroscopy: Theory and Applications: * Combines the theory, instrumentation and applications of x-ray absorption and emission spectroscopies which offer unique diagnostics to study almost any object in the Universe. * Is the go-to reference book in the subject for all researchers across multi-disciplines since intense beams from modern sources have revolutionized x-ray science in recent years * Is relevant to students, postdocurates and researchers working on x-rays and related synchrotron sources and applications in materials, physics, medicine, environment/geology, and biomedical materials
This review addresses the most relevant aspects of vibrational spectroscopies (IR, Raman and INS) applied to zeolites and zeotype materials. Surface Brønsted and Lewis acidity and surface basicity ...are treated in detail. The role of probe molecules and the relevance of tuning both the proton affinity and the steric hindrance of the probe to fully understand and map the complex site population present inside microporous materials are critically discussed. A detailed description of the methods needed to precisely determine the IR absorption coefficients is given, making IR a quantitative technique. The thermodynamic parameters of the adsorption process that can be extracted from a variable-temperature IR study are described. Finally, cutting-edge space- and time-resolved experiments are reviewed. All aspects are discussed by reporting relevant examples. When available, the theoretical literature related to the reviewed experimental results is reported to support the interpretation of the vibrational spectra on an atomic level.
This review addresses the most relevant aspects of vibrational spectroscopies (IR, Raman and INS) applied to zeolites and zeotype materials: acidity, basicity and site accessibility investigated by probes molecules; precise determination of the IR absorption coefficients; thermodynamic aspects of molecular adsorption; space and time resolved experiments.
This critical review describes the reactivity of heterogeneous catalysts from the point of view of four simple, but essential for Chemistry, molecules (namely dihydrogen, carbon monoxide, nitrogen ...monoxide and ethylene) that are considered as probes or as reactants in combination with "in situ" controlled temperature and pressure Infrared spectroscopy. The fundamental properties of H(2), CO, NO and C(2)H(4) are shortly described in order to justify their different behaviour in respect of isolated sites in different environments, extended surfaces, clusters, crystalline or amorphous materials. The description is given by considering some "key studies" and trying to evidence similarities and differences among surfaces and probes (572 references).
The use of x-ray absorption spectroscopy in determining the structure and reactivity of surface species in heterogeneous catalysis was investigated. Among the issues probed are x-ray beam ...optimization, cation-exchanged zeolites and space-resolved X-rays experiments.
Through a combined use of experimental and theoretical approaches such as XRPD, EXAFS, IR, and UV−vis spectroscopies and ab initio periodic DFT calculations, we report a detailed characterization of ...structural, vibrational, and electronic properties of UiO-66 (Zr-BDC MOF) in its hydroxylated and dehydroxylated forms. The stability of the materials with respect to the most common solvents, acids, and bases is determined by combining XRPD and TGA/MS techniques. The structures of the two forms of UiO-66 are refined through an interactive XRPD/EXAFS approach and validated by ab initio calculations. Experimental and calculated IR spectra are reported and compared to enlighten the nature of vibrational modes upon dehydroxylation and to show the complete reversibility of the dehydration/hydration phenomenon. Experimental and calculated band gaps are also reported and compared. In this work, we show the necessity to combine, in a synergic way, different experimental techniques and periodic ab initio approaches to disclose and fully understand the nature of complex novel materials such as UiO-66 on structural, vibrational, and electronic grounds. The correct structure refinement could not be possible using one of these three approaches alone, in particular, XRPD data were unable to detect an important distortion of the Zr6O6 units of the dehydrated material that was, however, foreseen in the ab initio calculations and measured in the EXAFS spectra.
In recent years synchrotron x-ray microprobes and nanoprobes have emerged as key characterization tools with a remarkable impact for different scientific fields including solid-state, applied, ...high-pressure, and nuclear physics, chemistry, catalysis, biology, and cultural heritage. This review provides a comparison of the different probes available for the space-resolved characterization of materials (i.e., photons, electrons, ions, neutrons) with particular emphasis on x rays. Subsequently, an overview of the optics employed to focus x rays and the most relevant characterization techniques using x rays (i.e., x-ray diffraction, wide-angle x-ray scattering, small-angle x-ray scattering, x-ray absorption spectroscopy, x-ray fluorescence, x-ray-excited optical luminescence, and photoelectron spectroscopy) is reported. Strategies suitable to minimize possible radiation damage induced by brilliant focused x-ray beams are briefly discussed. The general concepts are then exemplified by a selection of significant applications of x-ray microbeams and nanobeams to materials science. Finally, the future perspectives for the development of nanoprobe science at synchrotron sources and free-electron lasers are discussed.
We report the structure of the Zr metal–organic frameworks (MOFs) UiO-66 and UiO-67 to very fine detail using synchrotron single-crystal X-ray diffraction and the synthesis method used to obtain ...single crystals. Zr terephthalate MOF UiO-66 is known to have missing linkers, and the nature of these are shown to be coordinating water and solvent molecules. Single crystals of the isoreticular material UiO-67 does not show such missing linker defects.
The small-pore Cu-CHA zeolite is today the object of intensive research efforts to rationalize its outstanding performance in the NH3-assisted selective catalytic reduction (SCR) of harmful nitrogen ...oxides and to unveil the SCR mechanism. Herein we exploit operando X-ray spectroscopies to monitor the Cu-CHA catalyst in action during NH3-SCR in the 150-400 °C range, targeting Cu oxidation state, mobility, and preferential N or O ligation as a function of reaction temperature. By combining operando XANES, EXAFS, and vtc-XES, we unambiguously identify two distinct regimes for the atomic-scale behavior of Cu active-sites. Low-temperature SCR, up to ∼200 °C, is characterized by balanced populations of Cu(I)/Cu(II) sites and dominated by mobile NH3-solvated Cu-species. From 250 °C upward, in correspondence to the steep increase in catalytic activity, the largely dominant Cu-species are framework-coordinated Cu(II) sites, likely representing the active sites for high-temperature SCR.
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