Among the large family of metal–organic frameworks (MOFs), Zr-based MOFs, which exhibit rich structure types, outstanding stability, intriguing properties and functions, are foreseen as one of the most promising MOF materials for practical applications. Although this specific type of MOF is still in its early stage of development, significant progress has been made in recent years. Herein, advances in Zr-MOFs since 2008 are summarized and reviewed from three aspects: design and synthesis, structure, and applications. Four synthesis strategies implemented in building and/or modifying Zr-MOFs as well as their scale-up preparation under green and industrially feasible conditions are illustrated first. Zr-MOFs with various structural types are then classified and discussed in terms of different Zr-based secondary building units and organic ligands. Finally, applications of Zr-MOFs in catalysis, molecule adsorption and separation, drug delivery, and fluorescence sensing, and as porous carriers are highlighted. Such a review based on a specific type of MOF is expected to provide guidance for the in-depth investigation of MOFs towards practical applications.

Zr-based metal-organic frameworks: design, synthesis, structure, and applications.

It is well known that urbanization and industrialization have resulted in the rapidly increasing emissions of volatile organic compounds (VOCs), which are a major contributor to the formation of secondary pollutants (e.g., tropospheric ozone, PAN (peroxyacetyl nitrate), and secondary organic aerosols) and photochemical smog. The emission of these pollutants has led to a large decline in air quality in numerous regions around the world, which has ultimately led to concerns regarding their impact on human health and general well-being. Catalytic oxidation is regarded as one of the most promising strategies for VOC removal from industrial waste streams. This Review systematically documents the progresses and developments made in the understanding and design of heterogeneous catalysts for VOC oxidation over the past two decades. It addresses in detail how catalytic performance is often drastically affected by the pollutant sources and reaction conditions. It also highlights the primary routes for catalyst deactivation and discusses protocols for their subsequent reactivation. Kinetic models and proposed oxidation mechanisms for representative VOCs are also provided. Typical catalytic reactors and oxidizers for industrial VOC destruction are further discussed. We believe that this Review will provide a great foundation and reference point for future design and development in this field.

/pdf/recent-advances-in-the-catalytic-oxidation-of-volatile-zw2c35dbg7.pdf

Recent Advances in the Catalytic Oxidation of Volatile Organic Compounds: A Review Based on Pollutant Sorts and Sources.

This review will explore the influences of the active metal, support, promoter, preparation methods, calcination temperature, reducing environment, particle size and reactor choice on catalytic activity and carbon deposition for the dry reforming of methane Bimetallic (Ni−Pt, Ni−Rh, Ni−Ce, Ni−Mo, Ni−Co) and monometallic (Ni) catalysts are preferred for dry reforming compared to noble metals (Rh, Ru and Pt) due to their low-cost Investigation of support materials indicated that ceria−zirconia mixtures, ZrO2 with alkali metals (Mg2+, Ca2+, Y2+) addition, MgO, SBA-15, ZSM-5, CeO2, BaTiO3 and Ca08Sr02TiO3 showed improved catalytic activities and decreased carbon deposition The modifying effects of cerium (Ce), magnesium (Mg) and yttrium (Y) were significant for dry reforming of methane MgO, CeO2 and La2O3 promoters for metal catalysts supported on mesoporous materials had the highest catalyst stability among all the other promoters Preparation methods played an important role in the synthesis of smaller particle size and higher dispersion of active metals Calcination temperature and treatment duration imparted significant changes to the morphology of catalysts as evident by XRD, TPR and XPS Catalyst reduction in different environments (H2, He, H2/He, O2/He, H2−N2 and CH4/O2) indicated that probably the mixture of reducing agents will lead to enhanced catalytic activities Smaller particle size (

Dry reforming of methane: Influence of process parameters—A review

(Article begins on next page) Anyone can freely access the full text of works made available as \"Open Access\". Works made available under a Creative Commons license can be used according to the terms and conditions of said license. Use of all other works requires consent of the right holder (author or publisher) if not exempted from copyright protection by the applicable law. Availability: This is the author's manuscript

/pdf/reactivity-of-surface-species-in-heterogeneous-catalysts-1vtf7rqr9y.pdf

Reactivity of Surface Species in Heterogeneous Catalysts Probed by In Situ X-ray Absorption Techniques

Metal nanoparticles that comprise a few hundred to several thousand atoms have many applications in areas such as photonics, sensing, medicine and catalysis. Colloidal methods have proven particularly suitable for producing small nanoparticles with controlled morphologies and excellent catalytic properties. Ligands are necessary to stabilize nanoparticles during synthesis, but once the particles have been deposited on a substrate the presence of the ligands is detrimental for catalytic activity. Previous methods for ligand removal have typically involved thermal and oxidative treatments, which can affect the size or morphology of the particles, in turn altering their catalytic activity. Here, we report a procedure to effectively remove the ligands without affecting particle morphology, which enhances the surface exposure of the nanoparticles and their catalytic activity over a range of reactions. This may lead to developments of nanoparticles prepared by colloidal methods for applications in fields such as environmental protection and energy production.

Facile removal of stabilizer-ligands from supported gold nanoparticles

The effect of tungsten and barium oxides on the activity and durability of V2O5/TiO2 catalyst for NO reduction by NH3 was examined. Tungsten enhanced the NO removal activity of V2O5 catalyst supported on sulfur-free TiO2, while no effect of tungsten was observed for the V2O5 catalyst supported on sulfated TiO2. The tungsten oxide promotes the formation of polymeric vanadate that is a strong active reaction site for NO reduction by NH3. When both tungsten and sulfur simultaneously exist on the surface of V2O5/TiO2, the sulfur species seems to play a more important role for NO removal activity than tungsten. The tungsten oxide on the V2O5/TiO2 catalyst also enhances the activity for SO2 oxidation by promoting the adsorption of SO2, regardless of the presence of sulfur species on the catalyst surface. The NO removal activity of V2O5 catalyst supported on sulfur-free TiO2 has been significantly reduced by barium oxide, mainly due to the formation of inactive VOBa compound through the strong interaction of vanadia with barium oxide. No change of NO removal activity over V2O5-BaO/sulfated TiO2, however, was examined by the addition of barium oxide, since the structure of vanadium oxide was not altered on the surface of the sulfated TiO2. The SO2 oxidation reaction over V2O5-BaO/TiO2 catalysts was significantly suppressed by the addition of barium oxide to the catalyst. The barium oxide seems to reduce the redox ability of vanadium oxide on the catalyst surface as well as the adsorption capacity of SO2. Based on the temperature programmed reduction (TPR), Raman and XPS observations, the surface structure of vanadium and its interaction with tungsten and barium oxides has been illustrated when sulfur exists on the surface of TiO2.

Effect of promoters including WO3 and BaO on the activity and durability of V2O5/sulfated TiO2 catalyst for NO reduction by NH3

V2O5 supported on sulfated TiO2 catalyst was investigated by using Raman and infrared spectroscopies to examine the surface structure of vanadia and the hydroxyl groups of titania along with the sulfate species on the catalyst surface. The surface structure of vanadia plays a critical role, particularly for the reduction of NO by NH3. The polymeric vanadate species on the catalyst surface is the active reaction site for this reaction system. The surface sulfate species enhanced the formation of the polymeric vanadate by reducing the available surface area of the catalyst. The formation of the polymeric vanadate species on the catalyst surface also depends on the number of hydroxyl groups on the support. Both the sulfate and the vanadate species strongly interacted with the hydroxyl groups on titania. The fewer the number of the hydroxyl sites on the catalyst surface became by increasing the calcination temperatures, the more the polymeric vanadate species formed. A model was proposed to elucidate the progressive alteration of the surface structure of vanadia by the amounts of V2O5 loadings and the sulfate species on the catalyst surface.

Characteristics of V2O5 supported on sulfated TiO2 for selective catalytic reduction of NO by NH3

CuCl 2 /TiO 2 -based catalysts were examined to investigate the role of copper chloride for the oxidation of gaseous elemental mercury in selective catalytic reduction (SCR) process. CuCl 2 on CuCl 2 /TiO 2 catalyst was decomposed releasing Cl by calcination at high temperatures and restored to its original form by being exposed to gas phase HCl, reversibly. The activity for mercury oxidation was significantly increased with the increase of CuCl 2 loading and HCl concentration. CuCl 2 /TiO 2 catalysts revealed high activity for mercury oxidation even in the absence of HCl. This suggests that mercury oxidation could occur via a Mars–Maessen mechanism by which adsorbed or weakly bound Hg 0 would react with Cl in CuCl 2 that is replenished from gas phase HCl. However, the activity of CuCl 2 -loaded catalysts for NO removal considerably decreased with the increase of temperature above 300–350 °C, which may be due to the ability of CuCl 2 for NH 3 oxidation in SCR reaction.

Oxidation of gaseous elemental mercury by hydrochloric acid over CuCl2/TiO2-based catalysts in SCR process

A series of vanadia catalysts impregnated on titania pillared interlayered clays (Ti-PILCs) were prepared to identify the characteristics of vanadia on the surface of Ti-PILC for the selective catalytic reduction (SCR) of NO by NH3. V2O5/Ti-PILC exhibited superior performance as a novel SCR catalyst compared to conventional catalysts including V2O5/TiO2 and V2O5/Al2O3. NO removal activity over the supported vanadia catalyst is strongly influenced by the structure of vanadia species on the catalyst surface. The structure of vanadia species on various supports including TiO2, Al2O3, and SiO2 along with Ti-PILC has been examined by XRD, NMR and Raman analyses for the comparative study. Increasing the content of vanadia up to the monolayer coverage of the surface of Ti-PILC catalyst enhanced the ratio of the polymerized surface vanadia species to the isolated ones. These results are well correlated with TOF of vanadia on the catalyst surface for the reduction of NO by NH3.

Characteristics of vanadia on the surface of V2O5/Ti-PILC catalyst for the reduction of NOx by NH3

The N 2 O decomposition activity of Fe-ZSM-5 strongly depends on the iron content and the preparation methods, including wet (WIE) and solid state ion exchanges (SSIE). The state of Fe species formed on the surface of a series of Fe-ZSM-5 catalysts containing a variety of Fe contents with respect to the preparation method and their role for N 2 O decomposition activity have been systematically examined. The general trend for the decomposition activity of Fe-ZSM-5-SSIE is higher than that of Fe-ZSM-5-WIE, indicating the formation of a distinctive local structure of Fe on the catalyst surface during the course of the ion-exchange procedure. Based upon the Fourier transformed Fe K-edge EXAFS spectra for the series of Fe-ZSM-5-SSIE and -WIE catalysts, most of the Fe species on the surface of Fe-ZSM-5-SSIE with high Fe loading are well dispersed in the form of oxygen-bridged binuclear Fe species. The turnover frequency (TOF) for N 2 O decomposition under dry and wet conditions has been confirmed assuming that Fe-ZSM-5-SSIE samples with Fe/Al = 0.20 and Fe/Al = 0.65 only contain mononuclear and binuclear Fe species, respectively, as active reaction species on their surface. The high performance of Fe-ZSM-5-SSIE may be mainly due to the formation of the binuclear Fe species onto its surface during the preparation of the catalyst.

Sung-Won Ham

Papers

Effect of promoters including WO3 and BaO on the activity and durability of V2O5/sulfated TiO2 catalyst for NO reduction by NH3

Characteristics of V2O5 supported on sulfated TiO2 for selective catalytic reduction of NO by NH3

Oxidation of gaseous elemental mercury by hydrochloric acid over CuCl2/TiO2-based catalysts in SCR process

Characteristics of vanadia on the surface of V2O5/Ti-PILC catalyst for the reduction of NOx by NH3

N2O decomposition over wet- and solid-exchanged Fe-ZSM-5 catalysts