Understanding the nature of NH3-coordinated active sites and the complete reaction schemes for NH3-SCR using Cu-SAPO-34 catalysts.

Cu-SAPO-34 zeolite catalysts show excellent NH3-SCR performance at low temperature, which is due to the catalytic capacity of copper species. Isolated CuII ions and CuIIOH are active sites, but their nature and role are not fully understood. This paper reports the DFT calculations in combination with ab initio thermodynamics to investigate NH3 and H2O coordination to copper species under typical NH3-SCR reaction conditions. In the reduction part of the NH3-SCR reaction, NH2NO and NH4NO2 intermediates will form on CuII-2NH3/3NH3 and CuIIOH-2NH3 complexes, respectively. The Brønsted acid sites are crucial for the decomposition of these intermediates, rather than copper species. Furthermore, the decomposition of NH2NO is more energetically favorable than NH4NO2 which are formed on the Brønsted acid sites. In the re-oxidation part of the NH3-SCR reaction, O2 dissociation and NO2 formation occur on CuI-2NH3 complexes in the presence of NO, and the regeneration of CuIIOH-2NH3 requires the participation of H2O. The proposed complete mechanisms highlight the importance of ligand coordinated copper species for intermediate formation and O2 activation in NH3-SCR.

Rational tailoring of the electronic structure for the SrxNaTayO3 semiconductor: Insights into its enhanced photoactivity and optical property.

NaTaO3 (NTO), as a popular photocatalyst with the prominent redox ability, largely straddles across the conduction band minimum (CBM) and valence band maximum (VBM) edge over Fermi level. Pristine NTO exhibits the poor light-harvesting ability and the rapid recombination of electron-hole pairs. We proposed an effective method to improve the photocatalytic property of NTO (ABO3-type) by substituting B site with Sr. The SrxNaTayO3 (SNTO) exhibited the boosted photocatalytic activity toward tetracycline oxidation under solar light irradiation. The rate constant for S0.5NTO (molar ratio of Sr: Ta = 1 : 2) was 5.1 times higher than the pure NTO. DFT results indicated that the Sr 3d orbital combining the O 2p and Ta 5d hybrid orbitals, widened the VB of SNTO. The band gap was narrowed from 3.86 to 2.82 eV after Sr substitution, which enhanced its light-harvesting ability. The VBM moved upward for 1.42 V and the CBM moved upward for 0.38 V. The shifts of the CBM and VBM, together with the more stretched Ta-O-Ta configuration, highly facilitated the electron-hole pair separation in SNTO. These electronic structure changes accounted for the significant photocatalytic performance enhancement of NaTaO3 via Sr substitution for B-site-Ta.

Fabrication of Nanohybrid Spinel@CuO Catalysts for Propane Oxidation: Modified Spinel and Enhanced Activity by Temperature-Dependent Acid Sites.

Modulating the catalyst electronic structure is a promising direction to enhance the catalytic oxidation performance. Herein, we report an innovative synthesis of the nanohybrid spinel@CuO catalyst with a broad biphasic interface for propane oxidation. The reaction rate of spinel@CuO catalyst was significantly increased compared to the physically mixed spinel+CuO catalyst. Lattice distortions and severe blurring of lattice fringes adjacent to the interface (between the spinel and CuO) comes with the spinel@CuO system, which enhanced interfacial interaction to form defect structures. The cobalt cations were selectively doped into the spinel lattice and occupied both the A and the B sites, while the CuO was not affected. At lower temperatures (∼200 °C), the enrichment of Brønsted acid sites increased the adsorption energy of propane. At higher temperatures (∼350 °C), the A and B sites cobalt weakened the Cu-O bond to make the oxygen vacancies form more readily, thereby enriching the Lewis acid sites. The substitution doping also resulted in lattice distortion in the spinel species, promoting the formation of a defect structure. The broad interface and temperature-dependent acid sites were conducive to propane oxidation.

Insight into the effect of facet-dependent surface and oxygen vacancies of CeO2 for Hg removal: From theoretical and experimental studies.

The reaction mechanisms of Hg oxidation on CeO2(111) and (110) surface are clarified by a group of designed experiments and density functional theory (DFT) calculations. CeO2 nanorods and nanoparticles with exposure (110) and (111) faces were prepared by hydrothermal methods, and their morphological properties were investigated using XRD, XPS and HRTEM. Combined experimental and DFT results, the nanorods show better activity than nanoparticles. The total oxidation of Hg can be partially prohibited by the high barriers for the incorporated chlorine activation at reduced surfaces, due to the strong electronic repulsion of heavily accumulated charges. The energy barrier profiles suggest Hg oxidation is much more favorable on CeO2(110) surface than that on CeO2(111) surface. In the Hg oxidation via HCl and O2, the role of O2 is not only replenishment of lattice oxygen, but also could generate surface oxygen as active center for HCl active. The complete catalytic cycle can be identified as four parts: (i) HCl activated by lattice oxygen, (ii) Hg oxidation on defect surface, (iii) HCl activated by adsorbed oxygen and (iv) Hg oxidation on stoichiometric surface. The results of this study provide deep insights into the effects of CeO2 nanocatalyst morphology on the Hg oxidation.

The precursor-guided hydrothermal synthesis of CuBi2O4/WO3 heterostructure with enhanced photoactivity under simulated solar light irradiation and mechanism insight.

Z-scheme heterojunction can efficiently suppress the electron-holes recombination and promote the charges transfer rate, which result in the high photocatalytic performance. Herein, a flower-flake-sphere like CuBi2O4/WO3 hybrid photocatalyst was fabricated via a precursor-guided hydrothermal method. The morphology, structure, composition, chemical and electronic properties of the as-prepared samples were systematically investigated by multiple techniques (XRD, FT-IR, SEM, TEM, XPS, UV-vis, BET, PL, ESR. etc.). Particularly, the 60 wt% CuBi2O4/WO3 nanocomposite exhibited the highest photocatalytic activity for tetracycline (20 mg/L) degradation under simulated solar light irradiation. The rate constant was 0.0179 min-1, which was almost 8 times and 4.5 times higher than that of bulk WO3 and CuBi2O4, respectively. The experimental results confirmed that CuBi2O4 made a direct Z-scheme heterojunction by band alignment with WO3, which are conducive to the efficient charges separation and prolonged carriers lifetime. According to the quenching experiments, •OH and •O2- were testified to be the predominant active species. The electrons accumulated in the CuBi2O4 negative CB and the holes in the WO3 positive VB made significant contribution to the strong redox ability of the CuBi2O4/WO3 nanocomposite. This work provides some deep insights into the design of band-alignment-based Z-scheme heterostuctures, which is also applicable to other catalytic system.

Modified red mud catalyst for the selective catalytic reduction of nitrogen oxides: Impact mechanism of cerium precursors on surface physicochemical properties.

Red mud, as industrial solid waste, causes severe environmental problems such as soil alkalization and groundwater pollution. In this work, we researched and developed the red mud as a selective catalytic reduction catalyst for NOx removal with NH3 (NH3-SCR). After selective dissolution and specific heat treatment, different Ce precursors were used to modifying its physical and chemical properties. The results showed that Ce(NO3)3 and Ce(NH4)2(NO3)6 modified red mud (RMcn and RMcan) had excellent SCR performance below 300 °C. Ce(SO4)2 modified red mud (RMcs) showed relatively low NOx conversions at 200-300 °C. The redox property was improved with the Ce(NO3)3 and Ce(NH4)2(NO3)6, while depressed with the Ce(SO4)2. Agglomerates generated on the RMcs and blocked the accumulated pores due to the formation of Ce2(SO4)3. The surface acidity of RMcs enhanced with increased adsorption for ammonia. However, these new adsorbed ammonia species, highly related to the sulfate from the Ce2(SO4)3, were inert and did not react with the adsorbed or gaseous NO species at 200-300 °C. The abundant surface lattice oxygen from CeO2 microcrystals improved the catalytic oxidation capacity of the RMcn and RMcan.

Irregular influence of alkali metals on Cu-SAPO-34 catalyst for selective catalytic reduction of NOx with ammonia.

SCR activity of Cu-SAPO-34 catalyst was reduced by alkali metal ions. The alkali metals ions (Li+, Na+ and K+) have shown irregular influences on Cu-SAPO-34. The order of poisoning strengths under 400 °C was found to be: Na+ > K+ > Li+, which is not consistent with the basicities of their corresponding metals. Experimental results and calculations showed that the alkali metal ions readily replace H+ and Cu2+/Cu+ ions. These exchanges result in the loss of Brønsted acid sites and migration of isolated Cu2+ ions in Cu-SAPO-34, which decrease the NH3-SCR activity. Both the basicity and ion diameter will affect the exchanging behavior of an alkali ion. Na+ and Li+ ions will influence both H+ and Cu2+/Cu+ ions but K+ ions only preferably replace the H+. We hypothesize that K+ cannot enter into a small ring (6-membered ring) to replace a Cu2+/Cu+ ion because of its large ion diameter. The displaced Cu2+/Cu+ ions will transfer to adjacent unbonded Al site to form a CuAlO2 species.

Promoting effects of water on the NH3-SCR reaction over Cu-SAPO-34 catalysts: transient and permanent influences on Cu species.

Cu-SAPO-34 catalysts with varied Cu loadings were synthesized through ion exchange to study the influence of water on the NH3-SCR reaction. The catalytic activities were evaluated by selective catalytic reduction of NO under a reactant feed in the presence/absence of water. Transient experiments were designed to study the response of NO conversion to the presence of water. H2-TPR and DFT calculations were performed to study the reducibility of Cu species. NH3-TPD and XPS were conducted to reveal the migration of Cu species. The results show that water could remarkably improve NO reduction activities and the promoting effect is more significant on the catalyst with low Cu loading. Both transient and permanent influences were found in this promoting phenomenon. For the transient influence, water has been proved to accelerate the re-oxidation half-cycle. Moreover, water can enhance the promoting effect of the SCR feed on the migration of Cu species. These unanchored Cu ions migrate to defect sites to form active sites, which lead to a permanent influence of water.