Unveiling the Function of Oxygen Vacancy on Facet-Dependent CeO2 for the Catalytic Destruction of Monochloromethane: Guidance for Industrial Catalyst Design.

Secondary pollution remains a critical challenge for the catalytic destruction of chlorinated volatile organic compounds (CVOCs). By employing experimental studies and theoretical calculations, we provide valuable insights into the catalytic behaviors exhibited by ceria rods, cubes, and octahedra for monochloromethane (MCM) destruction, shedding light on the elementary reactions over facet-dependent CeO2. Our findings demonstrate that CeO2 nanorods with the (110) facet exhibit the best performance in MCM destruction, and the role of vacancies is mainly to form a longer distance (4.63 Å) of frustrated Lewis pairs (FLPs) compared to the stoichiometric surface, thereby enhancing the activation of MCM molecules. Subsequent molecular orbital analysis showed that the adsorption of MCM mainly transferred electrons from the 3σ and 4π* orbitals to the Ce 4f orbitals, and the activation was mainly caused by weakening of the 3σ bonding orbitals. Furthermore, isotopic experiments and theoretical calculations demonstrated that the hydrogen chloride generated is mainly derived from methyl in MCM rather than from water, and the primary function of water is to form excess saturated H on the surface, facilitating the desorption of generated hydrogen chloride.

Surface-Phosphorylated Ceria for Chlorine-Tolerance Catalysis.

An improved fundamental understanding of active site structures can unlock opportunities for catalysis from conceptual design to industrial practice. Herein, we present the computational discovery and experimental demonstration of a highly active surface-phosphorylated ceria catalyst that exhibits robust chlorine tolerance for catalysis. Ab initio molecular dynamics (AIMD) calculations and in situ near-ambient pressure X-ray photoelectron spectroscopy (in situ NAP-XPS) identified a predominantly HPO4 active structure on CeO2(110) and CeO2(111) facets at room temperature. Importantly, further elevating the temperature led to a unique hydrogen (H) atom hopping between coordinatively unsaturated oxygen and the adjacent P═O group of HPO4. Such a mobile H on the catalyst surface can effectively quench the chlorine radicals (Cl•) via an orientated reaction analogous to hydrogen atom transfer (HAT), enabling the surface-phosphorylated CeO2-supported monolithic catalyst to exhibit both expected activity and stability for over 68 days during a pilot test, catalyzing the destruction of a complex chlorinated volatile organic compound industrial off-gas.

Phosphotungstic Acid as a Dechlorination Agent Collaborates with CeO2 for Synergistic Catalytic Elimination of NOx and Chlorobenzene.

The development of efficient technologies for the synergistic catalytic elimination of NOx and chlorinated volatile organic compounds (CVOCs) remains challenging. Chlorine species from CVOCs are prone to catalyst poisoning, which increases the degradation temperature of CVOCs and fails to balance the selective catalytic reduction of NOx with the NH3 (NH3-SCR) performance. Herein, synergistic catalytic elimination of NOx and chlorobenzene has been originally demonstrated by using phosphotungstic acid (HPW) as a dechlorination agent to collaborate with CeO2. The conversion of chlorobenzene was over 80% at 270 °C, and the NOx conversion and N2 selectivity reached over 95% at 270-420 °C. HPW not only allowed chlorine species to leave as inorganic chlorine but also enhanced the BroÌ·nsted acidity of CeO2. The NH4+ produced in the NH3-SCR process can effectively promote the dechlorination of chlorobenzene at low temperatures. HPW remained structurally stable in the synergistic reaction, resulting in good water resistance and long-term stability. This work provides a cheaper and more environmentally friendly strategy to address chlorine poisoning in the synergistic reaction and offers new guidance for multipollutant control.

Polymerization State of Vanadyl Species Affects the Catalytic Activity and Arsenic Resistance of the V2O5-WO3/TiO2 Catalyst in Multipollutant Control of NOx and Chlorinated Aromatics.

The conventional V2O5-WO3/TiO2 catalyst suffers severely from arsenic poisoning, leading to a significant loss of catalytic activity. The doping of Al or Mo plays an important role in promoting the arsenic resistance on NH3 selective catalytic reduction (NH3-SCR), but their promotion mechanism remains in debate and has yet to be explored in multipollutant control (MPC) of NOx and chlorinated organics. Herein, our experimental characterizations and density functional theory (DFT) calculations confirmed that arsenic species preferentially adsorb on both Al and Mo to form arsenate, thereby avoiding bonding to the catalytically active V sites. More importantly, Al doping partially converted the polymeric vanadyl species into monomeric ones, thereby inhibiting the near-surface and bulk lattice oxygen mobility of the V2O5-WO3/TiO2 catalyst, while Mo doping resulted in vanadyl polymerization with an enriched V5+ chemical state and exhibited superior MPC activity and COx selectivity. Our work shows that antipoisoning catalysts can be designed with the combination of site protection and occurrence state modification of the active species.

Catalytic destruction of chlorobenzene over K-OMS-2: Inhibition of high toxic byproducts via phosphate modification.

In the process of catalytic destruction of chlorinated volatile organic compounds (CVOCs), the catalyst is prone to chlorine poisoning and produce polychlorinated byproducts with high toxicity and persistence, bringing great risk to atmospheric environment and human health. To solve these problems, this work applied phosphate to modify K-OMS-2 catalysts. The physicochemical properties of catalysts were determined by using X-ray powder diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), hydrogen temperature programmed reduction (H2-TPR), pyridine adsorption Fourier-transform infrared (Py-IR) and water temperature programmed desorption (H2O-TPD), and chlorobenzene was selected as a model pollutant to explore the catalytic performance and byproduct inhibition function of phosphating. Experimental results revealed that 1 wt.% phosphate modification yielded the best catalytic activity for chlorobenzene destruction, with the 90% conversion (T90) at approximately 247°C. The phosphating significantly decreased the types and yields of polychlorinated byproducts in effluent. After phosphating, we observed significant hydroxyl groups on catalyst surface, and the active center was transformed into Mn(IV)-O…H, which promoted the formation of HCl, and enhanced the dechlorination process. Furthermore, the enriched Lewis acid sites by phosphating profoundly enhanced the deep oxidation ability of the catalyst, which promoted a rapid oxidation of reaction intermediates, so as to reduce byproducts generation. This study provided an effective strategy for inhibiting the toxic byproducts for the catalytic destruction of chlorinated organics.

Synergistic Catalytic Elimination of NOx and Chlorinated Organics: Cooperation of Acid Sites.

The synergistic catalytic removal of NOx and chlorinated volatile organic compounds under low temperatures is still a big challenge. Generally, degradation of chlorinated organics demands sufficient redox ability, which leads to low N2 selectivity in the selective catalytic reduction of NOx by NH3 (NH3-SCR). Herein, mediating acid sites via introducing the CePO4 component into MnO2/TiO2 NH3-SCR catalysts was found to be an effective approach for promoting chlorobenzene degradation. The observation of in situ diffuse reflectance infrared Fourier transform (in situ DRIFT) and Raman spectra reflected that the Lewis acid sites over CePO4 promoted the nucleophilic substitution process of chlorobenzene over MnO2 by weakening the bond between Cl and benzene ring. Meanwhile, MnO2 provided adequate Brønsted acid sites and redox sites. Under the cooperation of Lewis and Brønsted acid sites, relying on the rational redox ability, chlorobenzene degradation was promoted with synergistically improved NH3-SCR activity and selectivity. This work offers a distinct pathway for promoting the combination of chlorobenzene catalytic oxidation and NH3-SCR, and is expected to provide a novel strategy for synergistic catalytic elimination of NOx and chlorinated volatile organic compounds.

Synergistic Elimination of NOx and Chlorinated Organics over VOx/TiO2 Catalysts: A Combined Experimental and DFT Study for Exploring Vanadate Domain Effect.

Vanadium-based catalysts have been extensively applied for the synergistic control of NOx and chlorinated organics. However, how the vanadia species affect the reaction activity and products distribution, and what are the dominant reaction sites of these vanadia species are still unknown. Herein, we investigated the reaction characteristics of monomeric and polymeric vanadate domains for the catalytically synergistic elimination of NOx and chlorobenzene (CB). Density functional theory (DFT) calculations and experimental investigations have been combined to clarify the effects of different vanadyl species on the synergistic reaction. It was noted that the main adsorption site of CB on the monomeric domain was V-OH bond, and that on the polymeric one was V═O bond. The monomeric vanadyl was favorable for converting the Lewis V═O into Brønsted V-OH, which provided sufficient H protons for HCl formation, whereas the polymeric species could effectively retain the V4+/V5+ redox cycle, and yielded superior activity in CB catalytic oxidation (CBCO) reaction. However, the abundant oxygen vacancies and the inclined accumulation of Cl by forming the V-Cl bands led to significant polychlorinated byproducts on the polymeric vanadyl catalysts. Our work gives the first insight into different vanadate domain effects on the synergistic reaction, and is expected to provide theoretical basis for efficient design of the vanadium-based catalysts toward multipollutants elimination.

V2O5-WO3/TiO2 Catalyst for Efficient Synergistic Control of NOx and Chlorinated Organics: Insights into the Arsenic Effect.

Municipal solid waste incineration and the iron and steel smelting industry can simultaneously discharge NOx and chlorinated organics, particularly polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). Synergistic control of these pollutants has been considered among the most cost-effective methods. This work combined experimental and computational methods to investigate the reaction characteristics of a catalytically synergistic approach and gives the first insight into the effect of arsenic (As) on the multipollutant conversion efficiency, synergistic reaction mechanism, and toxic byproduct distribution over a commercial V2O5-WO3/TiO2 catalyst. The loaded As2O3 species were shown to distinctly decrease the formation energy of an oxygen vacancy at the V-O-V site, which likely contributed to the extensive formation of more toxic polychlorinated byproducts in the synergistic reaction. The As2O5 species strongly attacked neighboring V═O sites forming the As-O-V bands. Such an interaction deactivated the deNOx reaction, but led to excessive NO being oxidized into NO2 that greatly promoted the V5+-V4+ redox cycle and in turn facilitated chlorobenzene (CB) oxidation. Subsequent density functional theory (DFT) calculation further reveals that both the As2O3 and As2O5 loadings can facilitate H2O adsorption on the V2O5-WO3/TiO2 catalyst, leading to competitive adsorption between H2O and CB, and thereby deactivate the CB oxidation with water stream.

Synergistic catalytic removal of NOx and chlorinated organics through the cooperation of different active sites.

The synergistic removal of NOx and chlorinated volatile organic compounds (CVOCs) has become the hot topic in the field of environmental catalysis. However, due to the trade-off effects between catalytic reduction of NOx and catalytic oxidation of CVOCs, it is indispensable to achieve well-matched redox property and acidity. Herein, synergistic catalytic removal of NOx and chlorobenzene (CB, as the model of CVOCs) has been originally demonstrated over a Co-doped SmMn2O5 mullite catalyst. Two kinds of Mn-Mn sites existed in Mn-O-Mn-Mn and Co-O-Mn-Mn sites were constructed, which owned gradient redox ability. It has been demonstrated that the cooperation of different active sites can achieve the balanced redox and acidic property of the SmMn2O5 catalyst. It is interesting that the d band center of Mn-Mn sites in two different sites was decreased by the introduction of Co, which inhibited the nitrate species deposition and significantly improved the N2 selectivity. The Co-O-Mn-Mn sites were beneficial to the oxidation of CB and it cooperates with Mn-O-Mn-Mn to promote the synergistic catalytic performance. This work paves the way for synergistic removal of NOx and CVOCs over cooperative active sites in catalysts.

A review of sources, environmental occurrences and human exposure risks of hexachlorobutadiene and its association with some other chlorinated organics.

Research on hexachlorobutadiene (HCBD) has increased since its listing in the Stockholm Convention on Persistent Organic Pollutants in 2011. However, thorough reports on recent data regarding this topic are lacking. Moreover, potential associations between HCBD and some chlorinated organics have usually been ignored in previous research. In this review, possible formation pathways and sources, current environmental occurrences and human exposure risks of HCBD are discussed, as well as the association with several organochlorine compounds. The results reveal that unintentional production and emission from industrial activities and waste treatments are the main sources of HCBD. Similar precursors are found for HCBD and chlorobenzenes, indicating the presence of common sources. Although recent data indicates that levels of HCBD in the environment are generally low, risks from human exposure to HCBD, together with other pollutants, may be high. More attention in the future needs to be paid to the mixed contamination of HCBD and other pollutants from common sources.

Chromium-zinc ferrite nanocomposites for the catalytic abatement of toxic environmental pollutants under ambient conditions.

Catalytic abatement of 4-chlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid in water was investigated by peroxide oxidation over chromium substituted zinc ferrite nanocomposites at ambient conditions. The structural and chemical properties of composites synthesized by sol-gel auto combustion method was studied by X-ray diffraction, Fourier Transform Infra-Red spectroscopy, Transmission Electron Microscopy, surface area, X-ray Fluorescence spectroscopy, Temperature Programmed Reduction and Desorption techniques. Complete removal of 4-CP, DCP and 2,4-D was achieved within 60, 75 and 90min with 96.7/90.5%, 93.88/77.23% and 88.55/62.1% of COD/TOC removal respectively at 298K and 343K. Influence of reaction variables including reaction temperature, oxidant concentration, substrate concentration, catalyst dosage and its composition on the removal efficiency was studied. Kinetic study revealed that wet peroxide oxidation followed a first order kinetic model with rate constant and activation energy of 3.5×10-2min-1/10.7kJ/mole, 9.5×10-3min-1/12.9kJ/mole and 2.29×10-2min-1/17.7kJ/mole respectively for 4-CP, DCP and 2,4-D. The results of five consecutive catalytic runs from X-ray diffraction, Brunauer Emmet Teller surface area and leaching studies from Atomic Absorption Spectrophotometry (AAS) revealed the excellent stability of the catalyst. Scavenging effect of n-butanol on hydroxyl radical indicated a heterogeneous free radical mechanism.

Adsorbed poly(aspartate) coating limits the adverse effects of dissolved groundwater solutes on Fe0 nanoparticle reactivity with trichloroethylene.

For in situ groundwater remediation, polyelectrolyte-modified nanoscale zerovalent iron particles (NZVIs) have to be delivered into the subsurface, where they degrade pollutants such as trichloroethylene (TCE). The effect of groundwater organic and ionic solutes on TCE dechlorination using polyelectrolyte-modified NZVIs is unexplored, but is required for an effective remediation design. This study evaluates the TCE dechlorination rate and reaction by-products using poly(aspartate) (PAP)-modified and bare NZVIs in groundwater samples from actual TCE-contaminated sites in Florida, South Carolina, and Michigan. The effects of groundwater solutes on short- and intermediate-term dechlorination rates were evaluated. An adsorbed PAP layer on the NZVIs appeared to limit the adverse effect of groundwater solutes on the TCE dechlorination rate in the first TCE dechlorination cycle (short-term effect). Presumably, the pre-adsorption of PAP "trains" and the Donnan potential in the adsorbed PAP layer prevented groundwater solutes from further blocking NZVI reactive sites, which appeared to substantially decrease the TCE dechlorination rate of bare NZVIs. In the second and third TCE dechlorination cycles (intermediate-term effect), TCE dechlorination rates using PAP-modified NZVIs increased substantially (~100 and 200%, respectively, from the rate of the first spike). The desorption of PAP from the surface of NZVIs over time due to salt-induced desorption is hypothesized to restore NZVI reactivity with TCE. This study suggests that NZVI surface modification with small, charged macromolecules, such as PAP, helps to restore NZVI reactivity due to gradual PAP desorption in groundwater.