Photocatalytic NO x removal and recovery: progress, challenges and future perspectives.

The excessive production of nitrogen oxides (NO x ) from energy production, agricultural activities, transportation, and other human activities remains a pressing issue in atmospheric environment management. NO x serves both as a significant pollutant and a potential feedstock for energy carriers. Photocatalytic technology for NO x removal and recovery has received widespread attention and has experienced rapid development in recent years owing to its environmental friendliness, mild reaction conditions, and high efficiency. This review systematically summarizes the recent advances in photocatalytic removal, encompassing NO x oxidation removal (including single and synergistic removal and NO3 - decomposition), NO x reduction to N2, and the emergent NO x upcycling into green ammonia. Special focus is given to the molecular understanding of the interfacial nitrogen-associated reaction mechanisms and their regulation pathways. Finally, the status and the challenges of photocatalytic NO x removal and recovery are critically discussed and future outlooks are proposed for their potential practical application.

Efficient and Durable Oxidation Removal of Formaldehyde over Layered Double Hydroxide Catalysts at Room Temperature.

Room temperature catalytic oxidation (RTCO) using non-noble metals has emerged as a highly promising technique for removal of formaldehyde (HCHO) under ambient conditions; however, non-noble catalysts still face the challenges related to poor water resistance and low stability under harsh conditions. In this study, we synthesized a series of layered double hydroxides (LDHs) incorporating various dual metals (MgAl, ZnAl, NiAl, NiFe, and NiTi) for formaldehyde oxidation at ambient temperature. Among the synthesized catalysts, the NiTi-LDH catalyst showed an HCHO removal efficiency and CO2 yield close to 100.0%, and exceptional water resistance and chemical stability on running 1300 min. The abundant hydroxyl groups in LDHs directly bonded with HCHO, leading to the production of CO2 and H2O, thus inhibiting the formation of CO, even in the absence of O2 and H2O. The coexistence of O2 effectively reduced the reaction barrier for H2O molecule dissociation, facilitating the formation of hydroxyl groups and their subsequent backfill on the catalyst surface. The mechanisms underlying the involvement and regeneration of hydroxyl groups in room temperature oxidation of formaldehyde were elucidated with the combined in situ DRIFTS, HCHO-TPD-MS, and DFT calculations. This work not only demonstrates the potential of LDH catalysts in environmental applications but also advances the understanding of the fundamental processes involved in room temperature oxidation of formaldehyde.

Dual function of H2O on interfacial intermediate conversion and surface poisoning regulation in simultaneous photodegradation of NO and toluene.

Co-existing air pollutants, especially NOx and VOCs, will generate secondary photochemical pollution under light irradiation. However, simultaneous elimination of multi-pollutants has long been a challenge. Photocatalysis could turn the reaction pathway between pollutants to convert them into harmless products, which is a promising technology for multi-pollutant control. Here we achieved synergistic photocatalytic degradation of NO and C7H8 on InOOH photocatalyst, and the performance can be adjusted by H2O through affecting the interaction between surface species and catalyst. In situ DRIFTS and GC-MS revealed that the improved efficiency originated from the fast conversion of C-N coupling intermediates led by additional H2O. Surface characterizations and DFT simulation determined that accumulated nitrates will compete with the adsorption of NO and C7H8, resulting in a decline in efficiency in the later stage. Although improved efficiency would bring more nitrates, as H2O has comparable adsorption to nitrate at the same site, high humidity can mitigate the deactivation. The photocatalyst can be also simply regenerated by water washing. This work reveals the complex interaction in the multi-pollutant system and provides guidelines for precisely regulating the synergistic removal of NOx and VOCs.

Highly Enhanced Photocatalytic NO Removal and Inhibited Peroxyacetyl Nitrate Formation in Synergistic Acetaldehyde Degradation.

The coexistence of NO and CH3CHO in the air is considered to produce secondary peroxyacetyl nitrate (PAN) under sunlight irradiation, threatening the ecological environment and public health. Herein, we provide a simple strategy for the photocatalytic removal of NO and acetaldehyde (CH3CHO) on Sr2Sb2O7. In comparison with the single removal, the nearly complete removal of NO is reached by deep oxidation to NO3- with the assistance of CH3CHO. The underlying mechanism is revealed by GC-MS, in situ DRIFTS, and density functional theory calculations. The intermediates •CH3 from CH3CHO and NO2- from NO tend to bond and further oxidize to CH3ONO2, thus promoting NO removal. CH3NO2 and CH3ONO2 are the key products instead of PAN on Sr2Sb2O7 from the synergistic degradation of NO and CH3CHO. This work brings new insights into reaction pathway regulation for promoting performance and suppressing byproducts during synergistic air pollutant removal.

Amorphous SnO2 decorated ZnSn(OH)6 promotes interfacial hydroxyl polarization for deep photocatalytic toluene mineralization.

Surface hydroxyl groups play a decisive role in the generation of hydroxyl radicals with stronger oxidizing ability, which is indispensable in photocatalytic VOCs removal, especially under the condition of low humidity. In this work, non-noble amorphous SnO2 decorated ZnSn(OH)6 (ZSH) was synthesized by an in-situ method. The charge transport, reactant activation and hydroxyl polarization are enhanced through decoration of amorphous SnO2 on ZSH. Combined with the designed experiment, in-situ EPR, DTF calculation and in-situ DRIFTS, the role and mechanism of interfacial hydroxyl polarization are revealed on SnO2 decorated ZnSn(OH)6. Compared with pristine ZSH and noble-metal modified ZSH, the toluene degradation rate of amorphous SnO2 decorated ZSH is increased by 13.0 and 3.8 times, and the toluene mineralization rate is increased by 5.2 and 2.2 times. The ZSH-24 sample maintains a high toluene degradation activity after 6 cyclic utilization without catalyst deactivation. This work emphasizes the role of non-noble metal and the origin of hydroxyl group polarization on ZnSn(OH)6 for photocatalytic VOCs mineralization.

The spatially separated active sites for holes and electrons boost the radicals generation for toluene degradation.

Hydroxyl (⸱OH) and superoxide (⸱O2-) radicals are the main drivers for photocatalysis in toluene degradation, but their generation mechanisms are still ambiguous due to the lack of direct evidence. The spatially separated active sites for holes and electrons can help to clarify the dynamic process of radicals generation. By performing theoretical calculations, it is demonstrated that the spatially separated active sites for holes and electrons on the Bi2O2CO3 surface can be constructed by introducing oxygen vacancies in the [Bi2O2]2+ layer. H2O and O2 molecules can be better adsorbed and activated at hole and electron active sites, separately. Accordingly, the pristine and defective Bi2O2CO3 are prepared. The dynamic behavior of H2O and O2 molecules at the matching active sites is revealed, which indicates the efficient adsorption of reactants and the substantial production of radicals. Significantly, the specificity of the spatially separated holes and electrons active sites for ⸱OH and ⸱O2- radicals generation, respectively, is demonstrated by in situ EPR with the H2O vapor atmosphere. This work provides a design concept for unraveling reaction mechanisms to realize controllable radicals generation.

Substitution of B-site in BaSb2O6 perovskite for surface lattice oxygen activation and boosted photocatalytic toluene mineralization.

Perovskite oxides possess significant prospects in environment application because of their compositional versatility and controllable band structure for redox reactions. Nevertheless, low charge separation and limited reactants activation restrict their performance for practical applications. In this work, we reveal that the electronic structure of BaSb2O6 can be modulated effectively by substituting B-site cations, leading to broadened light response range and promoted carrier separation. The Ga atoms substitute the Sb atoms to form GaO bonds and enable octahedral distortion, resulting in the electron transfer from Ga atom to O atoms and realizing lattice oxygen activation. The unique electronic localization in the BaSb2O6 surface facilitates the adsorption and activation of O2, H2O, toluene and reaction intermediates, thus enhancing ROS generation for toluene mineralization. Compared with the performance of pure BaSb2O6, the photocatalytic toluene degradation and mineralization of 5 wt% Ga-BaSb2O6 are increased by 4.5 times and 4.8 times without obvious deactivation. The reported facile and valid strategy for in situ controlling of B-site in perovskite and their unique effects on the electronic structure would benefit the development of high-performance perovskites for environmental applications.

Crystal-Structure-Dependent Photocatalytic Redox Activity and Reaction Pathways over Ga2O3 Polymorphs.

Differentiated crystal structures generally affect the surface physicochemical properties of catalysts, causing variety in catalytic activity between polymorphs. However, the underlying mechanism has not been completely revealed, especially the influence of surface physicochemical properties on photocatalytic redox activity and the reaction mechanism. In this work, we reveal the mechanism of surface redox properties on different crystal forms of gallium oxide from a molecular level. α-Ga2O3 and ß-Ga2O3 exhibit a slight difference in catalytic oxidation of organic pollutants due to comprehensive influencing factors, including their valence band position, reactive oxygen species, and pore structure properties related to the adsorption-reaction-desorption process. But the catalytic reduction ability of CO2 is obviously different due to the large differences of interaction between the surface of crystal structures and CO2 molecules, which are critical to determine the catalytic performance and reaction pathways. The enhanced adsorption and activation of CO2 on the α-Ga2O3 surface could promote the reduction reaction efficiency. Moreover, the large energy barrier of CH2* formation on ß-Ga2O3 makes the formation of methane (CH4) relatively difficult compared to that on α-Ga2O3. The yield rate of CH4 (1.8 µmol·g-1·h-1) on α-Ga2O3 is three times better than that on ß-Ga2O3 (CH4: 0.6 µmol·g-1·h-1). The current findings can offer novel insights into the understanding of crystal-structure-dependent photocatalytic performances and the design of new catalysts applied in energy conversion and environmental purification by crystal structure-tuning.

Surface Lattice Oxygen Activation on Sr2Sb2O7 Enhances the Photocatalytic Mineralization of Toluene: from Reactant Activation, Intermediate Conversion to Product Desorption.

Transition-metal oxide photocatalysis has attracted increasing attention in environmental remediation and solar energy conversion. Surface lattice oxygen is the key active site on the metal oxide, but its role and activation mechanism in the photocatalytic VOC mineralization are still unclear. In this work, we have demonstrated that Sr2Sb2O7 exhibits an excellent photocatalytic activity and stability compared to TiO2 (P25) in gaseous toluene mineralization because the lattice oxygen on Sr2Sb2O7 can be activated efficiently. The lattice oxygen of Sr2Sb2O7 promotes the adsorption and activation of O2 and H2O molecules and enhances the production of •O2- and •OH radicals, as confirmed by the electron spin resonance and DFT calculations. The in situ diffuse reflectance infrared Fourier transform spectroscopy spectra are applied to dynamically monitor the intermediate activation and selective conversion. Combined with DFT calculation, the role and the mechanism of lattice oxygen in photocatalysis have been revealed. Owing to the promoted surface lattice oxygen, the selectivity for benzoic acid formation is enhanced and final product desorption is promoted, which could largely advance the ring opening and mineralization of toluene. This work reveals the origin of lattice oxygen activation and the role for efficient VOC degradation at the atomic scale.

Nature-inspired CaCO3 loading TiO2 composites for efficient and durable photocatalytic mineralization of gaseous toluene.

The accumulation of intermediates or final products on TiO2 during photocatalytic volatile organic compounds (VOCs) degradation is typically neglected, despite the fact that it could result in the block of active sites and the deactivation of photocatalysts. Inspired from the natural formation of stalactite (CaCO3 + H2O + CO2 â†” Ca(HCO3)2), we fabricated CaCO3 loading TiO2 composites (CCT21) to realize the spontaneously transfer of accumulated final products (CO2 and H2O). Efficient and durable performance for gaseous toluene removal has been demonstrated and the cost of photocatalyst is greatly reduced by the comparison of specific activity. The introduction of CaCO3 induces the interaction between TiO2 and CaCO3 to stimulate abundant activated electrons for the improvement on the adsorption and activation of reactants and the transformation of photogenerated carriers, and most importantly, facilitates the transfer of final products to release active sites and thus suppress the deactivation of TiO2. Furthermore, we develop a facile method to immobilize CCT21 powder on flexible support, which greatly reduces the loss of photocatalysts and correspondingly enables the practical application of TiO2-based products. Therefore, this work presents a novel nature-inspired strategy to address the challenge of deactivation, and advances the development of photocatalytic technology for environmental remediation.

Selective biosorption of thorium (IV) from aqueous solutions by ginkgo leaf.

Low-cost biosorbents (ginkgo leaf, osmanthus leaf, banyan leaf, magnolia leaf, holly leaf, walnut shell, and grapefruit peel) were evaluated in the simultaneous removal of La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Yb3+, Lu3+, UO22+, Th4+, Y3+, Co2+, Zn2+, Ni2+, and Sr2+ from aqueous solutions. In single metal systems, all adsorbents exhibited good to excellent adsorption capacities toward lanthanides and actinides. In a simulated multicomponent mixed solution study, higher selectivity and efficiency were observed for Th4+ over other metal cations, with ginkgo leaves providing the highest adsorptivity (81.2%) among the seven biosorbents. Through optimization studies, the selectivity of Th4+ biosorption on ginkgo leaf was found to be highly pH-dependent, with optimum Th4+ removal observed at pH 4. Th4+ adsorption was found to proceed rapidly with an equilibrium time of 120 min and conform to pseudo-second-order kinetics. The Langmuir isotherm model best described Th4+ biosorption, with a maximum monolayer adsorption capacity of 103.8 mg g-1. Thermodynamic calculations indicated that Th4+ biosorption was spontaneous and endothermic. Furthermore, the physical and chemical properties of the adsorbent were determined by scanning electron microscopy, Brunauer-Emmett-Teller, X-ray powder diffraction, and Fourier transform infrared analysis. The biosorption of Th from a real sample (monazite mineral) was studied and an efficiency of 90.4% was achieved from nitric acid at pH 4 using ginkgo leaves.