In situ fabrication of atomically adjacent dual-vacancy sites for nearly 100% selective CH4 production.

The photocatalytic CO2-to-CH4 conversion involves multiple consecutive proton-electron coupling transfer processes. Achieving high CH4 selectivity with satisfactory conversion efficiency remains challenging since the inefficient proton and electron delivery path results in sluggish proton-electron transfer kinetics. Herein, we propose the fabrication of atomically adjacent anion-cation vacancy as paired redox active sites that could maximally promote the proton- and electron-donating efficiency to simultaneously enhance the oxidation and reduction half-reactions, achieving higher photocatalytic CO2 reduction activity and CH4 selectivity. Taking TiO2 as a photocatalyst prototype, the operando electron paramagnetic resonance spectra, quasi in situ X-ray photoelectron spectroscopy measurements, and high-angle annular dark-field-scanning transmission electron microscopy image analysis prove that the VTi on TiO2 as initial sites can induce electron redistribution and facilitate the escape of the adjacent oxygen atom, thereby triggering the dynamic creation of atomically adjacent dual-vacancy sites during photocatalytic reactions. The dual-vacancy sites not only promote the proton- and electron-donating efficiency for CO2 activation and protonation but also modulate the coordination modes of surface-bound intermediate species, thus converting the endoergic protonation step to an exoergic reaction process and steering the CO2 reduction pathway toward CH4 production. As a result, these in situ created dual active sites enable nearly 100% CH4 selectivity and evolution rate of 19.4 µmol g-1 h-1, about 80 times higher than that of pristine TiO2. Thus, these insights into vacancy dynamics and structure-function relationship are valuable to atomic understanding and catalyst design for achieving highly selective catalysis.

Therapeutic efficacy of recombinant human growth hormone in children with different etiologies of dwarfism from a pharmacoeconomic point of view.

Treatment outcomes for different causes of childhood dwarfism vary widely, and there are no studies on the economic burden of treatment in relation to outcomes. This paper compared the efficacy and healthcare costs per unit height of recombinant human growth hormone (rhGH) for the treatment of growth hormone deficiency (GHD) and idiopathic short stature (ISS) with a view to providing a more cost-effective treatment option for children. We retrospectively analyzed 117 cases (66 cases of GHD and 51 cases of ISS) of short-stature children who first visited Weifang People's Hospital between 2019.1 and 2022.1 and were treated with rhGH for 1 to 3 years to track the treatment effect and statistically analyzed by using paired t tests, non-parametric tests, and chi-square tests, to evaluate the efficacy of rhGH treatment for GHD and ISS children and the medicinal cost. The annual growth velocity (GV) of children with GHD and ISS increased the fastest during 3 to 6 months after treatment and then gradually slowed down. The GV of the GHD group was higher than that of the ISS group from 0 to 36 months after treatment (P < .05 at 3, 6, 9, and 12 months); the height standard deviation scores (HtSDS) of the children in the GHD and ISS groups increased gradually with the increase of the treatment time, and the changes in the height standard deviation scores (ΔHtSDS) of the GHD group were more significant than those of the ISS group (P < .05 at 3, 6, 9, and 12 months). (2) The medical costs in the pubertal group for a 1-cm increase in height were higher than those of children in the pre-pubertal group at the same stage (3 to 24 months P < .05). The longer the treatment time within the same group, the higher the medical cost of increasing 1cm height. RhGH is effective in treating children with dwarfism to promote height growth, and the effect on children with GHD is better than that of children with ISS; the earlier the treatment time, the lower the medical cost and the higher the comprehensive benefit.

Boosting exciton dissociation and charge transfer in CsPbBr3 QDs via ferrocene derivative ligation for CO2 photoreduction.

Photo-catalytic CO2 reduction with perovskite quantum dots (QDs) shows potential for solar energy storage, but it encounters challenges due to the intricate multi-electron photoreduction processes and thermodynamic and kinetic obstacles associated with them. This study aimed to improve photo-catalytic performance by addressing surface barriers and utilizing multiple-exciton generation in perovskite QDs. A facile surface engineering method was employed, involving the grafting of ferrocene carboxylic acid (FCA) onto CsPbBr3 (CPB) QDs, to overcome limitations arising from restricted multiple-exciton dissociation and inefficient charge transfer dynamics. Kelvin Probe Force Microscopy and XPS spectral confirmed successfully creating an FCA-modulated microelectric field through the Cs active site, thus facilitating electron transfer, disrupting surface barrier energy, and promoting multi-exciton dissociations. Transient absorption spectroscopy showed enhanced charge transfer and reduced energy barriers, resulting in an impressive CO2-to-CO conversion rate of 132.8 µmol g-1 h-1 with 96.5% selectivity. The CPB-FCA catalyst exhibited four-cycle reusability and 72 h of long-term stability, marking a significant nine-fold improvement compared to pristine CPB (14.4 µmol g-1 h-1). These results provide insights into the influential role of FCA in regulating intramolecular charge transfer, enhancing multi-exciton dissociation, and improving CO2 photoreduction on CPB QDs. Furthermore, these findings offer valuable knowledge for controlling quantum-confined exciton dissociation to enhance CO2 photocatalysis.

Ligand-mediated exciton dissociation and interparticle energy transfer on CsPbBr3 perovskite quantum dots for efficient CO2-to-CO photoreduction.

Perovskite quantum dots (PQDs) hold immense potential as photocatalysts for CO2 reduction due to their remarkable quantum properties, which facilitates the generation of multiple excitons, providing the necessary high-energy electrons for CO2 photoreduction. However, harnessing multi-excitons in PQDs for superior photocatalysis remains challenging, as achieving the concurrent dissociation of excitons and interparticle energy transfer proves elusive. This study introduces a ligand density-controlled strategy to enhance both exciton dissociation and interparticle energy transfer in CsPbBr3 PQDs. Optimized CsPbBr3 PQDs with the regulated ligand density exhibit efficient photocatalytic conversion of CO2 to CO, achieving a 2.26-fold improvement over unoptimized counterparts while maintaining chemical integrity. Multiple analytical techniques, including Kelvin probe force microscopy, temperature-dependent photoluminescence, femtosecond transient absorption spectroscopy, and density functional theory calculations, collectively affirm that the proper ligand termination promotes the charge separation and the interparticle transfer through ligand-mediated interfacial electron coupling and electronic interactions. This work reveals ligand density-dependent variations in the gas-solid photocatalytic CO2 reduction performance of CsPbBr3 PQDs, underscoring the importance of ligand engineering for enhancing quantum dot photocatalysis.

Halogen-Site Regulation in Cs3Bi2X9 Quantum Dots for Efficient and Selective Oxidation of Benzyl Alcohol Driven by Solar Light.

Sluggish charge kinetics and low selectivity limit the solar-driven selective organic transformations under mild conditions. Herein, an efficient strategy of halogen-site regulation, based on the precise control of charge transfer and molecule activation by rational design of Cs3Bi2X9 quantum dots photocatalysts, is proposed to achieve both high selectivity and yield of benzyl-alcohol oxidation. In situ PL spectroscopy study reveals that the Bi─Br bonds formed in the form of Br-associated coordination can enhance the separation and transfer of photoexcited carriers during the practical reaction. As the active center, the exclusive Bi─Br covalence can benefit the benzyl-alcohol activation for producing carbon-centered radicals. As a result, the Cs3Bi2Br9 with this atomic coordination achieves a conversion ratio of 97.9% for benzyl alcohol and selectivity of 99.6% for aldehydes, which are 56.9- and 1.54-fold higher than that of Cs3Bi2Cl9. Combined with quasi-in situ EPR, in situ ATR-FTIR spectra, and DFT calculation, the conversion of C6H5-CH2OH to C6H5-CH2* at Br-related coordination is revealed to be a determining step, which can be accelerated via halogen-site regulation for enhancing selectivity and photocatalytic efficiency. The mechanistic insights of this research elucidate how halogen-site regulation in favor of charge transfer and molecule activation toward efficient and selective oxidation of benzyl alcohol.

Comparison of haploidentical-allogeneic hematopoietic stem cell transplantation and intensive immunosuppressive therapy for patients with severe aplastic anemia with an absolute neutrophil count of zero: a retrospective study.

A retrospective analysis was conducted based on the clinical data from 60 patients older than 16 years from January 2016 to January 2021. All the patients were newly diagnosed with severe aplastic anemia (SAA) with an absolute neutrophil count (ANC) of zero. We compared the hematological response and survival of haploidentical-allogeneic hematopoietic stem cell transplantation (HID-HSCT) (n = 25) and intensive immunosuppressive therapy (IST) (n = 35) treatments. At six months, the overall response rate and complete response were significantly higher in the HID-HSCT group than those in the IST group (84.0% vs. 40.0%, P = 0.001; 80.0% vs. 17.1%, P = 0.001). With a median follow-up of 18.5 months (4.3~30.8 months), patients in the HID-HSCT group had longer overall survival and event-free survival (80.0% vs. 47.9%, P = 0.0419; 79.2% vs. 33.5%, P = 0.0048). These data suggested that HID-HSCT might be an effective alternative treatment option for adult patients with SAA with an ANC of zero, which requires further validation in an additional prospective study.

Nitrogen-Centered Lactate Oxidase Nanozyme for Tumor Lactate Modulation and Microenvironment Remodeling.

Designing nanozymes that match natural enzymes have always been an attractive and challenging goal. In general, researchers mainly focus on the construction of metal centers and the control of non-metallic ligands of nanozyme to regulate their activities. However, this is not applicable to lactate oxidase, i.e., flavoenzymes with flavin mononucleotide (FMN)-dependent pathways. Herein, we propose a coordination strategy to mimic lactate oxidase based on engineering the electronic properties at the N center by modulating the Co number near N in the Cox-N nanocomposite. Benefitting from the manipulated coordination fields and electronic structure around the electron-rich N sites, Co4N/C possesses a precise recognition site for lactate and intermediate organization and optimizes the absorption energies for intermediates, leading to superior oxidation of the lactate α-C-sp(3)-H bond toward ketone. The optimized nanozyme delivers much improved anticancer efficacy by reversing the high lactate and the immunosuppressive state of the tumor microenvironment, subsequently achieving excellent tumor growth and distant metastasis inhibition. The developed Co4N/C NEs open a new window for building a bridge between chemical catalysis and biocatalysis.

Piezoelectric Nanozyme for Dual-Driven Catalytic Eradication of Bacterial Biofilms.

Catalytic nanomedicine can in situ catalytically generate bactericidal species under external stimuli to defend against bacterial infections. However, bacterial biofilms seriously impede the catalytic efficacy of traditional nanocatalysts. In this work, MoSe2 nanoflowers (NFs) as piezoelectric nanozymes were constructed for dual-driven catalytic eradication of multi-drug-resistant bacterial biofilms. In the biofilm microenvironment, the piezoelectricity of MoSe2 NFs was cascaded with their enzyme-mimic activity, including glutathione oxidase-mimic and peroxidase-mimic activity. As a result, the oxidative stress in the biofilms was sharply elevated under ultrasound irradiation, achieving a 4.0 log10 reduction of bacterial cells. The in vivo studies reveal that the MoSe2 NFs efficiently relieve the methicillin-resistant Staphylococcus aureus bacterial burden in mice under the control of ultrasound at a low power density. Moreover, because of the surface coating of antioxidant poly(ethyleneimine), the dual-driven catalysis of MoSe2 NFs was retarded in normal tissues to minimize the off-target damage and favor the wound healing process. Therefore, the cascade of piezoelectricity and enzyme-mimic activity in MoSe2 NFs reveals a dual-driven strategy for improving the performance of catalytic nanomaterials in the eradication of bacterial biofilms.

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.

Dual-quantum-dots heterostructure with confined active interface for promoted photocatalytic NO abatement.

Constructing heterostructure is an effective way to fabricate advanced photocatalysts. However, the catalytic performance of typical common multi-dimensional bulk heterostructure still suffers from the limited active interface and inefficient carrier migration. Herein, we successfully synthesize the SnO2/Cs3Bi2I9 dual-quantum-dots nanoheterostructure (labeled as SCX, X = 1, 2, 3) for efficiently and stably photocatalytic NO removal under visible light irradiation. The NO removal rate of SC2 is almost 8 and 17 times higher than that of the single SnO2 and Cs3Bi2I9, respectively. Moreover, the SC2 photocatalyst shows only 3 % attenuation after five consecutive cycles, demonstrating good photocatalytic stability. Systematic experimental characterization and theoretical density functional theory calculations revealed that the high activity and stability of SCX originated from the efficient charge transfer at the confined interface between SnO2 and Cs3Bi2I9 quantum dots. This work provides a new perspective for constructing innovative dual-quantum-dots nanoheterostructure and assesses their potential in photocatalytic environmental applications.

Chemical Discrimination of Benzene Series and Molecular Recognition of the Sensing Process over Ti-Doped Co3O4.

This work achieved the chemical discrimination of benzene series (toluene, xylene isomers, and ethylbenzene gases) based on the Ti-doped Co3O4 sensor. Benzene series gases presented different gas-response features due to the differences in redox rate on the surface of the Ti-doped Co3O4 sensor, which created an opportunity to discriminate benzene series via the algorithm analysis. Excellent groupings were obtained via the principal component analysis. High prediction accuracies were acquired via k-nearest neighbors, linear discrimination analysis (LDA), and support vector machine classifiers. With the confusion matrix for the data set using the LDA classifier, the benzene series have been well classified with 100% accuracy. Furthermore, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory calculations were conducted to investigate the molecular gas-solid interfacial sensing mechanism. Ti-doped Co3O4 showed strong Lewis acid sites and adsorption capability toward reaction species, which benefited the toluene gas-sensing reaction and resulted in the highly boosted gas-sensing performance. Our research proposed a facile distinction methodology to recognize similar gases and provided new insights into the recognition of gas-solid interfacial sensing mechanisms.

Identification of deactivation-resistant origin of In(OH)3 for efficient and durable photodegradation of benzene, toluene and their mixtures.

Aromatic hydrocarbon is a representative type of VOCs, which causes adverse effects to human health. The degradation stability of aromatic hydrocarbon is of vital importance to commercializing a photocatalyst for its practical application. The most commonly used titanium dioxide photocatalyst (P25) was deactivated rapidly in the photocatalytic VOCs degradation process. In this work, the indium hydroxide (In(OH)3) photocatalyst was developed, which exhibited not only higher efficient activity but also ultra-stable stability for degradation of benzene, toluene and their mixtures. The origin of the activity difference between two catalysts was investigated by combined experimental and theoretical ways. Based on in situ DRIFTS and GC-MS, it was revealed that benzoic acid and carbonaceous byproducts were specifically formed and accumulated on P25, which were responsible for deactivation of photocatalyst. In contrast, as revealed by both DFT calculations and experimental results, the reaction pathway with byproducts blocking the active sites can be thermodynamically avoided on In(OH)3. This rendered high durability to In(OH)3 photocatalyst in degradations of aromatic pollutants. The elucidation of deactivation-resistant effect and reaction mechanism as an ideal photocatalyst for practical usage were provided.

Crystal-structure dependent reaction pathways in photocatalytic formaldehyde mineralization on BiPO4.

Formaldehyde as significant environmental hazard in air seriously harm the environment and human health. Although photocatalysis has demonstrated the possibility for HCHO degradation, it has long been limited by unsatisfied degradation efficiency and the unclear reaction mechanism. Here, we confirm that surface atomic arrangement of BiPO4 plays a critical role in photooxidation of HCHO via modulating the reaction pathway, offering 2.63 times enhancement of HCHO degradation efficiency. We dissect the processes in the photocatalytic reaction by DFT calculation, ROS monitoring, and in situ diffuse reflectance infrared Fourier transform spectra (DRIFTS) investigation. Specifically, we reveal that the controlling surface atomic arrangement could modulate adsorption model from single-point to bridging, and promote activation of small molecules. Concurrently, the active surface dependent on crystal structure facilitates the efficient transformation of intermediates (HCOOH*) (reducing energy barrier from 0.41 to -0.35 eV), producing final-product (H2CO3, ∆G = -0.35 eV) while suppressing toxic by-product (CO, ∆G = 0.32 eV), which contributes to the sustained deep mineralization of HCHO with enhancement by 61.4%. The findings are crucial as they provide crystal-structure related insights into the design of efficient catalysts for photocatalytic HCHO degradation. Ultimately, current molecular understanding should unlock the solar-driven catalytic pathways for other oxidation reactions.

Doping and facet effects synergistically mediated interfacial reaction mechanism and selectivity in photocatalytic NO abatement.

The surface atomic coordination and arrangement largely determine photocatalytic properties. Whereas, the intrinsic impact of surface microstructures on the reaction mechanism and pathway is still unclear. Herein, via constructing N-doped Bi2O2CO3 photocatalysts with diverse exposed facets, (1 1 0) and (0 0 1) facet, we testify that the pivotal roles of crystal facet and doping effect on the intermediate production and reactivity for photocatalytic nitric oxide (NO) abatement. The photoreactivity of N-doped Bi2O2CO3 is documented to be higher than that of the pure samples because of the enhanced light absorption and charge transfer. Further in situ probing experiments and theoretical calculations verify that the unique adsorption patterns and activated intermediates on the (1 1 0) facet facilitate the formation of final products and inhibit the generation of toxic NO2 by-product in terms of thermodynamics. More importantly, we found that the selective and nonselective oxidation processes are emerged over (1 1 0) and (0 0 1) facets of Bi2O2CO3, respectively.

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.

Rare-Earth Single-Atom La-N Charge-Transfer Bridge on Carbon Nitride for Highly Efficient and Selective Photocatalytic CO2 Reduction.

Photocatalytic CO2 conversion into valuable solar fuels is highly appealing, but lack of directional charge-transfer channel and insufficient active sites resulted in limited CO2 reduction efficiency and selectivity for most photocatalytic systems. Herein, we designed and fabricated rare-earth La single-atoms on carbon nitride with La-N charge-transfer bridge as the active center for photocatalytic CO2 reaction. The formation of La single-atoms was certified by spherical aberration-corrected HAADF-STEM, STEM-EELS, EXAFS, and theoretical calculations. The electronic structure of the La-N bridge enables a high CO-yielding rate of 92 µmol·g-1·h-1 and CO selectivity of 80.3%, which is superior to most g-C3N4-based photocatalytic CO2 reductions. The CO production rate remained nearly constant under light irradiation for five cycles of 20 h, indicating its stability. The closely combined experimental and DFT calculations clearly elucidated that the variety of electronic states induced by 4f and 5d orbitals of the La single atom and the p-d orbital hybridization of La-N atoms enabled the formation of charge-transfer channel. The La-N charge bridges are found to function as the key active center for CO2 activation, rapid COOH* formation, and CO desorption. The present work would provide a mechanistic understanding into the utilization of rare-earth single-atoms in photocatalysis for solar energy conversion.

Identification of Halogen-Associated Active Sites on Bismuth-Based Perovskite Quantum Dots for Efficient and Selective CO2-to-CO Photoreduction.

All-inorganic Pb-free bismuth (Bi) halogen perovskite quantum dots (PQDs) with distinct structural and photoelectric properties provide plenty of room for selective photoreduction of CO2. However, the efficient conversion of CO2-to-CO with high selectivity on Bi-based PQDs driven by solar light remains unachieved, and the precise reaction path/mechanism promoted by the surface halogen-associated active sites is still poorly understood. Herein, we screen a series of nontoxic and stable Cs3Bi2X9 (X = Cl, Br, I) PQDs for selective photocatalytic reduction of CO2-to-CO at the gas-solid interface. Among all the reported pure-phase PQDs, the as-synthesized Cs3Bi2Br9 PQDs exhibited the highest CO2-to-CO conversion efficiency generating 134.76 µmol g-1 of CO yield with 98.7% selectivity under AM 1.5G simulated solar illumination. The surface halogen-associated active sites and reaction intermediates were dynamically monitored and precisely unraveled based on in situ DRIFTS investigation. In combination with the DFT calculation, it was revealed that the surface Br sites allow for optimizing the coordination modes of surface-bound intermediate species and reducing the reaction energy of the rate-limiting step of COOH- intermediate formation from •CO2-. This work presents a mechanistic insight into the halogen-involved catalytic reaction mechanism in solar fuel production.

Capsaicin attenuates liver fibrosis by targeting Notch signaling to inhibit TNF-α secretion from M1 macrophages.

BACKGROUND: Capsaicin is a chili pepper extract with multiple therapeutic properties including anti-liver fibrosis. However, the paucity of its underlying mechanisms limited its widely clinical application. METHODS: In the present study, carbon tetrachloride (CCl4) was used to induce liver fibrosis in mice, and transforming growth factorß1 (TGFß1) was used to mimic liver fibrosis in vitro. Flow cytometry was conducted to determine the expression of CD80. The inflammatory factors level was examined by ELISA, and gene expression was detected by real-time PCR and western blot. RESULTS: Here, we show that capsaicin attenuates liver fibrosis progression by mediating macrophage inflammatory response. Capsaicin inhibited M1 polarization of macrophage by regulating Notch signaling leading to the reduced secretion of inflammatory cytokine TNF-α that correspondingly attenuates myofibroblasts regeneration and fibrosis formation of hepatocyte stellate cells (HSCs). CONCLUSION: Taken together, capsaicin alleviates liver fibrosis by inactivation of Notch signaling and further inhibiting TNF-α secretion from M1 macrophage. Targeting TNF-α or Notch signaling in macrophage represents a promising strategy to combat liver fibrosis.

La-doping induced localized excess electrons on (BiO)2CO3 for efficient photocatalytic NO removal and toxic intermediates suppression.

Photocatalysis technology has been extensively adopted to abate typical air pollutants. Nevertheless, it is a challenge to develop photocatalysts aiming to simultaneously improve photocatalytic selectivity and efficiency. In this study, to improve the photocatalytic selectivity and the performance of (BiO)2CO3 in the oxidation of NO to target products (NO2- /NO3-), we developed a novel method to construct La-doped (BiO)2CO3 (La-BOC) for forming localized excess electrons (Ex) on (BiO)2CO3 surface. The results indicate that the Ex could effectively accelerate the activation of reactants and promote charge separation and transfer. Under visible light, the gas molecules could capture the Ex and get activated to produce reactive oxygen species (ROS) with high oxidation ability, which enables complete oxidation of NO to target products instead of producing other toxic by-products. Due to the functionality of the Ex, the photocatalytic selectivity and efficiency of La-BOC have been synchronously improved. Combining experimental and theoretical methods, this work unravels the pathway of charge carriers transportation/transformation and elucidates the photocatalytic NO oxidation mechanism. The present work could provide a novel method to improve photocatalytic selectivity and activity for safe air pollutant abatement.

Theoretical design and experimental investigation on highly selective Pd particles decorated C3N4 for safe photocatalytic NO purification.

Rational design of highly active and selective photocatalyst for NO removal is significant for the commercial application of photocatalytic technology because the secondary byproduct caused by insufficient and non-selective pollutant oxidation process is a major challenge. In this work, Pd nanoparticles decorated C3N4 (PdCN) is designed by density functional theory (DFT) at first. The PdCN exhibits superiority to CN in terms of both kinetics and thermodynamics performances, as reflected in the lower activation barrier of rate-determining step and higher selectivity for the final product (nitrate) instead of toxic intermediate (NO2). The as-designed highly selective and efficient photocatalyst is then fabricated by a facile method with an extremely low content of Pd particles supported on C3N4. Compared to bare CN, the synthesized PdCN exhibits highly enhanced purification of NO in air and strong inhibition of toxic NO2 by-product as supported by in-situ DRIFTS investigation, which is consistent with the theoretical prediction. This work is a typical demonstration of setting up a bridge between theory and experiment to give a promising way to the rational design of advanced photocatalysts and atomic understanding of the reaction mechanism.