Liquid metal for high-entropy alloy nanoparticles synthesis.

High-entropy alloy nanoparticles (HEA-NPs) show great potential as functional materials1-3. However, thus far, the realized high-entropy alloys have been restricted to palettes of similar elements, which greatly hinders the material design, property optimization and mechanistic exploration for different applications4,5. Herein, we discovered that liquid metal endowing negative mixing enthalpy with other elements could provide a stable thermodynamic condition and act as a desirable dynamic mixing reservoir, thus realizing the synthesis of HEA-NPs with a diverse range of metal elements in mild reaction conditions. The involved elements have a wide range of atomic radii (1.24-1.97 Å) and melting points (303-3,683 K). We also realized the precisely fabricated structures of nanoparticles via mixing enthalpy tuning. Moreover, the real-time conversion process (that is, from liquid metal to crystalline HEA-NPs) is captured in situ, which confirmed a dynamic fission-fusion behaviour during the alloying process.

Spatial Distribution of Brønsted Acid Sites Determines the Mobility of Reactive Cu Ions in the Cu-SSZ-13 Catalyst during the Selective Catalytic Reduction of NOx with NH3.

The formation of dimer-Cu species, which serve as the active sites of the low-temperature selective catalytic reduction of NOx with NH3 (NH3-SCR), relies on the mobility of CuI species in the channels of the Cu-SSZ-13 catalysts. Herein, the key role of framework Brønsted acid sites in the mobility of reactive Cu ions was elucidated via a combination of density functional theory calculations, in situ impedance spectroscopy, and in situ diffuse reflectance ultraviolet-visible spectroscopy. When the number of framework Al sites decreases, the Brønsted acid sites decrease, leading to a systematic increase in the diffusion barrier for [Cu(NH3)2]+ and less formation of highly reactive dimer-Cu species, which inhibits the low-temperature NH3-SCR reactivity and vice versa. When the spatial distribution of Al sites is uneven, the [Cu(NH3)2]+ complexes tend to migrate from an Al-poor cage to an Al-rich cage (e.g., cage with paired Al sites), which effectively accelerates the formation of dimer-Cu species and hence promotes the SCR reaction. These findings unveil the mechanism by which framework Brønsted acid sites influence the intercage diffusion and reactivity of [Cu(NH3)2]+ complexes in Cu-SSZ-13 catalysts and provide new insights for the development of zeolite-based catalysts with excellent SCR activity by regulating the microscopic spatial distribution of framework Brønsted acid sites.

Age-Dependent Female Survival Advantage in Hepatocellular Carcinoma: A Multicenter Cohort Study.

BACKGROUND & AIMS: Hepatocellular carcinoma (HCC) has a higher incidence in males, but the association of sex with survival remains controversial. This study aimed to examine the effect of sex on HCC survival and its association with age. METHODS: Among 33,238 patients with HCC from 12 Chinese tertiary hospitals, 4175 patients who underwent curative-intent hepatectomy or ablation were analyzed. Cancer-specific survival (CSS) was analyzed using Cox regression and Kaplan-Meier methods. Two propensity score methods and multiple mediation analysis were applied to mitigate confounding. To explore the effect of estrogen, a candidate sex-specific factor that changes with age, female participants' history of estrogen use, and survival were analyzed. RESULTS: There were 3321 males and 854 females included. A sex-related disparity of CSS was present and showed a typical age-dependent pattern: a female survival advantage over males appeared at the perimenopausal age of 45 to 54 years (hazard risk [HR], 0.77; 5-year CSS, 85.7% vs 70.6%; P = .018), peaked at the early postmenopausal age of 55 to 59 years (HR, 0.57; 5-year CSS, 89.8% vs 73.5%; P = .015), and was not present in the premenopausal (<45 y) and late postmenopausal groups (≥60 y). Consistent patterns were observed in patients after either ablation or hepatectomy. These results were sustained with propensity score analyses. Confounding or mediation effects accounted for only 19.5% of sex survival disparity. Female estrogen users had significantly longer CSS than nonusers (HR, 0.74; 5-year CSS, 79.6% vs 72.5%; P = .038). CONCLUSIONS: A female survival advantage in HCC depends on age, and this may be associated with age-dependent, sex-specific factors.

Combined Experimental and Density Functional Theory Study on the Mechanism of the Selective Catalytic Reduction of NO with NH3 over Metal-Free Carbon-Based Catalysts.

Metal-free carbon-based catalysts are attracting much attention in the low-temperature selective catalytic reduction of NOx with NH3 (NH3-SCR). However, the mechanism of the NH3-SCR reaction on carbon-based catalysts is still controversial, which severely limits the development of carbon-based SCR catalysts. Herein, we successfully reconstructed carbon-based catalysts through oxidation treatment with nitric acid, thereby enhancing their low-temperature activity in NH3-SCR. Combining experimental results and density functional theory (DFT) calculations, we proposed a previously unreported NH3-SCR reaction mechanism over carbon-based catalysts. We demonstrated that C-OH and C-O-C groups not only effectively activate NH3 but also remarkedly promote the decomposition of intermediate NH2NO. This study enhances the understanding of the NH3-SCR mechanism on carbon-based catalysts and paves the way to develop low-temperature metal-free SCR catalysts.

Unexpected Promotion Effect of H2O on the Selective Catalytic Reduction of NOx with NH3 over Cu-SSZ-39 Catalysts.

Water molecules commonly inhibit the selective catalytic reduction (SCR) of NOx with NH3 on most catalysts, and water resistance is a long-standing challenge for SCR technology. Herein, by combining experimental measurements and density functional theory (DFT) calculations, we found that water molecules do not inhibit and even promote the NOx conversion to some extent over the Cu-SSZ-39 zeolites, a promising SCR catalyst. Water acting as a ligand on active Cu sites and as a reactant in the SCR reaction significantly improves the O2 activation performance and reduces the overall energy barrier of the catalytic cycle. This work unveils the mechanism of the unexpected promotion effect of water on the NH3-SCR reaction over Cu-SSZ-39 and provides fundamental insight into the development of zeolite-based SCR catalysts with excellent activity and water resistance.

Modulating the Electronic Structures of Pt on Pt/TiO2 Catalyst for Boosting Toluene Oxidation.

Surface hydroxyl groups commonly exist on the catalyst and present a significant role in the catalytic reaction. Considering the lack of systematical researches on the effect of the surface hydroxyl group on reactant molecule activation, the PtOx/TiO2 and PtOx-y(OH)y/TiO2 catalysts were constructed and studied for a comprehensive understanding of the roles of the surface hydroxyl group in the oxidation of volatiles organic compounds. The PtOx/TiO2 formed by a simple treatment with nitric acid presented greatly enhanced activity for toluene oxidation in which the turnover frequency of toluene oxidation on PtOx/TiO2 was around 14 times as high as that on PtOx-y(OH)y/TiO2. Experimental and theoretical results indicated that adsorption/activation of toluene and reactivity of oxygen atom on the catalyst determined the toluene oxidation on the catalyst. The removal of surface hydroxyl groups on PtOx promoted strong electronic coupling of the Pt 5d orbital in PtOx and C 2p orbital in toluene, facilitating the electron transfers from toluene to PtOx and subsequently the adsorption/activation of toluene. Additionally, the weak Pt-O bond promoted the activation of surface lattice oxygen, accelerating the deep oxidation of activated toluene. This study clarifies the inhibiting effect of surface hydroxyl groups on PtOx in toluene oxidation, providing a further understanding of hydrocarbon oxidation.

Laser Induced Coffee-Ring Structure through Solid-Liquid Transition for Color Printing.

Metallic micro/nano structures with special physicochemical properties have undergone rapid development owing to their broad applications in micromachines and microdevices. Ultrafast laser processing is generally accepted as an effective technology for functional structures manufacture, however, the controllable fabrication of specific metallic micro/nano structures remains a challenge. Here, this work proposes a novel strategy of laser induced transient solid-liquid transition to fabricate unique structures. Through modulating the transient state of metal from solid to liquid phase using the initial pulse excitation, the subsequent ultrafast pulse-induced recoil pressure can suppress the plasma emission and removal of liquid phase metals, resulting in the controllable fabrication of coffee-ring structures. The solid-liquid transition dynamics, which related with the transient reflectivity and plasma intensity, are revealed by established two temperature model coupled with molecular dynamics model. The coffee-ring structure exhibits tunable structure color owing to various optical response, which can be used for color printing with large scale and high resolution. This work provides a promising strategy for fabricating functional micro/nano structures, which can greatly broaden the potential applications.

Promoting Effect of Nitride as Support for Pd Hydrodechlorination Catalyst.

Pd-catalyzed reductive decontamination is considerably promising in the safe handling of various pollutants, and previous studies on heterogeneous Pd catalysts have demonstrated the key role of support in determining their catalysis performance. In this work, metal nitrides were studied as supports for Pd as a hydrodechlorination (HDC) catalyst. Density functional theory study showed that a transition metal nitride (TMN) support could effectively modulate the valence-band state of Pd. The upward shift of the d-band center reduced the energy barrier for water desorption from the Pd site to accommodate H2/4-chlorophenol and increased the total energy released during HDC. The theoretical results were experimentally verified by synthesizing Pd catalysts onto different metal oxides and the corresponding nitrides. All studied TMNs, including TiN, Mo2N, and CoN, showed satisfactorily stabilized Pd and render Pd with high dispersity. In line with theoretical prediction, TiN most effectively modulated the electronic states of the Pd sites and enhanced their HDC performance, with mass activity much higher than those of counterpart catalysts on other supports. The combined theoretical and experimental results shows that TMNs, especially TiN, are new and potentially important support for the highly efficient Pd HDC catalysts.

Safety and efficacy of microwave ablation for the treatment of low-risk papillary thyroid microcarcinoma: a prospective multicenter study.

OBJECTIVES: To assess the safety and efficacy of ultrasound-guided thermal ablation for low-risk papillary thyroid microcarcinoma (PTMC) via a prospective multicenter study. METHODS: From January 2017 through June 2021, low-risk PTMC patients were screened. The management details of active surveillance (AS), surgery, and thermal ablation were discussed. Among patients who accepted thermal ablation, microwave ablation (MWA) was performed. The main outcome was disease-free survival (DFS). The secondary outcomes were tumor size and volume changes, local tumor progression (LTP), lymph node metastasis (LNM), and complication rate. RESULTS: A total of 1278 patients were included in the study. The operation time of ablation was 30.21 ± 5.14 min with local anesthesia. The mean follow-up time was 34.57 ± 28.98 months. Six patients exhibited LTP at 36 months, of whom 5 patients underwent a second ablation, and 1 patient received surgery. The central LNM rate was 0.39% at 6 months, 0.63% at 12 months, and 0.78% at 36 months. Of the 10 patients with central LNM at 36 months, 5 patients chose ablation, 3 patients chose surgery and the other 2 patients chose AS. The overall complication rate was 1.41%, and 1.10% of patients developed hoarseness of the voice. All of the patients recovered within 6 months. CONCLUSIONS: Thermal ablation of low-risk PTMC was observed to be safe and efficacious with few minor complications. This technique may help to bridge the gap between surgery and AS as treatment options for patients wishing to have their PTMC managed in a minimally invasive manner. CLINICAL RELEVANCE STATEMENT: This study proved that microwave ablation is a safe and effective treatment method for papillary thyroid microcarcinoma. KEY POINTS: Percutaneous US-guided microwave ablation of papillary thyroid microcarcinoma is a very minimally invasive treatment under local anesthesia during a short time period. The local tumor progression and complication rate of microwave ablation in the treatment of papillary thyroid microcarcinoma are very low.

Mechanistic Insight into the Promotion of the Low-Temperature NH3-Selective Catalytic Reduction Activity over MnxCe1-xOy Catalysts: A Combined Experimental and Density Functional Theory Study.

CeO2 has attracted much attention in the field of selective catalytic reduction of NO with NH3 (NH3-SCR). However, poor low-temperature activity and a narrow operation window restrict the industrial application of Ce-based oxide catalysts. Herein, the low-temperature NH3-SCR activity of Ce-based oxide catalysts was dramatically improved by Mn doping, and the mechanism was elucidated at the atomic level by experimental measurements and density functional theory calculations. We found that the addition of Mn significantly promoted the formation of surface oxygen vacancies. The oxygen vacancies easily captured O2 in air and formed active oxygen species (superoxide and peroxide) on the surface. The surface active oxygen species efficiently oxidized NO into NO2 and then facilitated the "fast SCR" reaction. This study provides atomic-level insights into the promotion of the NH3-SCR activity over Mn-Ce composite oxides and is beneficial for the development of low-temperature Ce-based catalysts.

Neglected but Efficient Electron Utilization Driven by Biochar-Coactivated Phenols and Peroxydisulfate: Polyphenol Accumulation Rather than Mineralization.

We report an unrecognized but efficient nonradical mechanism in biochar-activated peroxydisulfate (PDS) systems. Combining a newly developed fluorescence trapper of reactive oxygen species with steady-state concentration calculations, we showed that raising pyrolysis temperatures of biochar (BC) from 400 to 800 °C remarkably enhanced trichlorophenol degradation but inhibited the catalytic production of radicals (SO4•- and •OH) in water and soil, thereby switching a radical-based activation into an electron-transfer-dominated nonradical pathway (contribution increased from 12.9 to 76.9%). Distinct from previously reported PDS* complex-determined oxidation, in situ Raman and electrochemical results of this study demonstrated that the simultaneous activation of phenols and PDS on the biochar surface triggers the potential difference-driven electron transfer. The formed phenoxy radicals subsequently undergo coupling and polymerization reactions to generate dimeric and oligomeric intermediates, which are eventually accumulated on the biochar surface and removed. Such a unique nonmineralizing oxidation achieved an ultrahigh electron utilization efficiency (ephenols/ePDS) of 182%. Through biochar molecular modeling and theoretical calculations, we highlighted the critical role of graphitic domains rather than redox-active moieties in lowering band-gap energy to facilitate electron transfer. Our work provides insights into outstanding contradictions and controversies related to nonradical oxidation and inspiration for more oxidant-saving remediation technologies.

Unveiling the Origin of Selectivity in the Selective Catalytic Reduction of NO with NH3 over Oxide Catalysts.

The trade-off between activity and selectivity is a century-old puzzle in catalysis. In the selective catalytic reduction of NO with NH3 (NH3-SCR), various typical oxide catalysts exhibit distinct characteristics of activity and selectivity: Mn-based catalysts show outstanding low-temperature activity and poor N2 selectivity, mainly caused by N2O formation, while Fe- and V-based catalysts possess inverse characteristics. The underlying mechanism, however, has remained elusive. In this study, by combining experimental measurements and density functional theory calculations, we demonstrate that the distinct difference in the selectivity of oxide catalysts is determined by the gap in the energy barriers between N2 formation and N2O formation from the consumption of the key intermediate NH2NO. The gaps in the energy barriers follow the order of α-MnO2 < α-Fe2O3 < V2O5/TiO2, in correspondence with the order of N2 selectivity of the catalysts. This work discloses the intrinsic link between the target reaction and side reactions in the selective catalytic reduction of NO, providing fundamental insights into the origin of selectivity.

Enhanced Hydrosaturation Selectivity and Electron Transfer for Electrocatalytic Chlorophenols Hydrogenation on Ru Sites.

Electrocatalytic hydrogenation is acknowledged as a promising strategy for chlorophenol dechlorination. However, the widely used Pd catalysts exhibit drawbacks, such as high costs and low selectivity for phenol hydrosaturation. Herein, we demonstrate the potential and mechanism of Ru in serving as a Pd substitute using 2,4,6-trichlorophenol (TCP) as a model pollutant. Up to 99.8% TCP removal efficiency and 99% selectivity to cyclohexanol, a value-added compound with an extremely low toxicity, were achieved on the Ru electrode. In contrast, only 66% of TCP was removed on the Pd electrode, with almost no hydrosaturation selectivity. The superiority of Ru over Pd was especially noteworthy in alkaline conditions or the presence of interfering species such as S2-. The theoretical simulation demonstrates that Ru possesses a hydrodechlorination energy barrier of 0.72 eV, which is comparable to that on Pd. Meanwhile, hydrosaturation requires an activation energy of 0.69 eV on Ru, which is much lower than that on Pd (0.92 eV). The main reaction mechanism on Ru is direct electron transfer, which is distinct from that on Pd (indirect pathway via atomic hydrogen, H*). This work thereby provides new insights into designing cost-effective electrocatalysts for halogenated phenol detoxification and resource recovery.

Uncovering the Dinuclear Mechanism of NO2-Involved NH3-SCR over Supported V2O5/TiO2 Catalysts.

Commercial vanadium oxide catalysts exhibit high efficiency for the selective catalytic reduction (SCR) of NO with NH3, especially in the presence of NO2 (i.e., occurrence of fast NH3-SCR). The high-activity sites and their working principle for the fast NH3-SCR reaction, however, remain elusive. Here, by combining in situ spectroscopy, isotopic labeling experiments, and density functional theory (DFT) calculations, we demonstrate that polymeric vanadyl species act as the main active sites in the fast SCR reaction because the coupling effect of the polymeric structure alters the elementary reaction step and effectively avoids the high energy barrier of the rate-determining step over monomeric vanadyl species. This study unveils the high-activity dinuclear mechanism of the NO2-involved SCR reaction over vanadia-based catalysts and provides a fundamental basis for developing high-efficiency and low V2O5-loading SCR catalysts.

A superior catalyst for ozone decomposition: NiFe layered double hydroxide.

Ground-level ozone is harmful to human beings and ecosystems, while room-temperature catalytic decomposition is the most effective technology for ozone abatement. However, solving the deactivation of existing metal oxide catalysts was caused by oxygen-containing intermediates is challenging. Here, we successfully prepared a two-dimensional NiFe layered double hydroxide (NiFe-LDH) catalyst via a facile co-precipitation method, which exhibited stable and highly efficient performance of ozone decomposition under harsh operating conditions (high space velocity and humidity). The NiFe-LDH catalyst with Ni/Fe = 3 and crystallization time over 5 hr (named Ni3Fe-5) exhibited the best catalytic performance, which was well beyond that of most existing manganese-based oxide catalysts. Specifically, under relative humidity of 65% and space velocity of 840 L/(g·hr), Ni3Fe-5 showed ozone conversion of 89% and 76% for 40 ppmV of O3 within 6 and 168 hr at room-temperature, respectively. We demonstrated that the layered structure of NiFe-LDH played a decisive role in its outstanding catalytic performance in terms of both activity and water resistance. The LDH catalysts fundamentally avoids the deactivation caused by the occupancy of oxygen vacancies by oxygen-containing species (H2O, O-, and O2-) in manganese-based oxide. This study indicated the promising application potential of LDHs than manganese-based oxide catalysts in removal of gaseous ozone.

A multicenter 10-year oncologic outcome of ultrasound-guided percutaneous microwave ablation of clinical T1 renal cell carcinoma: will it stand the test of time?

OBJECTIVES: We updated the experience on percutaneous microwave ablation for renal cell carcinoma with five-center data and long-term follow-up. METHODS: This retrospective study reviewed the T1N0M0 renal cell carcinoma patients who underwent microwave ablation between April 2006 and December 2019. Clinicopathological and procedural data were collected. Technical effectiveness and complications were assessed, and the Kaplan-Meier method was used for cancer-specific survival, disease-free survival, overall survival, and local neoplastic process analyses. RESULTS: A total of 323 consecutive patients (mean age, 62.9 years ± 14.0) with 371 biopsy-proved tumors (mean diameter, 2.9 cm ± 1.2) were enrolled, and 42.6% of the tumors were located adjacent to collecting system/bowel and technical effectiveness was achieved in 360 (97.0%) tumors. For 275 cT1a patients, during median follow-up time of 66.0 months (IQR, 58.4-73.6), 10-year local neoplastic processes, cancer-specific survival, disease-free survival, and overall survival rates were 1.9%, 87.4%, 71.8, and 67.5%, respectively. For 48 cT1b patients, during the median follow-up time of 30.4 months (IQR, 17.7-44.8), 5-year local tumor progression, cancer-specific survival, disease-free survival, and overall survival rates were 11.3%, 91.4%, 69.1, and 89.2%, respectively. Major complications showed no differences between cT1a (3.5%) and cT1b (6.9%) patients (p = 0.28). A clinical risk stratification system was developed based on multivariable model to predict DFS and CSS with c-indexes of 0.78 (95% CI: 0.71-0.85) and 0.77 (95% CI: 0.65-0.90), respectively. CONCLUSIONS: With matured follow-up at five institutions, ultrasound-guided percutaneous microwave ablation is a reliable treatment option for cT1a renal cell carcinoma even in dangerous location and appears to be promising for cT1b tumors. KEY POINTS: • To our knowledge, this is the first multicenter cohort of long-term oncologic outcomes with percutaneous MWA of cT1 RCC. • The predicting model we developed is accurate to predict the long-term DFS and CSS, which can help to provide a better MWA prognostication over routinely available clinical information. • The available evidence shows that microwave ablation of clinical stage T1 RCC is safe and reliable with promising long-term oncologic outcomes, especially for cT1a RCC with excellent 10-year results.

Effect of Hydroxyl Groups on Metal Anchoring and Formaldehyde Oxidation Performance of Pt/Al2O3.

Pt/Al2O3 catalysts showing excellent activity and stability have been used in various reactions, including HCHO oxidation. Herein, we prepared Pt-Na/Al2O3 catalysts with a Pt content of 0.05 wt % to reveal the key factors determining the anchoring of Pt as well as the catalytic activity and mechanism of HCHO oxidation. Pt-Na/nano-Al2O3 (denoted as Pt-Na/nAl2O3) catalysts with 0.05 wt % Pt content could completely oxidize HCHO to CO2 at room temperature, which is the lowest Pt content used in HCHO catalytic oxidation to our knowledge. After Na addition, terminal hydroxyl groups (denoted as HO-µter) on nano-Al2O3 were transformed to doubly bridging hydroxyl groups between Na and Al (denoted as HO-µbri(Na-Al)), which atomically dispersed Pt species. Pt anchoring further promoted the regeneration of HO-µbri(Na-Al) by activating O2 and H2O, oxidizing HCHO to CO2 directly by the fast reaction step ([HCOO-] + [OH]a → CO2 + H2O). Our study revealed that the HO-µbri(Na-Al) synergistically generated by HO-µter and Na species provided anchoring sites for Pt species.

Layered Double Hydroxide Catalysts for Ozone Decomposition: The Synergic Role of M2+ and M3.

In previous work, we successfully prepared a NiFe-layered double hydroxide (LDH) with superior activity and stability for catalytic ozone decomposition, which fundamentally avoids deactivation under high-humidity conditions. However, the role of the metal elements (M2+ and M3+) in LDH catalysts is not clear. Here, LDH materials containing different metals (NiFe, NiAl, NiMn, CoFe, and MgFe) were prepared by a simple co-precipitation method. It was found that the LDHs containing Ni2+ exhibited catalytic performance far superior to that of Co2+ and Mg2+ for ozone elimination, and NiFe-LDH had the best activity and stability among LDH materials prepared in this study. The NiFe-LDH can maintain 78% catalytic activity within 144 h at room temperature, even under a relative humidity of 65% and a space velocity of 840 L·g-1·h-1. Physicochemical characterizations demonstrated that chemical stability in an oxidizing atmosphere and the synergic role of M2+ and M3+ ions are crucial. The result of density functional theory calculation showed that the synergic role of Ni2+ and Fe3+ weakens the interaction between O and H in the O-H bond, which effectively lowers the reaction barrier of ozone decomposition compared with MgFe-LDH.

Si/Al Ratio Determines the SCR Performance of Cu-SSZ-13 Catalysts in the Presence of NO2.

A comparative study was performed to investigate the NH3-selective catalytic reduction (SCR) reaction activity of Cu-SSZ-13 zeolites having Si/Al ratios (SARs) of 5, 18, and 30. Remarkably, the Cu-SSZ-13 zeolite catalysts exhibited completely opposite behaviors as a function of SAR under standard SCR (SSCR) and fast SCR (FSCR) reaction atmospheres. Under SSCR conditions, the NOx conversion increased as expected with the decreasing SAR. Under FSCR conditions, however, the NOx conversion decreased as the SAR decreased, contrary to expectations. In this study, based on characterization of the catalysts by X-ray diffraction, transmission electron microscopy, electron paramagnetic resonance, H2-temperature-programmed reduction, temperature-programmed desorption, and diffuse reflectance infrared Fourier transform spectroscopy, together with theoretical calculations, the authors found that the amount of Brønsted acid sites goes up while the SAR goes down, leading to an increase in the accumulation of NH4NO3 under FSCR reaction conditions. Moreover, the accumulated NH4NO3 is of greater stability for those low SAR Cu-SSZ-13 catalysts. These two reasons cause the FSCR performance of Cu-SSZ-13 to decrease with a decrease in SAR. As a result, the NO2 effect on SCR activity changes from promotion to inhibition as the SAR decreases.

Generation and Release of OH Radicals from the Reaction of H2 O with O2 over Soot.

OH radicals in the air maintain the oxidizing power of the troposphere. A conventional view is that particulate matter (PM) in the atmosphere is a major sink of OH radicals, thereby lowering the oxidizing power of atmosphere in the event of high-level PM. By contrary, our joint experimental/theoretical study reveals a new mechanism for the generation of gaseous OH radicals by carbonaceous soot particles. We show that water and O2 react on carbonaceous surfaces and give rise to gaseous OH radicals under irradiation. With ample delocalized π electrons, carbonaceous surfaces enable the easy desorption of hydroxyl groups to produce gaseous OH radicals, evidenced by direct observation of the steady generation of OH radicals on a carbonaceous surface. Our results reveal a new chemical mechanism for the production of OH radicals.