Study on the mechanism of acid treatment La0.8Sr0.2Mn0.8Cu0.2O3 to improve the catalytic activity of formaldehyde at low temperature.

To address the issue of surface enrichment of A-site ions in perovskite and the resulting suppression of catalytic activity, the La0.8Sr0.2Mn0.8Cu0.2O3 was modified by treatment with dilute nitric acid (2 mol/L) and dilute acetic acid (2 mol/L). The results show that the effect of dilute nitric acid treatment on the morphology and catalytic activity of the catalyst is more significant. The specific surface area of the catalyst after dilute nitric acid treatment (268.78 m2/g) is seven times higher than before treatment (37.55 m2/g). The low-temperature catalytic oxidation activity of HCHO of the catalyst after dilute nitric acid treatment is significantly improved, achieving a 50% HCHO oxidation efficiency at 80 °C, while the original sample requires 127 °C to achieve a 50% HCHO conversion. The excellent catalytic activity of the catalyst after dilute nitric acid treatment is related to its large specific surface area, high surface-active site density, and abundant Mn4+ ions. Stability and water resistance experiments show that the catalyst after dilute nitric acid treatment has excellent reaction stability and good water resistance ability. The mechanism of the formaldehyde oxidation reaction is that formaldehyde is first oxidized to a dioxymethylene (DOM) intermediate and DOM dehydrogenation reaction is responsible for the formation of formate species (HCOO-).

Modeling the mechanisms of conifer mortality under seawater exposure.

Relative sea level rise (SLR) increasingly impacts coastal ecosystems through the formation of ghost forests. To predict the future of coastal ecosystems under SLR and changing climate, it is important to understand the physiological mechanisms underlying coastal tree mortality and to integrate this knowledge into dynamic vegetation models. We incorporate the physiological effect of salinity and hypoxia in a dynamic vegetation model in the Earth system land model, and used the model to investigate the mechanisms of mortality of conifer forests on the west and east coast sites of USA, where trees experience different form of sea water exposure. Simulations suggest similar physiological mechanisms can result in different mortality patterns. At the east coast site that experienced severe increases in seawater exposure, trees loose photosynthetic capacity and roots rapidly, and both storage carbon and hydraulic conductance decrease significantly within a year. Over time, further consumption of storage carbon that leads to carbon starvation dominates mortality. At the west coast site that gradually exposed to seawater through SLR, hydraulic failure dominates mortality because root loss impacts on conductance are greater than the degree of storage carbon depletion. Measurements and modeling focused on understanding the physiological mechanisms of mortality is critical to reducing predictive uncertainty.

Oxidation mechanism of HCHO on copper-manganese composite oxides catalyst.

Formaldehyde (HCHO) is a typical air pollutant that severely endangers human health. The Cu-Mn spinel-structure catalyst exhibits good catalytic oxidation activity for HCHO removal. Theoretical calculation study of density functional theory (DFT) was performed to provide an atomic-scale understanding for the oxidation mechanism of HCHO over CuMn2O4 surface. The results indicate that the (110) surface containing alternating three-coordinated Cu atom and three-coordinated Mn atom is more active for HCHO and O2 adsorption than the (100) surface. The Mars-van-Krevelen mechanism is dominant for HCHO catalytic oxidation. This reaction pathway of MvK mechanism includes HCHO adsorption and dehydrogenation dissociation, CO2 formation and desorption, O2 adsorption, H2O formation and surface restoration. In the complete catalytic cycle of HCHO oxidation, the second dehydrogenation (CHO* → CO* + H*) shows the highest energy barrier and is recognized as the rate-limiting step. The relationship of temperature and reaction rate constant is found to be positive by the kinetic analysis. The minimum activation energy of the MvK mechanism via the direct dehydrogenation pathway is 1.29 eV. This theoretical work provides an insight into the catalytic mechanism of HCHO oxidation over CuMn2O4 spinel.

Mechanistic insights into benzene oxidation over CuMn2O4 catalyst.

The spinel-type CuMn2O4 catalyst exhibits good catalytic activity towards benzene oxidation, but the catalytic oxidation mechanism is not established. Theoretical calculations were implemented to unearth the reaction mechanism of benzene catalytic oxidation over CuMn2O4 catalyst through density functional theory (DFT). The results indicate that benzene adsorption on both Cu-terminated and Mn-terminated surfaces are controlled by the chemisorption mechanism. The Cu-terminated surface is more active for benzene adsorption than the Mn-terminated surface. Cu atom is regarded as the primary active site. During benzene catalytic oxidation, benzene firstly undergoes dehydrooxidation reaction to generate phenoxy group (C6H6* → C6H5* → C6H5O*). Two reaction channels are responsible for the ring-opening and oxidation reactions of phenoxy group, including benzoquinone- and cyclopentadienyl-dominated channels. In the benzoquinone-dominated channel, C6H4O2* is produced from phenoxy dehydrogenation and oxidation, and then decomposes into acetylene via the ring-opening reaction (C6H4O2* → C4H2O2* → C4H2O4* → C2H2*). Compared with the benzoquinone-dominated channel, the cyclopentadienyl-dominated channel is dominant for phenoxy group oxidation. Phenoxy group decomposes to generate cyclopentadienyl. C5H5* is dehydrogenated and oxidized to form cyclopentadienone. Finally, C5H4O* is oxidized to form carbon dioxide through a nine-step reaction pathway. The ring-opening reaction (C5H4O* → C3H2O*) has the highest energy barrier of 283.45 kJ/mol, and is identified as the rate-determining step of benzene catalytic oxidation.

Understanding A-site tuning effect on formaldehyde catalytic oxidation over La-Mn perovskite catalysts.

A combination study of density functional theory (DFT) calculation and microkinetic analysis was carried out to investigate A-site tuning effect on formaldehyde (HCHO) oxidation over La-Mn perovskite catalysts (A = Sr, Ag, and Sn). The oxygen mobility of A-doped LaMnO3 catalysts and reaction mechanism of HCHO oxidation on catalyst surfaces were investigated. The microkinetic simulation was performed to quantitatively determine the activity of catalysts toward the HCHO catalytic oxidation. The results indicated that A-site tuning weakens the binding energy of Mn-O bond of LaMnO3 surface and facilitates the formation of surface oxygen vacancy. The presence of dopants can significantly reduce the activation energy of O2 dissociation, which ascribes to the facilitation of electron transfer between oxygen species and catalyst surfaces. The reaction cycle of HCHO oxidation contains seven steps: HCHO adsorption, HCHO* dehydrogenation, CHO* dehydrogenation, CO2 desorption, H2O desorption, O2 adsorption and oxygen vacancy recovery. The dopants promote HCHO adsorption and reduce the activation energy of HCHO oxidation. Two elementary steps control the overall reaction rate of HCHO oxidation. CHO* dehydrogenation step has the largest degree of rate control value at low temperature and O2 adsorption step controls the whole reaction at high temperature.

Mercury/oxygen reaction mechanism over CuFe2O4 catalyst.

CuFe2O4 is regarded as a promising candidate of catalyst for Hg0 oxidation in industrial flue gas. However, the microcosmic reaction mechanism governing mercury oxidation on CuFe2O4 remains elusive. Herein, experiments and quantum chemistry calculations were conducted for understanding the chemical reaction mechanism of oxygen-assisted mercury oxidation on CuFe2O4. CuFe2O4 shows the optimal catalytic activity towards mercury oxidation at 150 ºC. The reactivity difference of different lattice oxygen species is associated with its atomic coordination environment. The lattice oxygen coordinating with two octahedral Cu atoms and a tetrahedral Fe atom shows higher catalytic activity towards mercury oxidation than other lattice oxygen atoms. The inverse spinel structure of CuFe2O4 is favorable for O2 activation due to the Jahn-Teller effect, thereby promoting mercury oxidation. O2 molecule preferably adsorbs on iron active site and dissociates into active oxygen species. Hg0 oxidation is a three-step reaction process: Hg0 adsorption, Hg(ads) → HgO(ads), and HgO desorption. The energy barrier of mercury oxidation by chemisorbed oxygen is lower than that of mercury oxidation by lattice oxygen. The chemisorbed oxygen preserves higher reactivity towards mercury oxidation than lattice oxygen. Hg(ads) → HgO(ads) is the rate-determining step of mercury oxidation by chemisorbed oxygen because of the higher energy barrier of 116.94 kJ/mol. This work could provide the theoretical guidance for the diversified structure design of highly-efficient catalysts used for elemental mercury oxidation.

Nanosized Cu-In spinel-type sulfides as efficient sorbents for elemental mercury removal from flue gas.

Mercury emitted from human activities has received increasing attention because of its extreme toxicity, persistence and bioaccumulation. The development of highly-efficient sorbent with abundant active sites that exhibit high affinity toward Hg0 is the key challenge for elemental mercury capture at low temperature. Herein, Cu-In spinel-type sulfides were synthesized through a hydrothermal synthesis. The Hg0 removal performance of CuxIn2-xS2 sorbents was evaluated in the temperature range of 75 °C to 175 °C. The synthesized CuxIn2-xS2 sorbents showed excellent performance for Hg0 removal at low temperatures, which perfectly matches the optimal temperature of flue gas at the downstream of desulfurization system. Hg0 removal efficiency of CuxIn2-xS2 sorbents significantly improved as the Cu proportion increased. CuInS2 sorbent showed superior mercury removal performance, the mercury removal efficiency reached 99.6% at 125 °C. O2 and NO showed a slight inhibition on Hg0 capture. The coexistence of SO2 and H2O showed no obvious negative effects on Hg0 removal. The CuInS2 sorbent displayed a superior tolerance to SO2 and H2O. TPD and XPS analyses demonstrated that the adsorbed mercury mainly existed in the form of mercuric sulfides (HgS). Hg0 adsorption over CuInS2 sorbent occurred via the Mars-Maessen mechanism. In this mechanism, Hg0 vapor was physically adsorbed on CuInS2 sorbent and then converted to HgS. This study provides future potential for applying CuxIn2-xS2 sorbents to capture gaseous mercury at low temperature.

Reaction mechanism of dichloromethane oxidation on LaMnO3 perovskite.

The reaction mechanism of dichloromethane (CH2Cl2) oxidation on LaMnO3 catalyst was investigated using density functional theory calculations. The results showed that CH2Cl2 dechlorination proceeds via CH2Cl2 → CH2ClO → HCHO. The adsorbed Cl∗ and formaldehyde (HCHO) are identified as the important intermediates of CH2Cl2 dechlorination process. The dissociated Cl atoms prefer to adsorb on the surface Mn sites. Surface hydroxyl groups are not directly involved in the CH2Cl2 dechlorination process, but react with the adsorbed Cl∗ to form HCl. The energy barrier of HCl formation is lower than that of Cl2 formation, indicating that hydroxyl groups facilitate the removal of adsorbed Cl∗ species. Three possible pathways of HCHO oxidation with the assist of lattice oxygen, active oxygen atom and hydroxyl groups were investigated. HCHO catalytic oxidation contains four steps: HCHO → CHO → CO → H2O desorption → CO/CO2 desorption. Compared with the HCHO oxidation by lattice oxygen and hydroxyl groups, HCHO oxidation assisted with activated oxygen atom is more thermodynamically favorable. A complete catalytic cycle was proposed to understand the preferable reaction pathway for CH2Cl2 oxidation on LaMnO3 catalyst. The catalytic cycle includes CH2Cl2 dechlorination, HCl formation and HCHO oxidation. The microkinetic analysis indicates that there are four steps controlling the reaction cycle: CH2Cl2∗ + ∗ → CH2Cl∗ + Cl∗, CH2OCl∗ + Cl∗ → CH2O∗ + Cl∗, O2∗ + ∗ → 2O∗, and CHO2∗ + OH∗ → CO2 + H2O∗.

Charge-distribution modulation of copper ferrite spinel-type catalysts for highly efficient Hg0 oxidation.

Hg0 catalytic oxidation is an attractive approach to reduce mercury emissions from industrial activities. However, the rational design of highly active catalysts remains a significant challenge. Herein, the charge distribution modulation strategy was proposed to design novel catalysts: copper ferrite spinel-type catalysts were developed by introducing Cu2+ cations into octahedral sites to form electron-transfer environment. The synthesized catalysts with spinel-type stoichiometry showed superior catalytic performance, and achieved > 90 % Hg0 oxidation efficiency in a wide operation temperature window of 150-300 °C. The superior catalytic performance was closely associated with the mobile-electron environment of copper ferrite. Hg0 oxidation by HCl over copper ferrite followed the Eley-Rideal mechanism, in which physically adsorbed Hg0 reacted with active chlorine species. Density functional theory calculations revealed that octahedral Cu atom is the most active site of Hg0 adsorption on copper ferrite surface. Both direct oxidation pathway (Hg* → HgCl2*) and HgCl-mediated oxidation pathway (Hg* → HgCl* → HgCl2*) played important role in Hg0 oxidation over copper ferrite. HgCl2* formation was identified as the rate-limiting step of Hg0 oxidation. This work would provide a new perspective for the development of admirable catalysts with outstanding Hg0 oxidation performance.

Optimization of leaf morphology in relation to leaf water status: A theory.

The leaf economic traits such as leaf area, maximum carbon assimilation rate, and venation are all correlated and related to water availability. Furthermore, leaves are often broad and large in humid areas and narrower in arid/semiarid and hot and cold areas. We use optimization theory to explain these patterns. We have created a constrained optimization leaf model linking leaf shape to vein structure that is integrated into coupled transpiration and carbon assimilation processes. The model maximizes net leaf carbon gain (NPPleaf) over the loss of xylem water potential. Modeled relations between leaf traits are consistent with empirically observed patterns. As the results of the leaf shape-venation relation, our model further predicts that a broadleaf has overall higher NPPleaf compared to a narrowleaf. In addition, a broadleaf has a lower stomatal resistance compared to a narrowleaf under the same level of constraint. With the same leaf area, a broadleaf will have, on average, larger conduits and lower total leaf xylem resistance and thus be more efficient in water transportation but less resistant to cavitation. By linking venation structure to leaf shape and using water potential as the constraint, our model provides a physical explanation for the general pattern of the covariance of leaf traits through the safety-efficiency trade-off of leaf hydraulic design.

Catalytic reaction mechanism of formaldehyde oxidation by oxygen species over Pt/TiO2 catalyst.

Theoretical calculations based on density functional theory (DFT) were employed to uncover the molecular-level oxidation mechanism of HCHO over Pt/TiO2 surface. All the three possible reaction mechanisms including Eley-Rideal mechanism, Langmuir-Hinshelwood mechanism and Mars-Van Krevelen mechanism were deeply investigated to determine the primary channel of HCHO oxidation on Pt/TiO2 catalyst. The adsorption energies and geometries show that HCHO and O2 are chemically adsorbed on Pt and Ti sites of the Pt/TiO2 catalyst surface, respectively. The adsorption energy of O2 (-141.91 kJ/mol) is higher than that of HCHO (-122.03 kJ/mol). HCHO oxidation reaction mainly occurs through the Eley-Rideal mechanism: gaseous HCHO reacts with activated O produced from the dissociation reaction of molecular oxygen on Pt/TiO2 surface by comparing the three possible mechanisms. HCHO oxidation reaction prefers the pathway of HCHO → H2CO2 → HCO2 → CO2. In the whole HCHO oxidation reaction, the elementary reaction of HCO2 dehydrogenation presents the highest activation energy barrier of 230.45 kJ/mol. Therefore, HCO2 dehydrogenation is recognized as the rate-determining step. The proposed skeletal reaction scheme can be used to well understand the microcosmic reaction process of HCHO oxidation on Pt/TiO2 catalyst.

A complete catalytic reaction scheme for Hg0 oxidation by HCl over RuO2/TiO2 catalyst.

RuO2-based catalysts have attracted great attention in mercury emission control region due to their outstanding catalytic activity and long-term stability. Quantum chemistry calculation was performed to uncover the atomic-scale reaction mechanism of Hg0 oxidation by HCl over RuO2/TiO2 catalyst. The results indicate that Hg0 adsorption on RuO2/TiO2(110) surface is controlled by a weak chemisorption mechanism. The 5-fold coordinated surface Ru atom is identified as the active center for Hg0 adsorption. HgCl molecule serves as an intermediate connecting reactant state to product state. The weak interaction between HgCl2 and catalyst surface is favorable for product desorption. HCl activation is an O-assisted surface reaction process in which HCl is oxidized into active Cl atom for Hg0 oxidation. The heterolytic cleavage of HCl molecule occurs without noticeable activation energy barrier. Hg0 oxidation by HCl over RuO2/TiO2 catalyst proceeds through two independent reaction channels. The dominant reaction channel of Hg0 oxidation is identified as a four-step process. Finally, a complete catalytic cycle that can produce the correct stoichiometry was proposed to understand the heterogeneous reaction mechanism of Hg0 oxidation over RuO2/TiO2 catalyst. The catalytic cycle consists of HCl activation, mercury oxidation and surface reoxidation. Mercury oxidation is the rate-determining step of the catalytic cycle.