Insights into chromium removal mechanism by Ca-based sorbents from flue gas.

Chromium is a typical toxic pollution in sewage sludge incineration flue gas. Cr removal from flue gas is a challenge due to the high toxicity and valence variability of chromium. Ca-based sorbents, including CG-CaO, CA-CaO, and CCi-CaO, were developed for Cr capture by calcining calcium D-gluconate monohydrate, calcium acetate hydrate, and calcium citrate tetrahydrate, respectively. CG-CaO, CA-CaO, and CCi-CaO exhibit better Cr removal performance than traditional CaO. CA-CaO shows superior Cr adsorption ability due to the large BET surface area and pore volume. The Cr adsorption efficiency of CA-CaO is up to 94.79 % at 1000 °C. XRD and XPS results reveal that the adsorbed Cr contains Cr(III) and Cr(VI), and exists in the form of CaCr2O4 and CaCrO4. Cr adsorption on Ca-based sorbents is mainly controlled by adsorption and oxidation mechanism. The adsorption process of Cr on different Ca-based sorbents was described by four typical adsorption kinetic models. For CaO and CG-CaO, pseudo-first order model and Elovich model are suitable for the description of Cr adsorption. For CA-CaO and CCi-CaO, pseudo-second order model, Elovich model and Weber and Morris model fit well with the experimental values of Cr adsorption, suggesting that Cr adsorption on CA-CaO and CCi-CaO is controlled by a combined mechanism of chemisorption and intraparticle diffusion. The saturated adsorption capacity of CaO, CG-CaO, CA-CaO and CCi-CaO are evaluated to be 39.77, 48.98, 102.22 and 104.52 mg/g, respectively. The effects of incineration flue gas components on Cr adsorption were also explored. O2 shows no obvious influence on Cr adsorption over CA-CaO. HCl, SO2, NO and CO2 can inhibit Cr adsorption because of the competitive adsorption, and the inhibitory effect of SO2 is the strongest.

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-).

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.

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.

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.

TIAM2S as a novel regulator for serotonin level enhances brain plasticity and locomotion behavior.

TIAM2S, the short form of human T-cell lymphoma invasion and metastasis 2, can have oncogenic effects when aberrantly expressed in the liver or lungs. However, it is also abundant in healthy, non-neoplastic brain tissue, in which its primary function is still unknown. Here, we examined the neurobiological and behavioral significance of human TIAM2S using the human brain protein panels, a human NT2/D1-derived neuronal cell line model (NT2/N), and transgenic mice that overexpress human TIAM2S (TIAM2S-TG). Our data reveal that TIAM2S exists primarily in neurons of the restricted brain areas around the limbic system and in well-differentiated NT2/N cells. Functional studies revealed that TIAM2S has no guanine nucleotide exchange factor (GEF) activity and is mainly located in the nucleus. Furthermore, whole-transcriptome and enrichment analysis with total RNA sequencing revealed that TIAM2S-knockdown (TIAM2S-KD) was strongly associated with the cellular processes of the brain structural development and differentiation, serotonin-related signaling, and the diseases markers representing neurobehavioral developmental disorders. Moreover, TIAM2S-KD cells display decreased neurite outgrowth and reduced serotonin levels. Moreover, TIAM2S overexpressing TG mice show increased number and length of serotonergic fibers at early postnatal stage, results in higher serotonin levels at both the serum and brain regions, and higher neuroplasticity and hyperlocomotion in latter adulthood. Taken together, our results illustrate the non-oncogenic functions of human TIAM2S and demonstrate that TIAM2S is a novel regulator of serotonin level, brain neuroplasticity, and locomotion behavior.

Cost-Effective Manganese Ore Sorbent for Elemental Mercury Removal from Flue Gas.

Mercury capture from flue gas remains a challenge for environmental protection due to the lack of cost-effective sorbents. Natural manganese ore (NMO) was developed as a cost-effective sorbent for elemental mercury removal from flue gas. NMO sorbent showed excellent Hg0 removal efficiency (>90%) in a wide temperature window (100-250 °C) under the conditions of simulated flue gas. O2, NO, and HCl promoted Hg0 removal due to the surface reactions of Hg0 with these species. SO2 and H2O slightly inhibited Hg0 removal under the conditions of simulated flue gas. O2 addition could also weaken the inhibitory effect of SO2. NMO sorbent exhibited superior regeneration performance for Hg0 removal during ten-cycle experiments. Quantum chemistry calculations were used to identify the active components of NMO sorbent and to understand the atomic-level interaction between Hg0 and sorbent surface. Theoretical results indicated that Mn3O4 is the most active component of NMO sorbent for Hg0 removal. The atomic orbital hybridization and electrons sharing led to the stronger interaction between Hg0 and Mn3O4 surface. Finally, a chemical looping process based on NMO sorbent was proposed for the green recovery of Hg0 from flue gas. The low cost, excellent performance, superior regenerable properties suggest that the natural manganese ore is a promising sorbent for mercury removal from flue gas.