Catalytic carbon dioxide (CO2) hydrogenation to liquid fuels including methanol (CH3OH) has attracted great attention in recent years. In this work, density functional theory (DFT) calculations have been employed to study the reaction mechanisms of CO2 hydrogenation to CH3OH on Ga3Ni5(221) surfaces. The results show that all intermediates except for the O atom prefer to adsorb on Ni sites, and dissociative adsorption of hydrogen (H2) on the Ga3Ni5(221) surface is almost barrierless and highly exothermic, favoring CO2 hydrogenation. Moreover, the presence of Ga indeed enhances the dissociative adsorption of H2, and this is verified by the projected density of states (PDOS) analysis. Importantly, three possible reaction pathways based on formate (HCOO) and hydrocarboxyl (COOH) formations and reverse water gas shift (rWGS) with carbon monoxide (CO) hydrogenation have been discussed. It is found that CO2 reduction to CH3OH in these pathways prefers to occur entirely via the Langmuir–Hinshelwood (L–H) mechanism. COOH generation is the most favorable pathway because the HCOO and rWGS with CO hydrogenation pathways have high energy barriers and the resulting HCOOH intermediate in the HCOO pathway is unstable. In the COOH reaction pathway, CO2 is firstly hydrogenated to trans-COOH, followed by the formation of COH via three isomers of COHOH, its hydrogenation to trans-HCOH, and then the production of CH3OH via a CH2OH intermediate.

•We report a low cost and earth abundant PPy-modified Ni foam for the H2 evolution.•PPy-functionalized Ni foam shows a reasonable reusability.•In view of the cost, PPy-Ni foam shows a satisfactory performance comparable to Pt.•The combination of PPy and Ni formed a synergistic effect for the rapid trapping H+.Polypyrrole functionalized nickel foam is facilely prepared through the potentiostatic electrodeposition. The PPy-functionalized Ni foam functions as a hydrogen-evolution cathode in a rotating disk photocatalytic fuel cell, in which hydrogen energy and electric power are generated by consuming organic wastes. The PPy-functionalized Ni foam cathode exhibits stable catalytic activities after thirteen continuous runs. Compared with net or plate structure, the Ni foam with a unique three-dimensional reticulate structure is conducive to the electrodeposition of PPy. Compared with Pt-group electrode, PPy-coated Ni foam shows a satisfactory catalytic performance for the H2 evolution. The combination of PPy and Ni forms a synergistic effect for the rapid trapping and removal of proton from solution and the catalytic reduction of proton to hydrogen. The PPy-functionalized Ni foam could be applied in photocatalytic and photoelectrochemical generation of H2. In all, we report a low cost, high efficient and earth abundant PPy-functionalized Ni foam with a satisfactory catalytic activities comparable to Pt for the practical application of poly-generation of hydrogen and electricity.

N-doping technology is introduced to improve Co3O4’s Hg0 removal ability and anion activation ability for the first time. The adsorption tests show that N-doped Co3O4 has a higher SBET and greater Hg0 removal ability. The reaction mechanism has been carefully studied using a number of different analyses methods such as X-ray diffraction, Brunauer–Emmett–Teller, and X-ray photoelectron spectroscopy. The analysis results illustrate that N atoms have been doped into a Co3O4 matrix as anions and are thought to substitute for O atoms. Anions, such as Cl− and Br−, can be activated by N-doped Co3O4 and then oxidize Hg0. It is considered that nitrogen atoms in polycrystalline N-doped Co3O4 are responsible for the significant enhancement of Hg0 removal ability. Different NH4Cl or NH4Br adulteration values have been tested, and the results show that 50 mol % NH4Cl or 40 mol % NH4Br doped Co3O4 have the highest Hg0 removal ability. Compared with Co3O4, N-doped Co3O4 has a longer breakthrough time and better SO2 antipoisoning ability. On the basis of the above analyses, possible Hg0 oxidation mechanisms of N-doped Co3O4 are provided.

•Hg0 adsorption on low index CoMnO3 surface was predicted by DFT method.•Hg0 is adsorbed on the CoMnO3 surface with chemisorption interaction.•Hg0 has highest adsorption energy on CoMnO3 (1 0 0) surface with Hg-Mn mechanism.•The electron transfer of Hg0 has positive relationship with adsorption energy.The density functional theory (DFT) is applied to predict elemental mercury (Hg0) adsorption on CoMnO3 surface for the first time. GGA/PBE functional were selected to determine the potential Hg0 capture mechanisms. The results show that Hg0 has good affinity with CoMnO3 surfaces with chemical adsorption. The adsorption energy of Hg0-CoMnO3 (1 0 0), Hg0-CoMnO3 (1 0 1) and Hg0-CoMnO3 (1 1 0) are −85.225, −72.305 and −70.729 kJ/mol, respectively. The Hg-Mn and Hg-Co mechanisms were revealed on low index surfaces. Hg0 was oxidized to its valence state of 0.236 on Mn site in CoMnO3 (1 0 0) surface. The Hg-Co interaction mechanism occurred on Hg0-CoMnO3 (1 0 1) and Hg0-CoMnO3 (1 1 0) with 0.209e− and 0.189e− transformation, respectively. The PDOS analysis shows that Hg-Mn interaction depends on the hybridization of Hg(s- and d-orbitals) and Mn (s-, p- and d- orbitals). However, Hg-Co interaction stems from s- and d- orbitals of Hg, which only overlapping with d- and p- orbital of Co. Both the adsorption energy and electronic structure analysis indicated that CoMnO3 catalyst performed excellent in Hg0 oxidation. Exposing CoMnO3 (1 0 0) is most favorable in Hg0 control, which provides theoretical instruction on certain crystal plane synthesis in experiment.

AbstractHuangpu River is about 114.5 km from upriver Dianfeng to downriver Wusong, near the estuary of the Yangtze River. It plays a key role in supplying water for production, life, shipment and irrigation. With the industrial development, the pollution of the Huangpu River has become serious recently. The biological oxygen demand (BOD), total nitrogen (TN), total phosphorus (TP), oil, phenol and suspended solids (SS) were lower in the upstream sites than in the downstream sites, indicating pollutants being input along its course. Water quality was the worst in the Yangpu site, near the center of Shanghai City. Dissolved oxygen (DO) content was less than 2 mg/L in the site of Yangpu in July. Among relations between thirteen characteristics, relations between BOD, DO, TN, TP, NH4+-N, NO3−-N and the count of total bacteria or Escherichia coli were significant and interdependent. Inner relationships between these main characteristics in the Huangpu River were studied. High nutrient concentration led to growth of microorganisms, including E. coli. Degradation of organic matters and respiration of bacteria made oxygen concentration decreased in the water body, and DO was a key factor for nitrification-denitrification process of nitrogen. In the Yangpu site, DO was decreased to less than 3.0 mg/L with BOD higher than 7.5 mg/L in May and July. Low DO concentration will decrease nitrification rate. Nitrification need at higher DO value than other organic substrate oxidation. Consequently, river water contains low NO3−-N values with high amounts of TN and NH4+-N there. This will block the self-purification of surface water, by decreasing the rate of nitrification-denitrification transformation process in the water body.

Vertical and temporal distributions of N and P in soil solution in aquatic-terrestrial ecotone (ATE) of Taihu Lake were investigated, and the relations among N, P, ORP (oxidation reduction potential), TOC, root system biomass and microorganism were studied. As a whole, significant declines in TN, NO3−-N, DON (dissolved organic nitrogen) and TP concentration in soil solution have occurred with increase of the depth, and reached their minima at 60 cm depth, except for NH4+-N, which increased with depth. The concentration of TP increased gradually from spring to winter in the topsoil, the maximum 0.08 mg/L presented in the winter while the minimum 0.03 mg/L in spring. In the deeper layer, the concentration value of TP fluctuated little. As for the NO3−-N, its seasonal variation was significant at 20 cm depth, its concentration increased gradually from spring to autumn, and decreased markedly in winter. Vertical and temporal distribution of DON is contrary to that of NO3−-N. The results also show that the variation of N and P in the percolate between adjacent layers is obviously different. The vertical variation of TN, TP, NO3−-N, NH4+-N and DON is significant, of which the variation coefficient of NO3−-N along the depth reaches 100.23%, the highest; while the variation coefficient of DON is 41.14%, the smallest. The results of correlation analysis show that the concentration of nitrogen and phosphorus correlate significantly with TOC, ORP, root biomass and counts of nitrifying bacteria. Most nutrients altered much from 20 to 40 cm along the depth. However, DON changed more between 60 and 80 cm. Results show that soil of 0–60 cm depth is active rhizoplane, with strong capability to remove the nitrogen and phosphorus in ATE. It may suggest that there exists the optimum ecological efficiency in the depth of above 60 cm in reed wetland. This will be very significant for ecological restoration and reestablishment.

Catalytic carbon dioxide (CO2) hydrogenation to liquid fuels including methanol (CH3OH) has attracted great attention in recent years. In this work, density functional theory (DFT) calculations have been employed to study the reaction mechanisms of CO2 hydrogenation to CH3OH on Ga3Ni5(221) surfaces. The results show that all intermediates except for the O atom prefer to adsorb on Ni sites, and dissociative adsorption of hydrogen (H2) on the Ga3Ni5(221) surface is almost barrierless and highly exothermic, favoring CO2 hydrogenation. Moreover, the presence of Ga indeed enhances the dissociative adsorption of H2, and this is verified by the projected density of states (PDOS) analysis. Importantly, three possible reaction pathways based on formate (HCOO) and hydrocarboxyl (COOH) formations and reverse water gas shift (rWGS) with carbon monoxide (CO) hydrogenation have been discussed. It is found that CO2 reduction to CH3OH in these pathways prefers to occur entirely via the Langmuir–Hinshelwood (L–H) mechanism. COOH generation is the most favorable pathway because the HCOO and rWGS with CO hydrogenation pathways have high energy barriers and the resulting HCOOH intermediate in the HCOO pathway is unstable. In the COOH reaction pathway, CO2 is firstly hydrogenated to trans-COOH, followed by the formation of COH via three isomers of COHOH, its hydrogenation to trans-HCOH, and then the production of CH3OH via a CH2OH intermediate.