Fe-zeolites for the adsorption and oxidative degradation of nitroaromatic compounds in water.

Nitroaromatic compounds (NACs) are prominent explosives. In this context, these toxic substances were released into the environment and cause long-lasting groundwater contamination. In preparation of a possible in-situ remediation, colloidal Fe-zeolites were investigated for their capabilities as adsorbents and oxidation catalysts. It was shown that the Fe-zeolites FeBEA35 and FeFAU55 are potent inorganic adsorbents for NACs and simultaneously capable of activating H2O2 as Fenton-like oxidation catalysts. Adsorption isotherms of 15 NACs on both zeolites were measured to evaluate the option of coupling adsorptive contaminant enrichment with oxidative degradation. The faujasite-type zeolite FeFAU55 showed a distinct S-type adsorption behaviour and reached significantly higher NAC loadings of > 20 wt%. For FeBEA35, L-type adsorption isotherms and maximum loadings qmax of about 4 wt% were obtained. Degradation of all NACs, monitored by nitrate formation, was observed. Apparent rate constants of the NACs with hydroxyl radicals in a homogeneous, stoichiometric Fenton reaction were related to the heterogeneous system to examine the role of adsorption on the oxidative degradation. Beneficial influence of the adsorption on the oxidation rates was identified. The results of this work open up promising prospects for future application of Fe-zeolites for the in-situ remediation of NAC-contaminated groundwater.

Electrochemical CO2 reduction - The macroscopic world of electrode design, reactor concepts & economic aspects.

For the efficient electrochemical conversion of CO2 into valuable chemical feedstocks, a well-coordinated interaction of all electrolyzer compartments is required. In addition to the catalyst, whose role is described in detail in the part "Electrochemical CO2 Reduction toward Multicarbon Alcohols - The Microscopic World of Catalysts & Process Conditions" of this divided review, the general cell setups, design and manufacture of the electrodes, membranes used, and process parameters must be optimally matched. The authors' goal is to provide a comprehensive review of the current literature on how these aspects affect the overall performance of CO2 electrolysis. To be economically competitive as an overall process, the framework conditions, i.e., CO2 supply and reaction product treatment must also be considered. If the key indicators for current density, selectivity, cell voltage, and lifetime of a CO2 electrolyzer mentioned in the techno-economic consideration of this review are met, electrochemical CO2 reduction can make a valuable contribution to the creation of closed carbon cycles and to a sustainable energy economy.

Electrochemical CO2 reduction toward multicarbon alcohols - The microscopic world of catalysts & process conditions.

Tackling climate change is one of the undoubtedly most important challenges at the present time. This review deals mainly with the chemical aspects of the current status for converting the greenhouse gas CO2 via electrochemical CO2 reduction reaction (CO2RR) to multicarbon alcohols as valuable products. Feasible reaction routes are presented, as well as catalyst synthesis methods such as electrodeposition, precipitation, or sputtering. In addition, a comprehensive overview of the currently achievable selectivities for multicarbon alcohols in CO2RR is given. It is also outlined to what extent, for example, modifications of the catalyst surfaces or the use of bifunctional compounds the product distribution is shifted. In addition, the influence of varying electrolyte, temperature, and pressure is described and discussed.

In-situ treatment of herbicide-contaminated groundwater-Feasibility study for the cases atrazine and bromacil using two novel nanoremediation-type materials.

Two injectable reactive and sorption-active particle types were evaluated for their applicability in permeable reaction zones for in-situ removal of herbicides ("nanoremediation"). As model substances, atrazine and bromacil were used, two herbicides frequently occurring in groundwater. In order to provide recommendations for best use, particle performance was assessed regarding herbicide degradation and detoxification. For chemical reduction, Carbo-Iron® was studied, a composite material consisting of zerovalent iron and colloidal activated carbon. Carbo-Iron reduced bromacil with increased activity compared to nanoscale zerovalent iron (nZVI). The sole reaction product, 3-sec-butyl-6-methyluracil, showed 500-fold increase in half-maximal-effect concentration (EC50) towards the chlorophyte Scendesmus vacuolatus compared to the parent compound. The detoxification based on dehalogenation confirmed the dependency of the specific mode-of-action on the carbon-halide bond. For atrazine, neither nZVI nor Carbo-Iron showed significant degradation under the conditions applied. As novel subsurface treatment option, Trap-Ox® zeolite FeBEA35 was studied for generation of in-situ permeable oxidation barriers. Both adsorbed atrazine and bromacil underwent fast unselective oxidation. The transformation products of the Fenton-like reaction were identified, and oxidation pathways derived. For atrazine, a 300-fold increase in EC50 for S. vacuolatus was found over the duration of the reaction, and a loss of phytotoxicity to non-detectable levels for bromacil.