Surface Reconstruction of La2CuO4 during the Electrochemical Reduction of Carbon Dioxide to Ethylene and Its Benefits for Enhanced Performance.

Electrochemical reduction (ECR) of CO2 to C2H4 has a potential key role in realizing the carbon neutral future, which ultimately relies on the availability of an efficient electrocatalyst that can exhibit a high Faradaic efficiency (FE) for C2H4 production and robust, long-term operational stability. Here, for the first time, we report that upon applying reductive potential and electrolyte to the benchmark La2CuO4 catalyst, surface reconstruction occurred, i.e., the appearance of a distinctive phase evolution process over time, which was successfully monitored using ex situ powder XRD and operando Mott-Schottky (M-S) measurements of La2CuO4 samples that were soaked into the electrolyte and subjected to CO2-ECR for different durations. At the end of such a reconstruction process, an outermost layer consisting of lanthanum carbonate, a thin outer layer made of an amorphous Cu+ material formed over the core bulk La2CuO4, as confirmed by various characterization techniques, which resulted in the redistribution of interfacial electrons and subsequent formation of electron-rich and electron-deficient interfaces. This contributed to the enhancement in FE for C2H4, reaching as much as 58.7%. Such surface reconstruction-induced electronic structure tuning gives new explanations for the superior catalytic performance of La2CuO4 perovskite and also provides a new pathway to advance CO2-ECR technology.

Physicochemical characteristics of grease-trap wastewater with different potential mechanisms of FOG solid formation, separation, and accumulation inside grease traps.

This work investigates the physicochemical characteristics of grease-trap wastewater discharged from a large community market. It proposes potential mechanisms of fat, oil, and grease (FOG) solid formation, separation, and accumulation inside grease traps. Sixty-four samples, i.e., the floated scum, suspended solid-liquid wastewater, and settled sludge, were collected from the grease-trap inlet and outlet chambers. A lower pH of 5-6 at 25-29 °C inside the grease trap than those reported under the sewer conditions (pH 6-7) was revealed. A significant difference in solid and dissolved constituents was also discovered between the inlet and outlet chambers, indicating that the baffle wall could affect the separation mechanism. The sludge samples had 1.5 times higher total solids (TS) than the scum samples, i.e., 0.225 vs. 0.149 g g-1 TS, revealing that the sludge amount impacted more significantly the grease trap capacity and operation and maintenance. In contrast, the scum samples had 1.4 times higher volatile solids (VS) than the sludge samples, i.e., 0.134 vs. 0.096 g g-1 VS, matching with the 64.2 vs. 29.7% of carbon content from CHN analysis. About 2/3 of the free fatty acids (FFAs) with palmitic acids were the primary saturated FFAs, while the remaining 1/3 of unsaturated FFAs were found in the solid and liquid samples. Although up to 0.511 g g-1 FOG can be extracted from the scum samples, none from the sludge samples. More diverse minerals/metals other than Na, Cl, and Ca were found in the sludge samples than in the scum samples. Grease-trap FOG solids and open drain samples exhibited similar physicochemical properties to those reported in the literature. Four potential mechanisms (crystallization, emulsification, saponification, and baffling) were presented. This work offers insights into the physicochemical properties of grease-trap wastewater that can help explore its FOG solid formation, separation, and accumulation mechanisms inside a grease trap.

Fabricating an adsorbent and micro-nano bubble catalyst through confining maghemite in the ß cage of NaY zeolite.

This work reports the ion exchange fabrication of maghemite (γ-Fe2O3) modified NaY zeolite (Fe2O3@Y) with bifunction of adsorption and catalysis. The Fe3+ successfully replaced the Na+ in the ß cage of zeolite in the ion exchange process and coordinated with framework oxygens to form magnetic γ-Fe2O3. Therefore, most of the γ-Fe2O3 particles were confined in the ß cages, which resulted in the high dispersal and stability of the catalyst. The Fe2O3@Y could remove methylene blue (MB) model pollutants up to 59.02 and 61.47% through the adsorption and catalysis process, respectively. The hydrogen bond between the OH- ions around the Fe2O3@Y surface and the N and O presented in the MB molecules enabled the chemical adsorption to MB, which accorded with the pseudo-second-order kinetic model. Further, the H+ existed in the solution and the ß cage of zeolite promoted the collapse of micro-nano bubbles (MNBs). Then, the γ-Fe2O3 catalyst would be activated by high temperature and oxidated OH- to produce hydroxyl radicals for pollutant degradation. Thus, pollutant removal was attributed to the combined effects of adsorption and catalysis in the Fe2O3@Y + MNB system. In this work, the Fe2O3@Y was demonstrated as a potentially magnetic adsorbent or MNB catalyst for wastewater treatment.

Revealing the enhanced photoelectrochemical water oxidation activity of Fe-based metal-organic polymer-modified BiVO4 photoanode.

Metal-organic polymers (MOPs) can enhance the photoelectrochemical (PEC) water oxidation performance of BiVO4 photoanodes, but their PEC mechanisms have yet to be comprehended. In this work, we constructed an active and stable composite photoelectrode by overlaying a uniform MOP on the BiVO4 surface using Fe2+ as the metal ions and 2,5-dihydroxyterephthalic acid (DHTA) as ligand. Such modification on the BiVO4 surface yielded a core-shell structure that could effectively enhance the PEC water oxidation activity of the BiVO4 photoanode. Our intensity-modulated photocurrent spectroscopy analysis revealed that the MOP overlayer could concurrently reduce the surface charge recombination rate constant (ksr) and enhance the charge transfer rate constant (ktr), thus accelerating water oxidation activity. These phenomena can be ascribed to the passivation of the surface that inhibits the recombination of the charge carrier and the MOP catalytic layer that improves the hole transfer. Our rate law analysis also demonstrated that the MOP coverage shifted the reaction order of the BiVO4 photoanode from the third-order to the first-order, resulting in a more favorable rate-determining step where only one hole accumulation is required to overcome water oxidation. This work provides new insights into the reaction mechanism of MOP-modified semiconductor photoanodes.

Construction of Cu7 S4 @CuCo2 O4 Yolk-Shell Microspheres Composite and Elucidation of Its Enhanced Photocatalytic Activity, Mechanism, and Pathway for Carbamazepine Degradation.

Water pollution caused by the massive use of medicines has caused significant environmental problems. This work first reports the synthesis and characterization of the Cu7 S4 /CuCo2 O4 (CS/CCO) yolk-shell microspheres via hydrothermal and annealing methods, and then investigates their photocatalytic performance in removing organic water pollutants. The 10-CS/CCO composite with yolk-shell microspheres exhibits the highest photodegradation rate of carbamazepine (CBZ), reaching 96.3% within 2 h. The 10-CS/CCO also demonstrates more than two times higher photodegradation rates than the pure (Cu7 S4 ) CS and (CuCo2 O4 ) CCO. This outstanding photocatalytic performance can be attributed to the unique yolk-shell structure and the Z-scheme charge transfer pathway, reducing multiple reflections of the acting light. These factors enhance the light absorption efficiency and efficiently transfer photoexcited charge carriers. In-depth, photocatalytic degradation pathways of CBZ are systematically evaluated via the identification of degradation intermediates with Fukui index calculation. The insights gained from this work can serve as a guideline for developing low-cost and efficient Z-scheme photocatalyst composites with the yolk-shell structure.

Novel scheme towards interfacial charge transfer between ZnIn2S4 and BiOBr for efficient photocatalytic removal of organics and chromium (VI) from water.

Construction of Z-scheme heterostructure is an effective strategy to enhance the charge carriers' separation. However, successfully achieving this on the defect heterojunction to improve the photocatalytic activity remains challenging. This work successfully obtained sulfur vacancy in the ZnIn2S4/BiOBr (SZIS/BOB) heterojunction composites with S-O covalent bonding using a hydrothermal method. As a result, they exhibited superior photocatalytic and stability performance. The optimized SZIS/BOB-10 exhibited excellent rhodamine B degradation (95.2%) and chromium (VI) reduction (97.8%) within 100 min under visible light. The enhanced composites with S-vacancies, S-O bond, and internal electric field induced the Z-scheme charge transfer mechanism. We had verified this mechanism based on the surface photovoltage spectra, electron spin response spectra, and density functional theory calculations. This work not only provides valuable insights into designing photocatalysts with a direct Z scheme heterostructure but also delineates a promising strategy for developing efficient photocatalysts to degrade organic pollutants.