Sn-based film electrodeposited on Ag foil for selective electrochemical CO2 reduction to CO.

Electrochemical CO2 reduction (ECR) to valuable chemicals and fuels using renewable energy is a promising way to reduce carbon emission. Herein, Sn-based films were electrodeposited on Ag foil surfaces (Sn/Ag-y) for selective ECR to CO, where y represented the concentration of SnCl2 in the electrodeposition bath. The Sn/Ag-20 electrode achieved a high CO faradaic efficiency of 96.0% with a current density of 69.3 mA cm-2. The enhanced catalytic performance could be attributed to appropriate superficial properties, large electrochemical active surface areas, low charge transfer resistance, efficient stabilization capacity of the CO2˙- intermediates, and suitable combination with electrolytes.

Crystalline CdS/Amorphous Cd(OH)2 Composite for Electrochemical CO2 Reduction to CO in a Wide Potential Window.

Electrochemical CO2 reduction is a promising method for converting atmospheric CO2 into valuable low-carbon chemicals. In this study, a crystalline cadmium sulfide/amorphous cadmium hydroxide composite was successfully deposited on the carbon paper substrate surface by in-situ chemical bath deposition (named as c-CdS/a-Cd(OH)2/CP electrodes) for the efficient electrochemical CO2 reduction to produce CO. The c-CdS/a-Cd(OH)2/CP electrode exhibited high CO Faradaic efficiencies (>90 %) under a wide potential window of 1.0 V, with the highest value reaching ~100 % at the applied potential ranging from -2.16 V to -2.46 V vs. ferrocene/ferrocenium (Fc/Fc+), superior to the crystalline counterpart c-CdS/CP and c-CdS/c-Cd(OH)2@CP electrodes. Meanwhile, the CO partial current density reached up to 154.7 mA cm-2 at -2.76 V vs. Fc/Fc+ on the c-CdS/a-Cd(OH)2/CP electrode. The excellent performance of this electrode was mainly ascribed to its special three-dimensional structure and the introduction of a-Cd(OH)2. These structures could provide more active sites, accelerate the charge transfer, and enhance adsorption of *COOH intermediates, thereby improving the CO selectivity. Moreover, the electrolytes consisting of 1-butyl-3-methylimidazolium tetrafluoroborate and acetonitrile also enhanced the reaction kinetics of electrochemical CO2 reduction to CO.

Cd/Cd(OH)2 Nanosheets Enhancing the Electrocatalytic Activity of CO2 Reduction to CO.

Electric-driven conversion of carbon dioxide (CO2 ) to carbon monoxide (CO) under mild reaction conditions offers a promising approach to mitigate the greenhouse effect and the energy crisis. Surface engineering is believed to be one of the prospective methods for enhancing the electrocatalytic activity of CO2 reduction. Herein, hydroxyl (OH) groups were successfully introduced to cadmium nanosheets to form cadmium and cadmium hydroxide nanocomposites (i. e. Cd/Cd(OH)2 nanosheets) via a facile two-step method. The as-prepared Cd/Cd(OH)2 /CP (CP indicates carbon paper) electrode displays excellent electrocatalytic activity for CO2 reduction to produce CO. The Faradaic efficiency of CO reaches 98.3 % and the current density achieves 23.8 mA cm-2 at -2.0 V vs. Ag/Ag+ in a CO2 -saturated 30 wt% 1-butyl-3-methylimidazole hexafluorophosphate ([Bmim]PF6 )-65 wt% acetonitrile (CH3 CN)-5 wt% water (H2 O) electrolyte. And the CO partial current density can reach up to 71.6 mA cm-2 with the CO Faradaic efficiency of more than 85 % at -2.3 V vs. Ag/Ag+ , which stands out against Cd/CP, Cd(OH)2 /CP, and Cd/CdO/CP electrodes. The excellent electrocatalytic performance of the Cd/Cd(OH)2 /CP electrode can be attributed to its unique structural properties, suitable OH groups, perfect interaction with electrolyte, abundant active sites and fast electron transfer rate.

Degradation of anthraquinone dye reactive blue 19 using persulfate activated with Fe/Mn modified biochar: Radical/non-radical mechanisms and fixed-bed reactor study.

In this study, a heterogeneous activator was prepared via the Fe/Mn modification of sludge-derived biochar (Fe/MnBC) to achieve high-efficiency activation of persulfate (PS) for reactive blue 19 (RB19) degradation. The morphologies and chemical states of Fe/MnBC were examined by various characterizations. A comprehensive assessment was conducted to reveal the effects of biochar preparation conditions and system reaction conditions. According to the results of scavenger quenching experiments and electron paramagnetic resonance (EPR) testing, the mechanisms of Fe/MnBC combined PS system on RB19 degradation were proposed, including radical and non-radical mechanisms. The formation and involvement of sulfate radical (SO4·-), hydroxyl radical (OH·), and singlet oxygen (1O2) were proved in this system, and Fe(IV)/Mn(VII) was also speculated to participate in the non-radical degradation process. These findings give a new insight into the mechanisms of PS activated by metal-biochar composite. Besides, fixed-bed reactor (FBR) experiments indicated that the Fe/MnBC has considerable PS activation potential for dyes removal. The degradation process was further modeled by the central composite design (CCD-RSM) and artificial neural networks (ANN) methods. The statistical metrics and prediction indicated that the prediction results of ANN model were better than CCD-RSM model, and the ANN model could perfectly predict the reaction process of Fe/MnBC FBR for engineering applications.

Removal mechanisms of Cr(VI) and Cr(III) by biochar supported nanosized zero-valent iron: Synergy of adsorption, reduction and transformation.

In this study, sludge-derived biochar was prepared and utilized to support nano-zero-valent iron (NZVI-SDBC) for removing Cr(VI) and Cr(III) from aqueous solution with the aim of investigating their removal and transformation. Under the conditions of initial pH of 4, dosage of 1 g/L, temperature of 25 °C, and rotational speed of 160 rpm, 64.13% Cr species could be removed by NZVI-SDBC from Cr(VI) solution and 28.89% from Cr(III) solution. Coexisting ions experiments showed that Cu(II) and humic acids dramatically affected the removal of Cr(VI) and Cr(III), while the effect of Na(I) and Ca(II) was almost negligible. Based on this, through the coexistence and pre-loaded Cr(III) experiments, the conversion from Cr(VI) to Cr(III) was demonstrated to enhance the further attraction on Cr(VI) and promote the subsequent removal of Cr(VI). The SDBC of NZVI-SDBC could serve as electron shuttle mediator to facilitate the electron transfer between adsorbed Cr(VI) and NZVI for ortho-reduction. The transformation and removal mechanisms were further discussed by various characterizations. The kinetics of Cr(VI) removal suggested that the removal process of Cr(VI) could be divided into three phases dominated by different mechanisms (adsorption, direct/ortho reduction, electrostatic attraction), in which Cr(VI) and Cr(III) showed different behaviors of interaction. The removal of Cr(III) mainly depended on sufficient adsorption sites and the direct complexation with Fe(II). Finally, the reusability of NZVI-SDBC was assessed by adsorption/desorption recycling test. These results provided new insights into the removal and transformation mechanisms of Cr(VI) and Cr(III) by biochar-based nanocomposites.

Removal of hexavalent chromium by biochar supported nZVI composite: Batch and fixed-bed column evaluations, mechanisms, and secondary contamination prevention.

Conversion of carcinogenic Cr(VI) to less toxic Cr(III) has long been regarded as the most efficient and effective method to remediate Cr(VI)-contaminated water. However, the widely used reducing agents such as nano zero-valent iron (nZVI) and its derivatives often have low stability and their applications in water treatment may introduce secondary contaminations. To shed light on these, nZVI was loaded on sludge derived biochar to produce nZVI-BC composite for Cr(VI) removal. Batch experiments showed that Cr(VI) adsorption on nZVI-BC was endothermic and highly pH dependent. The adsorption kinetic and isotherm data were described by the pseudo second-order kinetic model and the Langmuir isotherm model, respectively. The removal of Cr(VI) by nZVI-BC was mainly through reduction-adsorption. After the experiment, nZVI-BC was transformed into a stable magnetic adsorbent that can be magnetically separated from aqueous phase during first circle application. In fix-bed columns, nZVI-BC also effectively removed Cr(VI) under various operation conditions and the Thomas and Yoon-Nelson models described the experimental breakthrough curves well. The post-adsorption nZVI-BC was re-pyrolyzed, which stabilized and reduced the bioavailability of Cr in the biochar. Re-pyrolysis thus can be used as an effective technology to reduce the environmental risks of post-adsorbent biochar for safe disposal.

Concurrent reduction-adsorption of chromium using m-phenylenediamine-modified magnetic chitosan: kinetics, isotherm, and mechanism.

Magnetic chitosan particles (MCS) were chemically grafted by m-phenylenediamine (mPD) forming a distinctive shell layer with abundant nitrogenous functional groups and used as an adsorbent for the effective removal of Cr(VI) from aqueous solution. By interaction among functional groups in the facile oxidative polymerization process, the grafting of mPD and its polymers on MCS surface was innovatively realized. Through Fourier-transformed infrared spectroscopy, energy dispersive spectrometer, X-ray photoelectron spectroscopy, etc., the chemical properties of MCS before and after modification were characterized and the concurrent reduction-adsorption mechanism in Cr(VI) adsorption by mPD-MCS was carefully analyzed. The maximal Cr(VI) removal performance of mPD-MCS reached 227.27 mg/g, which was significantly better than that of the original MCS. The analysis indicated that Cr(VI) could be efficiently reduced to Cr(III) and the removal of Cr(VI) and Cr(III) was through adsorption and chelation simultaneously by mPD-MCS. Results also indicated that the concurrent reduction-adsorption was enhanced by protonation of nitrogenous functional groups under low pH. The obtained results suggest that mPD-MCS has a good potential in removal and detoxication of Cr(VI) from aqueous solutions.

Investigating the sorption behavior of cadmium from aqueous solution by potassium permanganate-modified biochar: quantify mechanism and evaluate the modification method.

In this work, a KMnO4-modified-biochar-based composite material with manganese oxide produced at 600 °C was fabricated to investigate the sorption mechanism of Cd(II) and to comprehensively evaluate the effect of the modification on biochar properties. Cd(II) adsorption mechanisms were mainly controlled by interaction with minerals, complexation with oxygen-containing functional groups, and cation-π interaction. The sorption capacity was significantly reduced after a deash treatment of biochar, almost shrunk by 3 and 3.5 times for pristine biochar (PBC) and modified biochar (MBC). For deashed PBC, oxygen-containing functional groups were the main contributor toward Cd(II) adsorption while interaction with minerals was significantly compromised and became negligible. The sorption capacity was also apparently decreased after the deash treatment of MBC; however, for deashed MBC, interaction with minerals still was the main contributor to the sorption ability, which could be attributed to the mechanism of interaction of Cd(II) with loaded MnOx on biochar. Cation-π interaction in MBC was notably enhanced compared to PBC due to the oxidation of KMnO4 on biomass. Also, sorption performance by oxygen-containing functional groups was also enhanced. Hence, the modification by KMnO4 has a significant effect on the Cd(II) sorption performance of biochar.