Highly Active and Water-Resistant Cu-Doped OMS-2 Catalysts for CO Oxidation: The Importance of the OMS-2 Synthesis Method and Cu Doping.

Porous cryptomelane-type Mn oxide (OMS-2) has an outstanding redox property, making it a highly desirable substitute for noble metal catalysts for CO oxidation, but its catalytic activity still needs to be improved, especially in the presence of water. Given the strong structure-performance correlation of OMS-2 for oxidation reactions, herein, OMS-2 is synthesized by solid state (OMS-2S), reflux (OMS-2R), and hydrothermal (OMS-2H) methods, aiming to improve its CO oxidation performance through manipulating synthesis parameters to tailor its particle size, morphology, and crystallinity. Characterization shows that OMS-2S has the highest CO oxidation activity in the absence of water due to its low crystallinity, high specific surface area, large oxygen vacancy content, and good redox property, but the presence of water can greatly reduce its CO oxidation activity. Doping Cu into an OMS-2 can not only improve its CO oxidation activity but also greatly improve its water tolerance. The Cu-doped OMS-2S catalyst with ∼4 wt % Cu can achieve a T90 of 49 °C (1% CO/10% O2/N2 and WHSV = 60,000 mL·g-1·h-1), ranking among the lowest reported T90 values for Mn oxide-based CO oxidation catalysts, and it can maintain nearly 100% CO conversion in the presence of 5 vol % water for over 50 h. In situ DRIFTs characterization indicates that the good water resistance of Cu-doped OMS-2S can be attributed to the significantly suppressed surface hydroxyl group generation because of Cu doping. This work demonstrates the importance of the synthesis method and Cu doping in determining the CO oxidation activity and water resistance of OMS-2 and will provide guidance for synthesizing highly active and water-resistant CO oxidation catalysts.

Removal of Metal Ions in Phosphoric Acid by Electro-Electrodialysis with Cross-Linked Anion-Exchange Membranes.

There are numerous metallic impurities in wet phosphoric acid, which causes striking negative effects on industrial phosphoric acid production. In this study, the purification behavior of metallic impurities (Fe, Mg, Ca) from a wet phosphoric acid solution employing the electro-electrodialysis (EED) technology was investigated. The cross-linked polysulfone anion-exchange membranes (AEMs) for EED were prepared using N,N,N',N'-tetramethyl-1,6-hexanediamine (TMHDA) to achieve simultaneous cross-linking and quaternization without any cross-linkers or catalysts. The performance of the resulting membranes can be determined using quaternization reagents. When the molar ratio of trimethylamine/TMHDA/chloromethylated polysulfone is 3:1:1, the cross-linked membrane CQAPSU-3-1 exhibits lower water swelling and membrane area resistance than the non-cross-linked membrane. The low membrane area resistance of CQAPSU-3-1 with long alkyl chains is obtained due to the hydrophilic-hydrophobic microphase separation structure formed by TMHDA. EED experiments with different initial phosphoric acid concentrations of 0.52 and 1.07 M were conducted to evaluate the phosphoric acid purification of different AEMs. The results show that the EED experiments were more suitable for the purification of wet phosphoric acid solution at low concentrations. It was found that the phosphoric acid concentration in the anode compartment could be increased from 0.52 to 1.04 M. Through optimization, with an initial acid concentration of 0.52 M, CQAPSU-3-1 exhibits an enhanced metallic impurity removal ratio of higher than 72.0%, the current efficiency of more than 90%, and energy consumption of 0.48 kWh/kg. Therefore, CQAPSU-3-1 exhibits much higher purification efficiency than other membranes at a low initial phosphoric acid concentration, suggesting its potential in phosphoric acid purification application.

Multi-role graphitic carbon nitride-derived highly porous iron/nitrogen co-doped carbon nanosheets for highly efficient oxygen reduction catalyst.

Pyrolyzing precursors containing iron, nitrogen and carbon elements is a commonly used process for synthesizing FeNC catalysts for oxygen reduction reaction (ORR). Generally, aggregation of iron-based species is prone to occur because of a lack of chemical bonds between iron-based species and carbon matrix and synthesizing highly porous FeNC catalysts is difficult because carbon skeleton is prone to collapse during pyrolysis. Herein, highly porous FeNC catalysts with fine iron-based species are synthesized by selecting glucose as carbon source, FeCl3 as iron source, and urea-derived g-C3N4 as nitrogen source, iron anchoring and stabilizing species, and pore-forming template. The multi-role g-C3N4-derived catalyst synthesized at 1100 °C (FeNC1100) has fine iron-based species, large specific surface area (737 m2 g-1), and extremely high pore volume (2.66 cm3 g-1). Accordingly, FeNC1100 shows a larger half-wave potential (E1/2 = 0.894 V), a higher stability (ΔE1/2 = 6 mV) after 10,000 potential cycles in alkaline media, and a higher peak power density (P = 152 mW cm-2) when employed as ORR catalyst of zinc-air battery, which are all superior to those of the commercial Pt/C catalyst (E1/2 = 0.864 V, ΔE1/2 = 30 mV, P = 134 mW cm-2). The present work brings a new method for synthesizing highly porous FeNC catalysts decorated with fine active sites for ORR.

Electrogenerated alkaline hydrogen peroxide for rice straw pretreatment to enhance enzymatic hydrolysis.

In this work, alkaline hydrogen peroxide (AHP) solution with 1 wt% H2O2 was electrogenerated by oxygen reduction with a current efficiency of 75.2% in a home-made gas diffusion electrode-based electrochemical cell and used for rice straw pretreatment (0.1 g H2O2/g rice straw, 10% (w/v) biomass loading, 55 °C, 2 h). Results showed that the AHP pretreatment removed 97.56% of the initial lignin, 85.75% of the initial hemicellulose, and only 0.56% of the initial cellulose, and the specific surface area and porosity of the AHP pretreated rice straw (AHP-RS) were greatly increased. Saccharification results showed that after 48 h of enzymatic hydrolysis AHP-RS achieved a 3.2-fold increase in reducing sugar concentration compared to the untreated rice straw (5.81 and 1.81 g L-1), highlighting the potential use of this AHP solution for lignocellulose pretreatment.

Effect of iron salt type and dosing mode on Fenton-based pretreatment of rice straw for enzymatic hydrolysis.

Fenton-based processes with four different iron salts in two different dosing modes were used to pretreat rice straw (RS) samples to increase their enzymatic digestibility. The composition analysis shows that the RS sample pretreated by the dosing mode of iron salt adding into H2O2 has a much lower hemicellulose content than that pretreated by the dosing mode of H2O2 adding into iron salt, and the RS sample pretreated by the chloride salt-based Fenton process has a much lower lignin content and a slightly lower hemicellulose content than that pretreated by the sulphate salt-based Fenton process. The higher concentration of reducing sugar observed on the RS sample with lower lignin and hemicellulose contents justifies that the Fenton-based process could enhance the enzymic hydrolysis of RS by removing hemicellulose and lignin and increasing its accessibility to cellulase. FeCl3·6H2O adding into H2O2 is the most efficient Fenton-based process for RS pretreatment.

Ultrasound-assisted alkaline pretreatment for enhancing the enzymatic hydrolysis of rice straw by using the heat energy dissipated from ultrasonication.

Rice straw samples were exposed to ultrasound-assisted alkaline (NaOH) pretreatment by using the heat energy dissipated from ultrasonication to increase their enzymatic digestibility for saccharification. The characterization shows that the pretreatment could selectively remove lignin and hemicellulose without degrading cellulose, and increase porosity and surface area of rice straw. The porosity, surface area and cellulose content of rice straw increased with the increasing concentration of NaOH used. The rice straw sample pretreated by using the heat energy dissipated from ultrasonication has a higher surface area and a lower crystallinity index value than that pretreated by using the external source of heating, and the amount of reducing sugar released from the former sample at 48h of enzymatic saccharification, which is about 3.5 times as large as that from the untreated rice straw sample (2.91vs. 0.85gL-1), is slightly larger than that from the latter sample (2.91vs. 2.73gL-1). The ultrasound-assisted alkaline pretreatment by using the heat energy dissipated from ultrasonication was proved to be a reliable and effective method for rice straw pretreatment.

Pretreatment of rice straw by ultrasound-assisted Fenton process.

Fenton's reagent, ultrasound, and the combination of Fenton's reagent and ultrasound were used to pretreat rice straw (RS) to increase its enzymatic digestibility for saccharification. The characterization shows that compared with ultrasound, Fenton's reagent pretreatment was more efficient in increasing the specific surface area and decreasing the degree of polymerization (DP) of RS. The enzymatic hydrolysis results showed that the RS pretreated by ultrasound-assisted Fenton's reagent (U/F-RS), which exhibited the largest specific surface area and the lowest DP value, had the highest enzymatic activity, and the amount of reducing sugar released from U/F-RS at 48h of enzymatic saccharification is about 4 times as large as that from raw RS and 1.5 times as large as that from Fenton's reagent pretreated RS. The ultrasound-assisted Fenton process provides a reliable and effective method for RS pretreatment.

Depolymerization of microcrystalline cellulose by the combination of ultrasound and Fenton reagent.

In this study, the combined use of Fenton reagent and ultrasound to the pretreatment of microcrystalline cellulose (MCC) for subsequent enzyme hydrolysis was investigated. The morphological analysis showed that the aspect ratio of MCC was greatly reduced after pretreatment. The X-ray diffraction (XRD) and degree of polymerization (DP) analyses showed that Fenton reagent was more efficient in decreasing the crystallinity of MCC while ultrasound was more efficient in decreasing the DP of MCC. The combination of Fenton reaction and ultrasound, which produced the lowest crystallinity (84.8 ± 0.2%) and DP (124.7 ± 0.6) of MCC and the highest yield of reducing sugar (22.9 ± 0.3 g/100 g), provides a promising pretreatment process for MCC depolymerization.

[Separation and purification of total flavonids of Astragalus membranaceus with ethanol/phosphate aqueous two-phase system].

OBJECTIVE: To study separation and purification of flavonids with ethanol/phosphate aqueous two-phase system. METHOD: The diversity of phase separation ability and the distribution of target products in various systems were taken as indicators to analyze aqueous two-phase extraction systems and phase diagrams formed by ethanol and some common salts, screen out EtOH/ K2HPO4 system as the optimla system for extracting total flavonids, and study the impact of proportion of components in EtOH/K2 HPO4 system on the partition coefficient and phase ratio of flavonids. RESULT AND CONCLUSION: The EtOH/K2 HPO4 system with omegaEtOH 36.05% and omegaKHPO4 18.20% has been proved as the optimal conditions for separating and purifying total flavonoids of Astragalus (TFA). Under this optimal condition, the partition coefficient and the extraction yield of TFA reached 10.33 and 96.6%, respectively. After extraction, the contents of A. membranaceus saponins and A. membranaceus polysaccharides in top and bottom phases were determined at the same time, showing that A. membranaceus saponins in the removal rate reached 92.01%, and A. membranaceus polysaccharides were totally concentrated in bottom water phase, indicating a removal rate of 100%. Therefore, this is beneficial to separate and purify total flavonids from A. membranaceus crude extracts.