Yanhui Zheng

Volatile methyl siloxanes (VMS), which are considered to be the most troublesome impurities in current biogas-cleaning technologies, need to be removed. In this study, we fabricated a series of Fe₃O₄–urea-modified reduced graphene-oxide aerogels (Fe₃O₄–urea–rGOAs) by using industrial-grade graphene oxide as the raw material. A fixed-bed dynamic adsorption setup was built, and the adsorption properties of the Fe₃O₄–urea–rGOAs for hexamethyldisiloxane (L2, as a VMS model pollutant) were studied. The properties of the as-prepared samples were investigated by employing various characterization techniques (SEM, TEM, FTIR, XRD, Raman spectroscopy, and N₂ adsorption/desorption techniques). The results showed that the Fe₃O₄–urea–rGOA–0.4 had a high specific surface area (188 m² g⁻¹), large porous texture (0.77 cm³ g⁻¹), and the theoretical maximum adsorption capacity for L2 (146.5 mg g⁻¹). The adsorption capacity considerably increased with a decrease in the bed temperature of the adsorbents, as well as with an increase in the inlet concentration of L2. More importantly, the spent Fe₃O₄–urea–rGOA adsorbent could be readily regenerated and showed an excellent adsorption performance. Thus, the proposed Fe₃O₄–urea–rGOAs are promising adsorbents for removing the VMS in biogas.

Volatile methyl siloxanes (VMS) must be removed because the formation of silica in the combustion process seriously affects the resource utilization of biogas. Herein, a series of APTMS ((3–aminopropyl)trimethoxysilane)-modified activated porous carbon (APC) adsorbents (named APTMS@APC) were prepared for VMS efficient removal. The as-prepared adsorbents were characterized using SEM, FTIR, Raman, X-ray diffraction analyses, and N₂ adsorption/desorption. The results showed that the surface modification with APTMS enhanced the hydrophobicity of APC with the water contact angle increasing from 74.3° (hydrophilic) to 127.1° (hydrophobic), and meanwhile improved its texture properties with the S_BET increasing from 981 to 1274 m² g⁻¹. The maximum breakthrough adsorption capacity of APTMS@APC for hexamethyldisiloxane (L2, model pollutant) was 360.1 mg g⁻¹. Effects of an inlet L2 concentration (31.04–83.82 mg L⁻¹) and a bed temperature (0–50 °C) on the removal of L2 were investigated. Meanwhile, after five adsorption–desorption cycles, the APTMS@APC demonstrated a superior cycling performance. This indicated that the hydrophobic APTMS@APC has a great significance to remove VMS.

The utilisation of activated porous carbon (APC) for the removal of volatile methyl siloxane (VMS) has attracted significant research attention. However, the development of materials with high adsorption capacity remains a challenge. In this study, we successfully developed a high-specific-surface-area (2551 m² g⁻¹) APC material with a large porous texture (1.30 cm³ g⁻¹) using coconut shell waste and NaOH as the activating agent. The performance of the APC material in the removal of hexamethyldisiloxane (L2) was evaluated using a fixed-bed dynamic adsorption setup. Notably, at 0 °C, the APC demonstrated a remarkable L2 removal ability, achieving a breakthrough adsorption capacity of 898.6 mg g⁻¹. By increasing the inlet concentration of L2 and decreasing the temperature appropriately, the L2 adsorption capacity could be further improved. One advantage of APCs is their simple recycling process, which allows for sustained adsorption performance even after five consecutive cycles of adsorption and desorption. Therefore, the prepared APC material holds great promise as an efficient adsorbent for the removal of VMS.

In this work, the origins for the spectral difference between two isoflavones, formononetin (F) and ononin (FG), are revealed via a comparison study of the fluorescence molecular structure. The fluorescence enhancement of FG in hot alkaline conditions is reported for the first time. For F, there is almost no fluorescence under acidic conditions, but when the pH is >4.8, its fluorescence begins to increase due to the deprotonation of 7-OH. Under a pH between 9.3 and 12.0, the anionic form of F produces a strong and stable fluorescence. The fluorescence quantum yield (Yf) of F is measured to be 0.042. FG shows only weak fluorescence in aqueous solutions under a wide range of pH until it is placed in hot alkaline solutions, which is attributed to the cleavage reaction of the γ-pyrone ring in FG. The Yf of FG is determined to be 0.020. Based on the fluorescence sensitization methods of F and FG, the quantitative analysis and detection of two substances can be realized. The limit of the detections for F and FG are 2.60 ng·mL⁻¹ and 9.30 ng·mL⁻¹, respectively. The linear detection ranges of F and FG are 11.7~1860 ng·mL⁻¹ and 14.6~2920 ng·mL⁻¹, respectively. Although the structural relationship between F and FG is glycoside and aglycone, under hot alkaline conditions, the final products after the cleavage and hydrolysis reactions are essentially different. The different fluorescence characteristics between F and FG pave a way for further identification and a quantitative analysis of the corresponding components in Chinese herbal medicine.

In this study, β-cyclodextrin-modified reduced graphene oxide aerogels (β-CD-rGOAs) were synthesized via a one-step hydrothermal method and were used to remove hexamethyldisiloxane (L2) from biogas. The β-CD-rGOAs were characterized by the Brunner–Emmet–Teller technique, using Fourier-transform infrared spectroscopy, Raman spectrometry, scanning electron microscopy (SEM), contact angle measurements, and X-ray diffraction. The results of the characterizations indicate that β-CD was grafted onto the surface of rGOAs as a cross-linking modifier. The β-CD-rGOA had a three-dimensional, cross-linked porous structure. The maximum breakthrough adsorption capacity of L2 on β-CD-rGOA at 273 K was 111.8 mg g⁻¹. A low inlet concentration and bed temperature facilitated the adsorption of L2. Moreover, the β-CD-rGOA was regenerated by annealing at 80 °C, which renders this a promising material for removing L2 from biogas.

Chelerythrine (CH) and ethoxychelerythrine (ECH) are chemical reference substances for quality control of Chinese herbal medicines, and ECH is the dihydrogen derivative of CH. In this study, their fluorescence and absorption spectra, as well as their structural changes in different protic solvents were compared. It was observed that their emission fluorescence spectra in methanol were almost the same (both emitted at 400 nm), which may be attributed to the nucleophilic and exchange reactions of CH and ECH with methanol molecules with the common product of 6-methoxy-5,6-dihydrochelerythrine (MCH). When diluted with water, MCH was converted into CH, which mainly existed in the form of positively charged CH⁺ under acidic and near-neutral conditions with the fluorescence emission at 550 nm. With the increase of pH value of the aqueous solution, CH⁺ converted to 6-hydroxy-5,6-dihydrochelerythrine (CHOH) with the fluorescence emission at 410 nm. The fluorescence quantum yields of MCH and CHOH were 0.13 and 0.15, respectively, and both the fluorescence intensities were much stronger than that of CH⁺. It is concluded that CH and ECH can substitute each other in the same protic solvent, which was further verified by high-performance liquid chromatography. This study will help in the investigation of structural changes of benzophenanthridine alkaloids and will provide the possibility for the mutual substitution of standard substances in relevant drug testing.

Volatile methyl siloxanes (VMSs) as a trace impurity in biogas decreases its energy utilization, and thus need to be removed. In this paper, a one-step hydrothermal reduction was performed to produce three-dimensional reduced graphene oxide aerogels (rGOAs) using industrial-grade graphene oxide (IGGO) as raw material and vitamin C (VC) as a reductant to facilitate the fabrication of rGOAs. The synthesis of rGOAs was a simple, green, and energy-efficient process. The developed rGOAs were characterized using the Brunauer–Emmett–Teller method, Raman spectrometry, scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction measurements and contact angle. The results obtained showed that rGOA-1 with a VC/IGGO ratio of 1/1 (m/m) exhibited a hierarchical porous structure and super-hydrophobicity, yielding a high specific surface area (137.9 m² g⁻¹) and superior water contact angle (143.8°). The breakthrough adsorption capacity of rGOA-1 for hexamethyldisiloxane (L2, a VMS model) was 11 times higher than that of IGGO. Low inlet concentration and bed temperature were considered beneficial for the L2 adsorption. Interestingly, rGOA-1 was less sensitive to water, and it was readily regenerated for reuse by annealing at 80 °C. The rGOAs have been demonstrated to have great potential for the removal of siloxanes from biogas.

To expand the applications of graphene-based materials to biogas purification, a series of reduced graphene oxide aerogels (rGOAs) were prepared from industrial grade graphene oxide using a simple hydrothermal method. The influences of the hydrothermal preparation temperature on the textural properties, hydrophobicity and physisorption behavior of the rGOAs were investigated using a range of physical and spectroscopic techniques. The results showed that the rGOAs had a macro-porous three-dimensional network structure. Raising the hydrothermal treatment temperature reduced the number of oxygen-containing groups, whereas the specific surface area (S_BET), micropore volume (V_micro) and water contact angle values of the rGOAs all increased. The dynamic adsorption properties of the rGOAs towards hexamethyldisiloxane (L2) increased with increasing hydrothermal treatment temperature and the breakthrough adsorption capacity showed a significant linear association with S_BET, V_micro and contact angle. There was a significant negative association between the breakthrough time and inlet concentration of L2, and the relationship could be reliably predicted with a simple empirical formula. L2 adsorption also increased with decreasing bed temperature. Saturated rGOAs were readily regenerated by a brief heat-treatment at 100 °C. This study has demonstrated the potential of novel rGOA for applications using adsorbents to remove siloxanes from biogas.