## 优先发表

, doi: 10.19906/j.cnki.JFCT.2022029

, doi: 10.19906/j.cnki.JFCT.2022066

, doi: 10.19906/j.cnki.JFCT.2022052

, doi: 10.19906/j.cnki.JFCT.2022062

, doi: 10.19906/j.cnki.JFCT.2022065

, doi: 10.19906/j.cnki.JFCT.2022055

Carbon dioxide capture and utilization (CCU) is the best way to solve the problem of reducing concentration of carbon dioxide in the atmosphere, and it has a good prospect for development. On this basis, chemical researchers have explored the methods of synthesizing valuable organic compounds with CO2 as carbon source. The oxazolidinones are commonly used to synthesize drugs, and they are significant in organic synthesis as chiral molecules and intermediates. The synthetic methods of oxazolidinones have emerged in recent years. Furthermore, the methods of using carbon dioxide as a carbon source have attracted many researchers. In earlier years, people explored cycloaddition reactions of carbon dioxide and aziridines to synthesize oxazolidinones, and they took alkali metals, Cr, Al or other metals as catalysts to improve the efficiency of the reactions. Because of the cost and the principle of green synthesis, it is more suitable for large-scale reaction to select cheap and easily available ionic liquids or no catalysts. In addition, carbon dioxide and compounds such as β-amino alcohols, unsaturated amines and 1, 2-dihalohydrogenated compounds can obtain moderate or even excellent yields under different reaction conditions. In this paper, we summarized the synthetic methods of oxazolidinones using CO2 with different raw materials in recent years. Carbon dioxide capture and utilization (CCU) is the best way to solve the problem of reducing concentration of carbon dioxide in the atmosphere, and it has a good prospect for development. On this basis, chemical researchers have explored the methods of synthesizing valuable organic compounds with CO2 as carbon source. The oxazolidinones are commonly used to synthesize drugs, and they are significant in organic synthesis as chiral molecules and intermediates. The synthetic methods of oxazolidinones have emerged in recent years. Furthermore, the methods of using carbon dioxide as a carbon source have attracted many researchers. In earlier years, people explored cycloaddition reactions of carbon dioxide and aziridines to synthesize oxazolidinones, and they took alkali metals, Cr, Al or other metals as catalysts to improve the efficiency of the reactions. Because of the cost and the principle of green synthesis, it is more suitable for large-scale reaction to select cheap and easily available ionic liquids or no catalysts. In addition, carbon dioxide and compounds such as β-amino alcohols, unsaturated amines and 1, 2-dihalohydrogenated compounds can obtain moderate or even excellent yields under different reaction conditions. In this paper, we summarized the synthetic methods of oxazolidinones using CO2 with different raw materials in recent years.

, doi: 10.19906/j.cnki.JFCT.2022064

, doi: 10.19906/j.cnki.JFCT.2022050

, doi: 10.19906/j.cnki.JFCT.2022046

, doi: 10.19906/j.cnki.JFCT.2022057

, doi: 10.19906/j.cnki.JFCT.2022043

, doi: 10.19906/j.cnki.JFCT.2022020

, doi: 10.19906/j.cnki.JFCT.2022049

Low-rank coal is rarely used in the industry of carbonized briquette due to its poor cohesiveness. In order to replace lump coal and utilize low-rank pulverized coal as much as possible in a carbonized briquette process, washing oil residue (WOR) was used as an enhanced binder to enhance the bonding strength of resulted carbonized briquette. The effects of blending ratio and carbonization temperatures on binding strength were investigated, and moreover, a reasonable bonding mechanism was deduced. The results showed that the best crushing strength was obtained when the weight ratio of WOR and low-rank coal is 3∶7 at 800 °C, and its crushing strength of M25 (M25) can reach to 97%, while the thermoplastic properties of WOR is thought to be responsible for the obtained good crushing strength, where WOR can be softened and coated on the surface of coal particles during carbonization, and then a coal-binder interface can be formed, resulting in the loose inert coal particles can be combined and the strength of coke is improved significantly. Low-rank coal is rarely used in the industry of carbonized briquette due to its poor cohesiveness. In order to replace lump coal and utilize low-rank pulverized coal as much as possible in a carbonized briquette process, washing oil residue (WOR) was used as an enhanced binder to enhance the bonding strength of resulted carbonized briquette. The effects of blending ratio and carbonization temperatures on binding strength were investigated, and moreover, a reasonable bonding mechanism was deduced. The results showed that the best crushing strength was obtained when the weight ratio of WOR and low-rank coal is 3∶7 at 800 °C, and its crushing strength of M25 (M25) can reach to 97%, while the thermoplastic properties of WOR is thought to be responsible for the obtained good crushing strength, where WOR can be softened and coated on the surface of coal particles during carbonization, and then a coal-binder interface can be formed, resulting in the loose inert coal particles can be combined and the strength of coke is improved significantly.

, doi: 10.19906/j.cnki.JFCT.2022024

, doi: 10.19906/j.cnki.JFCT.2022026

, doi: 10.19906/j.cnki.JFCT.2022018

, doi: 10.19906/j.cnki.JFCT.2022023

, doi: 10.19906/j.cnki.JFCT.2022035

, doi: 10.19906/j.cnki.JFCT.2022025

CO2电催化还原合成高附加值燃料为CO2转化利用提供了一条可持续发展的途径。然而，开发具有优异催化活性和产物选择性的电催化剂仍面临巨大的挑战。本研究制备了铜改性黄铁矿催化剂CuxFe1−xS2，采用XRD、XPS、SEM等表征分析方法研究了催化剂的物理化学性质，并研究了催化剂的CO2电催化还原活性和产物选择性。实验结果表明，Cu掺杂可以调控催化剂纳米片的尺寸，同时可以抑制FeS2在空气中的氧化。Cu0.33Fe0.67S2比FeS2表现出更好的催化反应活性，在(−1.5) − (−1.6) V vs. RHE，CO2电催化还原的含碳产物法拉第效率为50.8%，电流密度为23.8 mA/cm2。相比于FeS2催化剂，电流密度提高了71.2%。Cu0.09Fe0.91S2在−1.3 V vs. RHE下生成C3H6的法拉第效率为21.8%，显著高于目前文献中已报道的数值。因此，CuxFe1−xS2是一种比较有前景的CO2电催化还原催化剂。 CO2电催化还原合成高附加值燃料为CO2转化利用提供了一条可持续发展的途径。然而，开发具有优异催化活性和产物选择性的电催化剂仍面临巨大的挑战。本研究制备了铜改性黄铁矿催化剂CuxFe1−xS2，采用XRD、XPS、SEM等表征分析方法研究了催化剂的物理化学性质，并研究了催化剂的CO2电催化还原活性和产物选择性。实验结果表明，Cu掺杂可以调控催化剂纳米片的尺寸，同时可以抑制FeS2在空气中的氧化。Cu0.33Fe0.67S2比FeS2表现出更好的催化反应活性，在(−1.5) − (−1.6) V vs. RHE，CO2电催化还原的含碳产物法拉第效率为50.8%，电流密度为23.8 mA/cm2。相比于FeS2催化剂，电流密度提高了71.2%。Cu0.09Fe0.91S2在−1.3 V vs. RHE下生成C3H6的法拉第效率为21.8%，显著高于目前文献中已报道的数值。因此，CuxFe1−xS2是一种比较有前景的CO2电催化还原催化剂。

, doi: 10.19906/j.cnki.JFCT.2022072

A series of Co-doped Mn oxide catalysts with different Co/Mn molar ratios were prepared by co-precipitation method, which was systematically characterized by XRD, SEM, H2-TPR and NH3-TPD etc. Co-doped Mn oxide catalysts are evaluated for NH3-SCR activity and resistance to SO2 and/or H2O, and the Co(1)-MnOx catalyst with Mn/Co molar ratio of 1:1 performs the best catalytic performance, which achieved higher than 90% NOx conversion in the temperature range of 100−275 °C and possessed better SO2 and H2O resistance. The Co(1)-MnOx catalyst presented a sphere-like structure possessing a relatively large surface area. Doping of cobalt greatly improved the high-valent metal ions and chemisorbed oxygen content of Co(1)-MnOx catalyst surface, and the catalyst possessed abundant active species and acid sites and apparent activation energy of the catalyst was reduced, which makes Co(1)-MnOx a highly effective NH3-SCR catalyst. A series of Co-doped Mn oxide catalysts with different Co/Mn molar ratios were prepared by co-precipitation method, which was systematically characterized by XRD, SEM, H2-TPR and NH3-TPD etc. Co-doped Mn oxide catalysts are evaluated for NH3-SCR activity and resistance to SO2 and/or H2O, and the Co(1)-MnOx catalyst with Mn/Co molar ratio of 1:1 performs the best catalytic performance, which achieved higher than 90% NOx conversion in the temperature range of 100−275 °C and possessed better SO2 and H2O resistance. The Co(1)-MnOx catalyst presented a sphere-like structure possessing a relatively large surface area. Doping of cobalt greatly improved the high-valent metal ions and chemisorbed oxygen content of Co(1)-MnOx catalyst surface, and the catalyst possessed abundant active species and acid sites and apparent activation energy of the catalyst was reduced, which makes Co(1)-MnOx a highly effective NH3-SCR catalyst.

, doi: 10.19906/j.cnki.JFCT.2022056

Nitrogen-doped carbons (Nano-NC) are often employed as functional supports for boosting oxygen reduction reaction (ORR) over Pt-based catalysts, however, the mechanism of N doping on the adsorption and activation of molecular oxygen on Pt active sites is still not clear. Herein, Nano-NCs as the supports were prepared by a facile NH3 antipyretic method, which allowed to tune the kinds of nitrogen species in carbon matrix and their contents by adjusting the NH3 antipyretic temperatures.With such an exquisite control, the Pt nanoparticles loaded on the as-obtained Nano-NC showed an optimal Pt particle size (2.10 nm), a higher content of Pt0, a large electrochemically active surface area, and fast electron transport ability. As a consequence, the Pt/Nano-NC-800 catalyst with the optimal N-doping showed an outstanding ORR performance with half-wave potential of 0.80 V vs. RHE, limit diffusion current of 5.37 mA/cm2 and improved methanol/CO anti-poisoning, which is superior to the commercial Pt/C catalyst (20%, JM), and most of previously reported Pt-based catalysts. This work may pave a way for the design of the advanced supports for Pt-based catalysts for the ORR applications. Nitrogen-doped carbons (Nano-NC) are often employed as functional supports for boosting oxygen reduction reaction (ORR) over Pt-based catalysts, however, the mechanism of N doping on the adsorption and activation of molecular oxygen on Pt active sites is still not clear. Herein, Nano-NCs as the supports were prepared by a facile NH3 antipyretic method, which allowed to tune the kinds of nitrogen species in carbon matrix and their contents by adjusting the NH3 antipyretic temperatures.With such an exquisite control, the Pt nanoparticles loaded on the as-obtained Nano-NC showed an optimal Pt particle size (2.10 nm), a higher content of Pt0, a large electrochemically active surface area, and fast electron transport ability. As a consequence, the Pt/Nano-NC-800 catalyst with the optimal N-doping showed an outstanding ORR performance with half-wave potential of 0.80 V vs. RHE, limit diffusion current of 5.37 mA/cm2 and improved methanol/CO anti-poisoning, which is superior to the commercial Pt/C catalyst (20%, JM), and most of previously reported Pt-based catalysts. This work may pave a way for the design of the advanced supports for Pt-based catalysts for the ORR applications.

Co/HZSM-5 catalyst was fabricated for catalytic dehydrogenation of propane to propylene, which was pretreated to allow the reaction to react at low temperatures. A response surface approach was employed to examine the effect of process conditions on the reaction. The morphological and oxidative performance of Co/HZSM-5 was characterized by XRD, XPS, SEM, NH3-TPD, H2-TPR, and nitrogen physical absorption-desorption. Besides, the in-situ catalyst performance was evaluated by a fixed-bed reactor. Combining the actual experimental conditions, the optimal process conditions parameters obtained by the response surface method were as follows: a reaction temperature of 461 °C, a Co loading of 2.4%, and a GHSV of 4300 h−1. At this point, the propylene yield reached 27.7% and the corresponding propylene selectivity was up to 93.8 %. Co/HZSM-5 catalyst was fabricated for catalytic dehydrogenation of propane to propylene, which was pretreated to allow the reaction to react at low temperatures. A response surface approach was employed to examine the effect of process conditions on the reaction. The morphological and oxidative performance of Co/HZSM-5 was characterized by XRD, XPS, SEM, NH3-TPD, H2-TPR, and nitrogen physical absorption-desorption. Besides, the in-situ catalyst performance was evaluated by a fixed-bed reactor. Combining the actual experimental conditions, the optimal process conditions parameters obtained by the response surface method were as follows: a reaction temperature of 461 °C, a Co loading of 2.4%, and a GHSV of 4300 h−1. At this point, the propylene yield reached 27.7% and the corresponding propylene selectivity was up to 93.8 %.
, doi: 10.19906/j.cnki.JFCT.2022028

Oxidation treated carbon materials for exploiting highly efficient and stable loaded catalysts have been proven to be valid. In this work, the surfaces of carbon aerogels (CA) were functionalized with different oxidizing agents, i.e., H2O2 and HNO3. A series of Ru-supported catalysts on carbon aerogels (CA) with/without functionalized were prepared by the impregnation strategy. The impact of oxidation treatment on the texture features of carbon aerogels, the types and contents of formed surface oxygen-containing functional groups, the metal-support interactions and the Fischer-Tropsch synthesis reaction performances of i the catalysts were systematically investigated. Our results showed that Ru/CA catalyst without oxidation treatment displayed the highest initial activity but the poor stability, while the Ru/CA−H2O2 catalyst exhibited excellent activity and C5+ selectivity. The oxidation treatment increased the carbon aerogels defects, thereby broadening the specific surface area. The increased content of oxygen-containing functional groups on the surface enhanced the interaction between the support and Ru nanoparticles and improved the stability of the catalyst. Nevertheless, the excessive oxygen-containing functional groups on the surface decreased the activity and the C5+ selectivity of carbon aerogels-loaded Ru catalysts. Oxidation treated carbon materials for exploiting highly efficient and stable loaded catalysts have been proven to be valid. In this work, the surfaces of carbon aerogels (CA) were functionalized with different oxidizing agents, i.e., H2O2 and HNO3. A series of Ru-supported catalysts on carbon aerogels (CA) with/without functionalized were prepared by the impregnation strategy. The impact of oxidation treatment on the texture features of carbon aerogels, the types and contents of formed surface oxygen-containing functional groups, the metal-support interactions and the Fischer-Tropsch synthesis reaction performances of i the catalysts were systematically investigated. Our results showed that Ru/CA catalyst without oxidation treatment displayed the highest initial activity but the poor stability, while the Ru/CA−H2O2 catalyst exhibited excellent activity and C5+ selectivity. The oxidation treatment increased the carbon aerogels defects, thereby broadening the specific surface area. The increased content of oxygen-containing functional groups on the surface enhanced the interaction between the support and Ru nanoparticles and improved the stability of the catalyst. Nevertheless, the excessive oxygen-containing functional groups on the surface decreased the activity and the C5+ selectivity of carbon aerogels-loaded Ru catalysts.

Direct methanol fuel cell (DMFC) is a potential commercial fuel cell technology that is presently hindered by the expensive noble metal materials of the anode. Developing a method to obtain a uniformly dispersed metal phosphide catalyst with narrow size distribution is still a challenge. In this work, cobalt oxide was deposited on carbon cloth (CC) through atomic layer deposition (ALD), then cobalt phosphide was obtained after the phosphorization process. By changing the number of ALD-based ozone pulses (ALD-O3) for CC, the nucleation and growth modes of cobalt oxide (ALD-CoOx) on the CC were regulated, and CoPx nanoparticles with small particle size and uniform distribution were obtained. The optimized CoPx-based catalyst with 40 cycles of ALD-O3 treatment (CoPx/40-CC) exhibits excellent activity (153 mA/cm2) toward methanol electrocatalytic oxidation reaction in the alkaline solution, which is higher than the catalyst prepared by impregnation (Imp-CoPx/CC), although the CoPx loading of CoPx/40-CC is lower than that of Imp-CoPx/CC. The results indicate that the enhanced activity benefits from the small particle size and the uniform CoPx distribution, which promote the electron-transfer and mass transport kinetics of the methanol electro-oxidation process. Direct methanol fuel cell (DMFC) is a potential commercial fuel cell technology that is presently hindered by the expensive noble metal materials of the anode. Developing a method to obtain a uniformly dispersed metal phosphide catalyst with narrow size distribution is still a challenge. In this work, cobalt oxide was deposited on carbon cloth (CC) through atomic layer deposition (ALD), then cobalt phosphide was obtained after the phosphorization process. By changing the number of ALD-based ozone pulses (ALD-O3) for CC, the nucleation and growth modes of cobalt oxide (ALD-CoOx) on the CC were regulated, and CoPx nanoparticles with small particle size and uniform distribution were obtained. The optimized CoPx-based catalyst with 40 cycles of ALD-O3 treatment (CoPx/40-CC) exhibits excellent activity (153 mA/cm2) toward methanol electrocatalytic oxidation reaction in the alkaline solution, which is higher than the catalyst prepared by impregnation (Imp-CoPx/CC), although the CoPx loading of CoPx/40-CC is lower than that of Imp-CoPx/CC. The results indicate that the enhanced activity benefits from the small particle size and the uniform CoPx distribution, which promote the electron-transfer and mass transport kinetics of the methanol electro-oxidation process.

, doi: 10.19906/j.cnki.JFCT.2022034

, doi: 10.19906/j.cnki.JFCT.2022027

, doi: 10.19906/j.cnki.JFCT.2022063

CO2甲烷化反应是一个十分复杂的多相催化过程，在反应过程中会产生各种各样的中间体，其反应路径目前还存在许多争议和矛盾。深入系统地研究CO2甲烷化反应中催化剂表面中间体的演变过程，可以进一步从机理的角度优化催化剂的设计方案，提高催化性能。本文主要基于原位红外光谱表征技术，总结梳理了最近关于CO2甲烷化反应路径研究的相关工作，着重探讨了负载型催化剂的活性金属、载体、助剂、合成方法等因素对CO2甲烷化反应路径的影响以及由此对催化剂性能所产生的积极效果。同时针对现阶段所面临的争论点，即反应气CO2与H2的活化位点、催化剂的活性位点以及未来可行的研究方法进行了详细论述。 CO2甲烷化反应是一个十分复杂的多相催化过程，在反应过程中会产生各种各样的中间体，其反应路径目前还存在许多争议和矛盾。深入系统地研究CO2甲烷化反应中催化剂表面中间体的演变过程，可以进一步从机理的角度优化催化剂的设计方案，提高催化性能。本文主要基于原位红外光谱表征技术，总结梳理了最近关于CO2甲烷化反应路径研究的相关工作，着重探讨了负载型催化剂的活性金属、载体、助剂、合成方法等因素对CO2甲烷化反应路径的影响以及由此对催化剂性能所产生的积极效果。同时针对现阶段所面临的争论点，即反应气CO2与H2的活化位点、催化剂的活性位点以及未来可行的研究方法进行了详细论述。

, doi: 10.19906/j.cnki.JFCT.2022060

, doi: 10.19906/j.cnki.JFCT.2022022

Hydrogen production from electrolyzed water driven by sustainable energy is an effective way to achieve the hydrogen economy with zero carbon emission. Alkaline electrocatalytic hydrogen evolution reaction(HER) is one of the main energy transforming processes in the field of electrolytic water technology. The development of active and cost-effective nonprecious catalytic electrodes is of great importance to alkaline hydrogen evolution reaction. Amorphous nanosized nickel-boron alloy particles (NiB-COS) have been obtained by using chitosan oligosaccharides (COS) as a stabilizer via chemical reduction method. The as-prepared electrocatalysts have been used for the hydrogen evolution reaction (HER). The electrocatalysts have been characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), inductively coupled plasma analysis (ICP) and X-ray photoelectron spectroscopy (XPS). NiB-COS displays a significant increase in hydrogen evolution reaction properties in alkaline media, affording low overpotentials of 49.4 mV at 10 mA/cm2 and 15.1 mV onset overpotential for the hydrogen evolution reaction. Tafel slope of NiB-COS is 86.1 mV/decade. Remarkably, the formation of a nickel-boron alloyed phase and the decrease of particle size are helpful to improve HER activity of NiB-COS. The experimental data indicated that the NiB-COS showed excellent long-term stability as a very active electrocatalyst. Hydrogen production from electrolyzed water driven by sustainable energy is an effective way to achieve the hydrogen economy with zero carbon emission. Alkaline electrocatalytic hydrogen evolution reaction(HER) is one of the main energy transforming processes in the field of electrolytic water technology. The development of active and cost-effective nonprecious catalytic electrodes is of great importance to alkaline hydrogen evolution reaction. Amorphous nanosized nickel-boron alloy particles (NiB-COS) have been obtained by using chitosan oligosaccharides (COS) as a stabilizer via chemical reduction method. The as-prepared electrocatalysts have been used for the hydrogen evolution reaction (HER). The electrocatalysts have been characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), inductively coupled plasma analysis (ICP) and X-ray photoelectron spectroscopy (XPS). NiB-COS displays a significant increase in hydrogen evolution reaction properties in alkaline media, affording low overpotentials of 49.4 mV at 10 mA/cm2 and 15.1 mV onset overpotential for the hydrogen evolution reaction. Tafel slope of NiB-COS is 86.1 mV/decade. Remarkably, the formation of a nickel-boron alloyed phase and the decrease of particle size are helpful to improve HER activity of NiB-COS. The experimental data indicated that the NiB-COS showed excellent long-term stability as a very active electrocatalyst.

In this work we report the feasible modification of graphitic carbon nitride (g-C3N4) polymer through a post-functionalization progress. The resultant photocatalyst exhibits boron doping and mesoporous structure with a high surface area of 125 m2/g, leading in an increased surface activity for photocatalytic water splitting reaction. X-ray diffraction, X-ray photoelectron spectroscopy, PL emission spectra and UV-vis spectra were used to detect the properties of as-prepared samples. Based on X-ray photoelectron spectroscopy analysis, boron is proposed to dope in the g-C3N4 lattice. Optical studies indicated that boron doped g-C3N4 exhibits enhanced and extended light absorbance in the visible-light region and a much lower intensity of PL emission spectra compared to pure g-C3N4. As a result, boron doped g-C3N4 shows activity of 10.2 times higher than the pristine g-C3N4 for photocatalytic hydrogen evolution. Thi work may provide a way to design efficient and mesoporous photocatalysts through post modification. In this work we report the feasible modification of graphitic carbon nitride (g-C3N4) polymer through a post-functionalization progress. The resultant photocatalyst exhibits boron doping and mesoporous structure with a high surface area of 125 m2/g, leading in an increased surface activity for photocatalytic water splitting reaction. X-ray diffraction, X-ray photoelectron spectroscopy, PL emission spectra and UV-vis spectra were used to detect the properties of as-prepared samples. Based on X-ray photoelectron spectroscopy analysis, boron is proposed to dope in the g-C3N4 lattice. Optical studies indicated that boron doped g-C3N4 exhibits enhanced and extended light absorbance in the visible-light region and a much lower intensity of PL emission spectra compared to pure g-C3N4. As a result, boron doped g-C3N4 shows activity of 10.2 times higher than the pristine g-C3N4 for photocatalytic hydrogen evolution. Thi work may provide a way to design efficient and mesoporous photocatalysts through post modification.

, doi: 10.19906/j.cnki.JFCT.2022040

NaHCO3是一种高效的烟气脱酸剂，但脱酸过程中NaHCO3对于SeO2的吸附效果及机理尚不明确。本文通过吸附实验探究了140−220 ℃下NaHCO3对SeO2的吸附性能，通过一系列表征解析了吸附后的样品中硒的总量、价态和形态，结合密度泛函理论计算，探讨了NaHCO3对SeO2的吸附机理。结果表明，NaHCO3对SeO2的吸附性能随温度的升高而增加，在吸附过程中同时发生NaHCO3向Na2CO3的分解反应，分解后产生的Na2CO3吸附活性更强。SeO2吸附过程属于SeO2中Se原子与Na2CO3表面O原子成键的化学吸附，吸附产物以亚硒酸盐为主。 NaHCO3是一种高效的烟气脱酸剂，但脱酸过程中NaHCO3对于SeO2的吸附效果及机理尚不明确。本文通过吸附实验探究了140−220 ℃下NaHCO3对SeO2的吸附性能，通过一系列表征解析了吸附后的样品中硒的总量、价态和形态，结合密度泛函理论计算，探讨了NaHCO3对SeO2的吸附机理。结果表明，NaHCO3对SeO2的吸附性能随温度的升高而增加，在吸附过程中同时发生NaHCO3向Na2CO3的分解反应，分解后产生的Na2CO3吸附活性更强。SeO2吸附过程属于SeO2中Se原子与Na2CO3表面O原子成键的化学吸附，吸附产物以亚硒酸盐为主。

To explore the catalytic performance of three perovskites (LaBO3--LaCoO3, LaFeO3, LaNiO3), the experimental characterization methods (GC−MS, FT−IR, elemental analysis) and DFT calculation were combined for researching liquefaction of lignin. The effects of time, temperature, catalyst dosage and B cation on the conversion rate, bio-oil yield and bio-oil component distribution were investigated. The results showed that all the three catalysts could promoted the liquefaction of lignin to produce aromatic compounds. Among them, LaCoO3 had the greatest promoting on bio-oil yield, and the highest bio-oil yield of 67.20wt% was obtained at 180 °C for 60 min over 5wt% LaCoO3, followed by LaNiO3 and LaFeO3. The relative content of mono-aromatic compounds reached 89.59% under LaCoO3. Mechanism studies suggested that the adsorption of oxygen atoms on the surface of LaBO3 crystal with lignin reduced the dissociation energy of bonds of lignin. Moreover, LaCoO3 had moderate redox capacity, largest adsorption energy, loose and porous morphology, which could effectively promoted the fracture of C−C and CAr−OCH3 of lignin, so that achieved macromolecular depolymerization and demethoxylation reaction to produce high value-added compounds such as phenol. To explore the catalytic performance of three perovskites (LaBO3--LaCoO3, LaFeO3, LaNiO3), the experimental characterization methods (GC−MS, FT−IR, elemental analysis) and DFT calculation were combined for researching liquefaction of lignin. The effects of time, temperature, catalyst dosage and B cation on the conversion rate, bio-oil yield and bio-oil component distribution were investigated. The results showed that all the three catalysts could promoted the liquefaction of lignin to produce aromatic compounds. Among them, LaCoO3 had the greatest promoting on bio-oil yield, and the highest bio-oil yield of 67.20wt% was obtained at 180 °C for 60 min over 5wt% LaCoO3, followed by LaNiO3 and LaFeO3. The relative content of mono-aromatic compounds reached 89.59% under LaCoO3. Mechanism studies suggested that the adsorption of oxygen atoms on the surface of LaBO3 crystal with lignin reduced the dissociation energy of bonds of lignin. Moreover, LaCoO3 had moderate redox capacity, largest adsorption energy, loose and porous morphology, which could effectively promoted the fracture of C−C and CAr−OCH3 of lignin, so that achieved macromolecular depolymerization and demethoxylation reaction to produce high value-added compounds such as phenol.

, doi: 10.19906/j.cnki.JFCT.2022074

, doi: 10.19906/j.cnki.JFCT.2022073

The complexity and diversity of lignin derived bio-oil (LDB) has posed a great challenge to the subsequent processing and utilization. In this work, HZSM-5 was modified by sodium hydroxide and followed by Ni, Cu and Ru species. LDB was used as the raw biocrude to prepare bio-oil rich in aromatic hydrocarbons with modified HZSM-5 catalysts under supercritical ethanol conditions (320 °C, 14 MPa). Results showed that the desilicated HZSM-5 with the loading of Ni, Cu and Ru (Ni-Cu-Ru/DeHZSM-5) exhibited the best catalytic performance with a high relative amount of aromatic hydrocarbons of 28.95%. After catalytic hydrodeoxygenation (HDO) of LDB, 80.40% upgraded bio-oil (UBO) with 96.32% energy recovery was obtained in the presence of Ni-Cu-Ru/DeHZSM-5. Demethoxylation and dehydration were the main reactions in the catalytic HDO process. Potential reaction pathways of guaiacol, syringol and cresol were also proposed in this paper. The heating value of UBO reached 35.22 MJ/kg compared with LDB, which was increased by 19.80%. The water content and viscosity of UBO were also significantly improved. The micro-mesoporous structure of modified HZSM-5 with loading of Ni, Cu and Ru was beneficial to promote the yield of the aromatic hydrocarbons. The complexity and diversity of lignin derived bio-oil (LDB) has posed a great challenge to the subsequent processing and utilization. In this work, HZSM-5 was modified by sodium hydroxide and followed by Ni, Cu and Ru species. LDB was used as the raw biocrude to prepare bio-oil rich in aromatic hydrocarbons with modified HZSM-5 catalysts under supercritical ethanol conditions (320 °C, 14 MPa). Results showed that the desilicated HZSM-5 with the loading of Ni, Cu and Ru (Ni-Cu-Ru/DeHZSM-5) exhibited the best catalytic performance with a high relative amount of aromatic hydrocarbons of 28.95%. After catalytic hydrodeoxygenation (HDO) of LDB, 80.40% upgraded bio-oil (UBO) with 96.32% energy recovery was obtained in the presence of Ni-Cu-Ru/DeHZSM-5. Demethoxylation and dehydration were the main reactions in the catalytic HDO process. Potential reaction pathways of guaiacol, syringol and cresol were also proposed in this paper. The heating value of UBO reached 35.22 MJ/kg compared with LDB, which was increased by 19.80%. The water content and viscosity of UBO were also significantly improved. The micro-mesoporous structure of modified HZSM-5 with loading of Ni, Cu and Ru was beneficial to promote the yield of the aromatic hydrocarbons.

, doi: 10.19906/j.cnki.JFCT.2022071

, doi: 10.19906/j.cnki.JFCT.2022070

, doi: 10.19906/j.cnki.JFCT.2022069

, doi: 10.19906/j.cnki.JFCT.2022068

, doi: 10.19906/j.cnki.JFCT.2022038

, doi: 10.19906/j.cnki.JFCT.2022031

, doi: 10.19906/j.cnki.JFCT.2022030

, doi: 10.19906/j.cnki.JFCT.2022037

, doi: 10.19906/j.cnki.JFCT.2022044

Herein, SiO2 supported metallic Ni (Ni/SiO2) and bimetallic Ni-Zn (NixZn/SiO2) (x represents the Ni/Zn atomic ratio) catalysts were prepared by the incipient wetness impregnation method and their activities were tested in vapor phase hydrodeoxygenation (HDO) of anisole under 0.1 MPa. It has been found The characterization results show that the Ni-Zn alloy forms in NixZn/SiO2 after reduction at 550 °C, and the a suitable Ni/Zn atomic ratio (30) leads to smaller metal crystallites alloy particle size and consequently more H2 adsorption amount than others. In the HDO reaction, the formation of Ni-Zn alloy facilitates the direct deoxygenation pathway and suppresses CO methanation and C−C bond hydrogenolysis, which is ascribed to the isolation effect of the Ni atoms by the oxophilic Zn ones. Ni30Zn/SiO2 gives not only higher anisole conversion but also higher selectivity to benzene than Ni/SiO2. Therefore, the introduction of a suitable amount of oxophilic Zn in Ni/SiO2 promotes the HDO of anisole to benzene. Finally, we suggest propose that the Ni30Zn/SiO2 deactivation is related to the surface oxidation of Ni-Zn alloy and carbonaceous deposit carbon deposition on the catalyst surface. Herein, SiO2 supported metallic Ni (Ni/SiO2) and bimetallic Ni-Zn (NixZn/SiO2) (x represents the Ni/Zn atomic ratio) catalysts were prepared by the incipient wetness impregnation method and their activities were tested in vapor phase hydrodeoxygenation (HDO) of anisole under 0.1 MPa. It has been found The characterization results show that the Ni-Zn alloy forms in NixZn/SiO2 after reduction at 550 °C, and the a suitable Ni/Zn atomic ratio (30) leads to smaller metal crystallites alloy particle size and consequently more H2 adsorption amount than others. In the HDO reaction, the formation of Ni-Zn alloy facilitates the direct deoxygenation pathway and suppresses CO methanation and C−C bond hydrogenolysis, which is ascribed to the isolation effect of the Ni atoms by the oxophilic Zn ones. Ni30Zn/SiO2 gives not only higher anisole conversion but also higher selectivity to benzene than Ni/SiO2. Therefore, the introduction of a suitable amount of oxophilic Zn in Ni/SiO2 promotes the HDO of anisole to benzene. Finally, we suggest propose that the Ni30Zn/SiO2 deactivation is related to the surface oxidation of Ni-Zn alloy and carbonaceous deposit carbon deposition on the catalyst surface.

, doi: 10.19906/j.cnki.JFCT.2022032

, doi: 10.19906/j.cnki.JFCT.2022036

, doi: 10.19906/j.cnki.JFCT.2022033

, doi: 10.19906/j.cnki.JFCT.2022059

Methyl N-phenylcarbamate (MPC) is an important intermediate for the synthesis of diphenylmethane diisocyanate (MDI), and its preparation using CO2 or its equivalents/derivatives as carbon source represents a green and sustainable manner for fine chemicals synthesis. This review will highlight the development of MPC synthetic methods from the viewpoint of chemical fixation of CO2. The contents mainly include the introduction of MPC synthesis through CO2 equivalents (urea or phenyl urea) alcoholysis, dimethyl carbonate (DMC) aminolysis, and the coupling of DMC and diphenyl urea. Further more, one-pot synthesis of carbamates/MPC from aliphatic amines/aniline, CO2 and alcohols is highlighted which represents one of the most promising schemes in direct CO2 utilization. What is more, the reaction mechanisms and selection of catalysts are also discussed in detail. The advances will provide important theories on further improving the efficiency of green catalysis and sustainable chemical processes. Methyl N-phenylcarbamate (MPC) is an important intermediate for the synthesis of diphenylmethane diisocyanate (MDI), and its preparation using CO2 or its equivalents/derivatives as carbon source represents a green and sustainable manner for fine chemicals synthesis. This review will highlight the development of MPC synthetic methods from the viewpoint of chemical fixation of CO2. The contents mainly include the introduction of MPC synthesis through CO2 equivalents (urea or phenyl urea) alcoholysis, dimethyl carbonate (DMC) aminolysis, and the coupling of DMC and diphenyl urea. Further more, one-pot synthesis of carbamates/MPC from aliphatic amines/aniline, CO2 and alcohols is highlighted which represents one of the most promising schemes in direct CO2 utilization. What is more, the reaction mechanisms and selection of catalysts are also discussed in detail. The advances will provide important theories on further improving the efficiency of green catalysis and sustainable chemical processes.

, doi: 10.19906/j.cnki.JFCT.2022058

, doi: 10.19906/j.cnki.JFCT.2022054

, doi: 10.19906/j.cnki.JFCT.2022053

, doi: 10.19906/j.cnki.JFCT.2022051

A highly efficient cerium-modified Cu/hexagonal mesoporous silica (xCe-Cu/HMS) catalyst for the vapor-phase hydrogenation of dimethyl oxalate (DMO) into ethylene glycol (EG) was prepared using an ammonia evaporation method. The Ce promoter can significantly improve the performance of the catalyst, and the best catalytic performance was obtained after the introduction of 1.2 wt% Ce promoter on Cu/HMS. The DMO conversion and EG selectivity got to unprecedented 99.6% and 96.3%, respectively, under moderate conditions (200 °C, 2.0 MPa, H2/DMO = 100 and LHSVDMO = 1.2 h−1). Characterization results revealed that Ce modification can enhance the interaction between Cu and the support, improve the dispersion of Cu on HMS, and maintain the appropriate ratio of Cu+/ (Cu+ + Cu0). In this study, a simple and low-cost method was used to synthesize Ce-modified Cu-HMS catalysts, which showed excellent catalytic performance in conversion of DMO to EG under moderate conditions. A highly efficient cerium-modified Cu/hexagonal mesoporous silica (xCe-Cu/HMS) catalyst for the vapor-phase hydrogenation of dimethyl oxalate (DMO) into ethylene glycol (EG) was prepared using an ammonia evaporation method. The Ce promoter can significantly improve the performance of the catalyst, and the best catalytic performance was obtained after the introduction of 1.2 wt% Ce promoter on Cu/HMS. The DMO conversion and EG selectivity got to unprecedented 99.6% and 96.3%, respectively, under moderate conditions (200 °C, 2.0 MPa, H2/DMO = 100 and LHSVDMO = 1.2 h−1). Characterization results revealed that Ce modification can enhance the interaction between Cu and the support, improve the dispersion of Cu on HMS, and maintain the appropriate ratio of Cu+/ (Cu+ + Cu0). In this study, a simple and low-cost method was used to synthesize Ce-modified Cu-HMS catalysts, which showed excellent catalytic performance in conversion of DMO to EG under moderate conditions.

, doi: 10.19906/j.cnki.JFCT.2022048

, doi: 10.19906/j.cnki.JFCT.2022045

, doi: 10.19906/j.cnki.JFCT.2022041

, doi: 10.19906/j.cnki.JFCT.2022042

, doi: 10.19906/j.cnki.JFCT.2022039

Oxidation treated carbon materials for the exploitation of efficient and stable loaded catalysts have been proven to be valid. The surfaces of carbon aerogels (CA) were functionalized with different oxidizing agents, H2O2 and HNO3. A series of Ru-supported catalysts were prepared by impregnation on carbon aerogel (CA) with/without functionalized. The impact of oxidation treatment on the texture features of carbon aerogels, the types and contents of formed surface oxygen-containing functional groups, the metal-support interactions and the Fischer-Tropsch synthesis reaction performance of the catalysts were systematically investigated using XRD, Raman spectra, N2-physisorption, H2-TPR, FTIR and XPS. The experimental results showed that Ru/CA catalyst displayed the highest initial activity but poor stability. In contrast, the Ru/CA-H2O2 catalyst exhibited excellent activity and C5+ selectivity. Characterization results demonstrated that the oxidation treatment increased the carbon aerogels defects, thereby enhanced the specific surface area. The increased content of oxygen-containing functional groups on the surface enhanced the interaction between the support and Ru nanoparticles and improved the stability of the catalyst. Nevertheless, the excessive oxygen-containing functional groups on the surface decrease the activity and C5+ selectivity of carbon aerogels-loaded Ru catalysts. Oxidation treated carbon materials for the exploitation of efficient and stable loaded catalysts have been proven to be valid. The surfaces of carbon aerogels (CA) were functionalized with different oxidizing agents, H2O2 and HNO3. A series of Ru-supported catalysts were prepared by impregnation on carbon aerogel (CA) with/without functionalized. The impact of oxidation treatment on the texture features of carbon aerogels, the types and contents of formed surface oxygen-containing functional groups, the metal-support interactions and the Fischer-Tropsch synthesis reaction performance of the catalysts were systematically investigated using XRD, Raman spectra, N2-physisorption, H2-TPR, FTIR and XPS. The experimental results showed that Ru/CA catalyst displayed the highest initial activity but poor stability. In contrast, the Ru/CA-H2O2 catalyst exhibited excellent activity and C5+ selectivity. Characterization results demonstrated that the oxidation treatment increased the carbon aerogels defects, thereby enhanced the specific surface area. The increased content of oxygen-containing functional groups on the surface enhanced the interaction between the support and Ru nanoparticles and improved the stability of the catalyst. Nevertheless, the excessive oxygen-containing functional groups on the surface decrease the activity and C5+ selectivity of carbon aerogels-loaded Ru catalysts.