Pub Date : 2025-01-03DOI: 10.1007/s10562-024-04900-x
Yumin Pan, Tingting Xie, Jiming Peng, Cuihui Cao, Bi-Qun Zou
Known for its exceptional light-absorbing properties, conjugated organic molecule are capable of efficiently converting solar energy into chemical energy, providing a new avenue for the utilization of renewable energy. In this work, we successfully synthesized and designed a conjugated organic molecule with 4,7-di(9H-carbazol-9-yl)benzo[c][1,2,5]thiadiazole (B2Cz). In trifluoromethylation reactions, B2Cz exhibits unique activity by activating C–H bonds to selectively introduce trifluoromethyl groups. Furthermore, B2Cz acts as a photo-cocatalyst alongside NiBr2 in C–N coupling reactions, which demonstrated excellent synergistic catalytic effects. This catalytic system not only enhances reaction efficiency but also significantly advances environmental friendliness and sustainability.
{"title":"Unveiling the Synthetic Potential of Conjugated Organic Molecule as Efficient Photo-catalytic Trifluoromethylation and Photo-cocatalytic C–N Coupling Reaction","authors":"Yumin Pan, Tingting Xie, Jiming Peng, Cuihui Cao, Bi-Qun Zou","doi":"10.1007/s10562-024-04900-x","DOIUrl":"10.1007/s10562-024-04900-x","url":null,"abstract":"<div><p>Known for its exceptional light-absorbing properties, conjugated organic molecule are capable of efficiently converting solar energy into chemical energy, providing a new avenue for the utilization of renewable energy. In this work, we successfully synthesized and designed a conjugated organic molecule with 4,7-di(9<i>H</i>-carbazol-9-yl)benzo[<i>c</i>][1,2,5]thiadiazole (<b>B2Cz</b>). In trifluoromethylation reactions, <b>B2Cz</b> exhibits unique activity by activating C–H bonds to selectively introduce trifluoromethyl groups. Furthermore, <b>B2Cz</b> acts as a photo-cocatalyst alongside NiBr<sub>2</sub> in C–N coupling reactions, which demonstrated excellent synergistic catalytic effects. This catalytic system not only enhances reaction efficiency but also significantly advances environmental friendliness and sustainability.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 2","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912963","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In order to meet the increasingly stringent emission regulations for NOx in the exhaust gas of engines, selective catalytic reduction (SCR) technology is extensively studied and practiced. The key to this technology is the catalyst utilized in the chemical reactions of SCR. It is required to develop the SCR catalyst with good low-temperature performance and a wide active temperature window. A series of Cerium-based metal oxides TiCemWrO2−δ synthesized by solution combustion synthesis is studied in this paper. The SCR activity test was used to select the catalyst with the best performance. The NO conversion rate of the best catalyst in our studies reached 80% at 150 °C, kept 100% from 200 °C to 420 °C and the N2 selectivity remained above 95% for 100–500 °C. The SO2 resistance test was carried out at 250 °C and proved that our catalyst had good SO2 resistance. During the test, the NO conversion rate slightly decreased while 100 ppm SO2 was injected, but it remained above 80% for 24 h. The NO conversion rate recovered to the original value when the SO2 supply was cut off. The N2 selectivity remained at 100% throughout the process. Catalysts were characterized using BET, XRD, and SEM methods. In-situ DRIFTS method was used to study the reaction mechanism of the TiCe0.2W0.2O2−δ catalyst. It showed that the NH4+ species absorbed on the Brønsted acid played a dominant role in the SCR reactions. The bridge nitrate resulted from the NO absorption and gas phase NO was involved in the reaction. In conclusion, the mechanism studied included two routes of L-H and E-R.
{"title":"Study on Cerium-Based Catalysts TiCe0.2W0.2O2−δ for Selective Catalytic Reduction of NOx at Low Temperature","authors":"Bin Guan, Junyan Chen, Zhongqi Zhuang, Lei Zhu, Zeren Ma, Xuehan Hu, Chenyu Zhu, Sikai Zhao, Kaiyou Shu, Hongtao Dang, Junjie Gao, Luyang Zhang, Tiankui Zhu, Zhen Huang","doi":"10.1007/s10562-024-04914-5","DOIUrl":"10.1007/s10562-024-04914-5","url":null,"abstract":"<div><p>In order to meet the increasingly stringent emission regulations for NO<sub>x</sub> in the exhaust gas of engines, selective catalytic reduction (SCR) technology is extensively studied and practiced. The key to this technology is the catalyst utilized in the chemical reactions of SCR. It is required to develop the SCR catalyst with good low-temperature performance and a wide active temperature window. A series of Cerium-based metal oxides TiCe<sub>m</sub>W<sub>r</sub>O<sub>2−δ</sub> synthesized by solution combustion synthesis is studied in this paper. The SCR activity test was used to select the catalyst with the best performance. The NO conversion rate of the best catalyst in our studies reached 80% at 150 °C, kept 100% from 200 °C to 420 °C and the N<sub>2</sub> selectivity remained above 95% for 100–500 °C. The SO<sub>2</sub> resistance test was carried out at 250 °C and proved that our catalyst had good SO<sub>2</sub> resistance. During the test, the NO conversion rate slightly decreased while 100 ppm SO<sub>2</sub> was injected, but it remained above 80% for 24 h. The NO conversion rate recovered to the original value when the SO<sub>2</sub> supply was cut off. The N<sub>2</sub> selectivity remained at 100% throughout the process. Catalysts were characterized using BET, XRD, and SEM methods. In-situ DRIFTS method was used to study the reaction mechanism of the TiCe<sub>0.2</sub>W<sub>0.2</sub>O<sub>2−δ</sub> catalyst. It showed that the NH<sub>4</sub><sup>+</sup> species absorbed on the Brønsted acid played a dominant role in the SCR reactions. The bridge nitrate resulted from the NO absorption and gas phase NO was involved in the reaction. In conclusion, the mechanism studied included two routes of L-H and E-R.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 2","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142913012","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Keggin trimetallic polyoxometalates of [A-β-SiW9Fe3O37]7− and [A-β-SiW9Co3O37]10− were immobilized into the porous metal–organic framework MIL-101(Cr). The structures and properties were characterized with high-resolution transmission electron microscopies (HRTEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectrometer (EDS), Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), nitrogen adsorption–desorption isotherm and zeta potential analysis. In this approach, the SiW9Fe3O37@MIL-101 and SiW9Co3O37@MIL-101 composites were synthesized with spherical particles consisting of high surface area (the BET surface area 1368.1 and 1275.8 m2/g respectively) and uniform pore size (2.10 and 2.13 nm respectively). The SiW9Fe3O37@MIL-101 and SiW9Co3O37@MIL-101 catalysts demonstrated exceptional performance in synthesizing 5-substituted 1H tetrazoles and oxidation sulfide to sulfones. Incorporating SiW9Fe3O37 and SiW9Co3O37 polyoxometalates into the MIL-101 matrix provided a high surface area and this unique structure allowed enhanced accessibility of reactants to the catalytic sites.
{"title":"Keggin Trimetallo-POM@MIL-101(Cr), Synthesis, Characterization and Catalytic Applications","authors":"Negin Teymouri, Roushan Khoshnavazi, Somayeh Molaei, Nahid Ghadermazi","doi":"10.1007/s10562-024-04885-7","DOIUrl":"10.1007/s10562-024-04885-7","url":null,"abstract":"<div><p>The Keggin trimetallic polyoxometalates of [A-β-SiW<sub>9</sub>Fe<sub>3</sub>O<sub>37</sub>]<sup>7−</sup> and [A-β-SiW<sub>9</sub>Co<sub>3</sub>O<sub>37</sub>]<sup>10−</sup> were immobilized into the porous metal–organic framework MIL-101(Cr). The structures and properties were characterized with high-resolution transmission electron microscopies (HRTEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectrometer (EDS), Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD)<i>,</i> nitrogen adsorption–desorption isotherm and zeta potential analysis. In this approach, the SiW<sub>9</sub>Fe<sub>3</sub>O<sub>37</sub>@MIL-101 and SiW<sub>9</sub>Co<sub>3</sub>O<sub>37</sub>@MIL-101 composites were synthesized with spherical particles consisting of high surface area (the BET surface area 1368.1 and 1275.8 m<sup>2</sup>/g respectively) and uniform pore size (2.10 and 2.13 nm respectively). The SiW<sub>9</sub>Fe<sub>3</sub>O<sub>37</sub>@MIL-101 and SiW<sub>9</sub>Co<sub>3</sub>O<sub>37</sub>@MIL-101 catalysts demonstrated exceptional performance in synthesizing 5-substituted 1<i>H</i> tetrazoles and oxidation sulfide to sulfones. Incorporating SiW<sub>9</sub>Fe<sub>3</sub>O<sub>37</sub> and SiW<sub>9</sub>Co<sub>3</sub>O<sub>37</sub> polyoxometalates into the MIL-101 matrix provided a high surface area and this unique structure allowed enhanced accessibility of reactants to the catalytic sites.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 2","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-02DOI: 10.1007/s10562-024-04895-5
Tatyana S. Bogomolova, Marina Yu. Smirnova, Mikhail V. Parfenov, Svetlana V. Cherepanova, Maxim A. Panafidin, Oleg V. Klimov, Alexander S. Noskov
A series of supported Ni phosphide bifunctional hydroisomerization catalysts (Ni2P/ZSM-23/Al2O3) was synthesized by means of Ni hypophosphite reduction at different temperatures. The structure and morphology of Ni phosphide phase were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The surface chemical analysis was performed using X-ray photoelectron spectroscopy (XPS). The hydro/dehydrogenation and acid functions of catalysts were characterized by CO chemisorption, NH3-TPD and IR-spectroscopy of adsorbed pyridine (IR-Py). The reduction of supported precursor at the temperature lying in the range of 550–650 ⁰С resulted in high activity and iso-selectivity in n-decane conversion. The reduction of the supported component at 500 ⁰C or re-reduction of ex-situ reduced and passivated catalysts at 450 ⁰C led to the formation of impurities of other Ni phosphides such as NiP and Ni5P4 and had a negative impact on n-decane conversion. Both the Brønsted acidity and Ni2P dispersion of the catalysts declined with increasing Ni2P content which were accompanied by a drop in their activity without loss of iso-selectivity.
{"title":"ZSM-23-Supported Nickel Phosphide Catalysts for n-Alkane Hydroisomerization","authors":"Tatyana S. Bogomolova, Marina Yu. Smirnova, Mikhail V. Parfenov, Svetlana V. Cherepanova, Maxim A. Panafidin, Oleg V. Klimov, Alexander S. Noskov","doi":"10.1007/s10562-024-04895-5","DOIUrl":"10.1007/s10562-024-04895-5","url":null,"abstract":"<div><p>A series of supported Ni phosphide bifunctional hydroisomerization catalysts (Ni<sub>2</sub>P/ZSM-23/Al<sub>2</sub>O<sub>3</sub>) was synthesized by means of Ni hypophosphite reduction at different temperatures. The structure and morphology of Ni phosphide phase were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The surface chemical analysis was performed using X-ray photoelectron spectroscopy (XPS). The hydro/dehydrogenation and acid functions of catalysts were characterized by CO chemisorption, NH<sub>3</sub>-TPD and IR-spectroscopy of adsorbed pyridine (IR-Py). The reduction of supported precursor at the temperature lying in the range of 550–650 ⁰С resulted in high activity and iso-selectivity in n-decane conversion. The reduction of the supported component at 500 ⁰C or re-reduction of ex-situ reduced and passivated catalysts at 450 ⁰C led to the formation of impurities of other Ni phosphides such as NiP and Ni<sub>5</sub>P<sub>4</sub> and had a negative impact on n-decane conversion. Both the Brønsted acidity and Ni<sub>2</sub>P dispersion of the catalysts declined with increasing Ni<sub>2</sub>P content which were accompanied by a drop in their activity without loss of iso-selectivity.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 2","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912896","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-02DOI: 10.1007/s10562-024-04854-0
Rutuja Ganesh Maske, Pundlik Rambhau Bhagat
A convenient method for the C–N bond formation via Brønsted acid functionalized porphyrin (BAFPc) catalyzed reaction of aryl halides with benzimidazole was achieved. In this work, novel BAFPc photocatalyst bearing sulfonic acid functionality, was synthesized, and characterized using 1H NMR, 13C NMR, FT-IR, BET, and elemental analysis by SEM/EDAX. The proton level by Hammett acidity function (H0 = 0.923) and energy band gap (Eg = 1.26 eV) were determined by UV–Visible spectrophotometer. The present metal-free environmental benign route afforded C–N coupling under irradiation of LED-light in lab-made photoreactor in absence of strong base/additive at normal conditions. The photocatalytic reaction was found to be suitable with a variety of aryl halides, (X = Cl, Br) comprising activating and deactivating groups, offering the N-arylated products under given conditions affording satisfactory yield (60 and 58%). Further, this methodology can also be predominantly employed for the construction of C–N derivatives of different heterocycles under optimized conditions with good to admirable yields (49–67%). Moreover, the optimized protocol exhibited competence for C–N coupling of benzyl chloride and benzimidazole to afford drug intermediates like Chlormidazole with good yield (62%). Furthermore, BAFPc, was recycled for 6 times using model reaction supporting heterogeneous and environmental benign protocol.
{"title":"LED-Light Induced Novel Additive/Base/Metal Free Brønsted Acid Functionalized Porphyrin to Afford N-Arylated Benzimidazole","authors":"Rutuja Ganesh Maske, Pundlik Rambhau Bhagat","doi":"10.1007/s10562-024-04854-0","DOIUrl":"10.1007/s10562-024-04854-0","url":null,"abstract":"<div><p>A convenient method for the C–N bond formation via Brønsted acid functionalized porphyrin (BAFPc) catalyzed reaction of aryl halides with benzimidazole was achieved. In this work, novel BAFPc photocatalyst bearing sulfonic acid functionality, was synthesized, and characterized using <sup>1</sup>H NMR, <sup>13</sup>C NMR, FT-IR, BET, and elemental analysis by SEM/EDAX. The proton level by Hammett acidity function (H<sub>0</sub> = 0.923) and energy band gap (Eg = 1.26 eV) were determined by UV–Visible spectrophotometer. The present metal-free environmental benign route afforded C–N coupling under irradiation of LED-light in lab-made photoreactor in absence of strong base/additive at normal conditions. The photocatalytic reaction was found to be suitable with a variety of aryl halides, (X = Cl, Br) comprising activating and deactivating groups, offering the N-arylated products under given conditions affording satisfactory yield (60 and 58%). Further, this methodology can also be predominantly employed for the construction of C–N derivatives of different heterocycles under optimized conditions with good to admirable yields (49–67%). Moreover, the optimized protocol exhibited competence for C–N coupling of benzyl chloride and benzimidazole to afford drug intermediates like Chlormidazole with good yield (62%). Furthermore, BAFPc, was recycled for 6 times using model reaction supporting heterogeneous and environmental benign protocol.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 2","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912899","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
UiO–66–NH2(Ti/Zr) modified by Ti metal oxide (TiO2) was used to catalyze the hydrolysis of cellulose to prepare 5-HMF. Under the optimal reaction conditions of H2O(NaCl)/THF(1/4 mL), 190 °C, 2 h and 50 mg UNT-3(Ti/Zr) (TiO2 and UiO–66–NH2 with mass of 1.5 and 0.1 g, respectively), the yield of 5-hydroxymethylfurfural reached 59.88%. UiO–66–NH2(Ti/Zr) nanocomposites with different mass ratios were successfully prepared by simple solvent evaporation method. SEM and TEM have shown that the modified UiO–66–NH2(Ti/Zr) are wrapped into sphere by TiO2 densely attached to the surface of UiO–66–NH2, which provides favorable conditions for the uniform dispersion of TiO2 and coordination of the Lewis acidic site of UiO–66–NH2. NH3–TPD results confirmed the existence of super-strong, strong, middle and weak acid sites in UiO–66–NH2(Ti/Zr), and Py-FTIR confirmed the existence of Brønsted and Lewis acids. After four cycles, the yield of 5-HMF and FUR decreased slightly from 59.88 to 51.89% and 9.11 to 7.66%, respectively, and the yield of 5-HMF could still remain above 50%. The results showed that the modified composite treatment of TiO2 with rich Lewis acid/base and UiO–66–NH2 could provide a certain idea for the extensive application of biomass research in the future.
{"title":"Synthesis of UiO–66–NH2(Ti/Zr) and its Catalytic Conversion of Cellulose to 5-HMF","authors":"Lingling Xu, Xiaomei Pan, Lijing Gao, Ruiping Wei, Jihang Li, Xiu Wen, Yuanzhuang Li, Guomin Xiao","doi":"10.1007/s10562-024-04851-3","DOIUrl":"10.1007/s10562-024-04851-3","url":null,"abstract":"<div><p>UiO–66–NH<sub>2</sub>(Ti/Zr) modified by Ti metal oxide (TiO<sub>2</sub>) was used to catalyze the hydrolysis of cellulose to prepare 5-HMF. Under the optimal reaction conditions of H<sub>2</sub>O(NaCl)/THF(1/4 mL), 190 °C, 2 h and 50 mg UNT-3(Ti/Zr) (TiO<sub>2</sub> and UiO–66–NH<sub>2</sub> with mass of 1.5 and 0.1 g, respectively), the yield of 5-hydroxymethylfurfural reached 59.88%. UiO–66–NH<sub>2</sub>(Ti/Zr) nanocomposites with different mass ratios were successfully prepared by simple solvent evaporation method. SEM and TEM have shown that the modified UiO–66–NH<sub>2</sub>(Ti/Zr) are wrapped into sphere by TiO<sub>2</sub> densely attached to the surface of UiO–66–NH<sub>2</sub>, which provides favorable conditions for the uniform dispersion of TiO<sub>2</sub> and coordination of the Lewis acidic site of UiO–66–NH<sub>2</sub>. NH<sub>3</sub>–TPD results confirmed the existence of super-strong, strong, middle and weak acid sites in UiO–66–NH<sub>2</sub>(Ti/Zr), and Py-FTIR confirmed the existence of Brønsted and Lewis acids. After four cycles, the yield of 5-HMF and FUR decreased slightly from 59.88 to 51.89% and 9.11 to 7.66%, respectively, and the yield of 5-HMF could still remain above 50%. The results showed that the modified composite treatment of TiO<sub>2</sub> with rich Lewis acid/base and UiO–66–NH<sub>2</sub> could provide a certain idea for the extensive application of biomass research in the future.</p><h3>Graphic Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 2","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912894","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-02DOI: 10.1007/s10562-024-04899-1
Jinhai Hu, Guanhong He, Kai Zhang, Yilin Wu, Hong Yan
Photocatalysis purifies industrial paper wastewater by selectively breaking bonding bonds in lignin. To address the shortcomings of single photocatalysts such as narrow photoresponsive region, high photogenerated carrier complexation rate, and low photocatalytic activity. In this paper, Mg and N doped carbon quantum dots (Mg/N doped CQDs) were prepared by hydrothermal method. Then Zn4In2S7 series catalysts with different loadings (0, 0.3, 0.6, 1.2 wt %) of Mg/N doped CQDs (denoted as ZIS 350 °C, ZIS-3 350 °C, ZIS-6 350 °C, ZIS-12 350 °C) were constructed based on condensation reflux and inert gas calcination method. The catalyst possesses highly efficient visible light-catalyzed depolymerization of sodium lignosulfonate (SLS), an industrial waste material. From the BET curve, the specific surface area of ZIS-6 350 °C was the largest. The composite of Mg/N doped CQDs reduced the band gap of Zn4In2S7 while promoting the separation and transfer of photogenerated electrons/holes, as confirmed by DRS, Mott-Schottky, transient photocurrent and EIS analyses. From the photocatalytic activity test, the photocatalytic depolymerization of lignin by ZIS-6 350 °C was increased by 21.2% compared with that of ZIS 350 °C, and the reactions all follow the pseudo first order kinetic model. A possible photocatalytic mechanism was proposed based on the active species capture experiments.
{"title":"Novel Zn4In2S7 Loaded Mg/N Doped CQDs Composites with Improved Visible-Light Photocatalytic Properties for Depolymerization of Sodium Lignosulfonate","authors":"Jinhai Hu, Guanhong He, Kai Zhang, Yilin Wu, Hong Yan","doi":"10.1007/s10562-024-04899-1","DOIUrl":"10.1007/s10562-024-04899-1","url":null,"abstract":"<div><p>Photocatalysis purifies industrial paper wastewater by selectively breaking bonding bonds in lignin. To address the shortcomings of single photocatalysts such as narrow photoresponsive region, high photogenerated carrier complexation rate, and low photocatalytic activity. In this paper, Mg and N doped carbon quantum dots (Mg/N doped CQDs) were prepared by hydrothermal method. Then Zn<sub>4</sub>In<sub>2</sub>S<sub>7</sub> series catalysts with different loadings (0, 0.3, 0.6, 1.2 wt %) of Mg/N doped CQDs (denoted as ZIS 350 °C, ZIS-3 350 °C, ZIS-6 350 °C, ZIS-12 350 °C) were constructed based on condensation reflux and inert gas calcination method. The catalyst possesses highly efficient visible light-catalyzed depolymerization of sodium lignosulfonate (SLS), an industrial waste material. From the BET curve, the specific surface area of ZIS-6 350 °C was the largest. The composite of Mg/N doped CQDs reduced the band gap of Zn<sub>4</sub>In<sub>2</sub>S<sub>7</sub> while promoting the separation and transfer of photogenerated electrons/holes, as confirmed by DRS, Mott-Schottky, transient photocurrent and EIS analyses. From the photocatalytic activity test, the photocatalytic depolymerization of lignin by ZIS-6 350 °C was increased by 21.2% compared with that of ZIS 350 °C, and the reactions all follow the pseudo first order kinetic model. A possible photocatalytic mechanism was proposed based on the active species capture experiments.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 2","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This research introduces a groundbreaking bifunctional ionic catalyst, L-proline taurinate, synthesized in water using biodegradable materials, aligning with green chemistry principles. The structure of the synthesized catalyst was characterized using FT-IR, 1H NMR, 13C NMR, and HRMS. The ionic nature of the catalyst was validated through density functional theory analysis. The catalyst demonstrated exceptional efficiency in the green synthesis of 2-amino-3-cyano-4H-pyrans and pyran-annulated heterocyclic scaffolds. A total of 23 compounds were synthesized in less than 10 min with excellent yields (86–98%), through the Knoevenagel-Michael-cyclization coupling reaction of aldehydes, 1,3-diketones, and malononitrile. The substrate versatility was demonstrated with substituted aromatic and heterocyclic aldehydes, along with 1,3-dicarbonyl compounds like dimedone, 1,3-cyclohexanedione, and 4-hydroxy-2H-chromen-2-one, as well as barbituric acid, 2-thiobarbituric acid, and 3-methyl-1-phenyl-2-pyrazoline-5-one. This robust protocol boasts features such as one-pot, single-step, three-component operations, easy catalyst separation and recycling potential, broad applicability to various substrates, and suitability for gram-scale production. This innovative approach represents a major stride in sustainable catalytic technology and green chemical procedures, paving the way for future advancements in eco-friendly synthesis techniques.
{"title":"Synthesis and Application of L-Proline Taurinate as a Novel Bifunctional Ionic Catalyst for the Highly Efficient Synthesis of 2-Amino-3-Cyano-4H-Pyrans and Pyran-Annulated Heterocycles","authors":"Sunita Teli, Shivani Soni, Pankaj Teli, Mehul Darji, Anu Manhas, Shikha Agarwal","doi":"10.1007/s10562-024-04892-8","DOIUrl":"10.1007/s10562-024-04892-8","url":null,"abstract":"<div><p>This research introduces a groundbreaking bifunctional ionic catalyst, L-proline taurinate, synthesized in water using biodegradable materials, aligning with green chemistry principles. The structure of the synthesized catalyst was characterized using FT-IR, <sup>1</sup>H NMR, <sup>13</sup>C NMR, and HRMS. The ionic nature of the catalyst was validated through density functional theory analysis. The catalyst demonstrated exceptional efficiency in the green synthesis of 2-amino-3-cyano-4<i>H</i>-pyrans and pyran-annulated heterocyclic scaffolds. A total of 23 compounds were synthesized in less than 10 min with excellent yields (86–98%), through the Knoevenagel-Michael-cyclization coupling reaction of aldehydes, 1,3-diketones, and malononitrile. The substrate versatility was demonstrated with substituted aromatic and heterocyclic aldehydes, along with 1,3-dicarbonyl compounds like dimedone, 1,3-cyclohexanedione, and 4-hydroxy-2<i>H</i>-chromen-2-one, as well as barbituric acid, 2-thiobarbituric acid, and 3-methyl-1-phenyl-2-pyrazoline-5-one. This robust protocol boasts features such as one-pot, single-step, three-component operations, easy catalyst separation and recycling potential, broad applicability to various substrates, and suitability for gram-scale production. This innovative approach represents a major stride in sustainable catalytic technology and green chemical procedures, paving the way for future advancements in eco-friendly synthesis techniques.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 2","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142913043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-02DOI: 10.1007/s10562-024-04893-7
Sukanya Sharma, Vrinda Sharma, Surbhi Sharma, Gunjan Vaid, Satya Paul
In the pursuit of advanced catalytic materials, the synergistic integration of diverse components within a single platform has emerged as a transformative strategy. This paper unveils the synthesis of Cu nanoparticles immobilized on different magnetic metal–organic frameworks [NH2-MIL-101(Fe), MIL-101(Fe) and MIL-101(Cr)]. The main focus of the present work is to study the effect of different metal ion and ligand of the framework on the catalytic activity of Cu nanoparticles. The catalytic potential of synthesized catalysts was compared for C–N coupling and reductive degradation of organic dyes. Among the three synthesized catalysts, Cu@NH2-MIL-101(Fe)/Fe3O4 demonstrated high activity attributed to the synergistic interaction between NH2-MIL-101(Fe) and Cu as well as due to higher immobilization of catalytically active Cu nanoparticles. The catalyst offered virtues like mild reaction conditions, magnetically separable, ligand-free conditions, high product yield; and turnover number in the range of 3.68 to 5.46. Moreover, the catalyst maintains its structural integrity, chemical properties and effective magnetic response after five catalytic cycles, as demonstrated by FTIR, XRD, XPS and VSM analysis of the recycled catalyst.
{"title":"Cu Nanoparticles Decorated on Magnetic NH2-MIL-101(Fe): A Highly Active Catalyst for C–N Coupling and Reductive Degradation of Dyes","authors":"Sukanya Sharma, Vrinda Sharma, Surbhi Sharma, Gunjan Vaid, Satya Paul","doi":"10.1007/s10562-024-04893-7","DOIUrl":"10.1007/s10562-024-04893-7","url":null,"abstract":"<div><p>In the pursuit of advanced catalytic materials, the synergistic integration of diverse components within a single platform has emerged as a transformative strategy. This paper unveils the synthesis of Cu nanoparticles immobilized on different magnetic metal–organic frameworks [NH<sub>2</sub>-MIL-101(Fe), MIL-101(Fe) and MIL-101(Cr)]. The main focus of the present work is to study the effect of different metal ion and ligand of the framework on the catalytic activity of Cu nanoparticles. The catalytic potential of synthesized catalysts was compared for C–N coupling and reductive degradation of organic dyes. Among the three synthesized catalysts, Cu@NH<sub>2</sub>-MIL-101(Fe)/Fe<sub>3</sub>O<sub>4</sub> demonstrated high activity attributed to the synergistic interaction between NH<sub>2</sub>-MIL-101(Fe) and Cu as well as due to higher immobilization of catalytically active Cu nanoparticles. The catalyst offered virtues like mild reaction conditions, magnetically separable, ligand-free conditions, high product yield; and turnover number in the range of 3.68 to 5.46. Moreover, the catalyst maintains its structural integrity, chemical properties and effective magnetic response after five catalytic cycles, as demonstrated by FTIR, XRD, XPS and VSM analysis of the recycled catalyst.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 2","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912893","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The SnO2/SnS2 composite photocatalyst with mesoporous structure and Type-II heterojunction was successfully constructed, and sulfonamide antibiotics were used as the target degrader to explore the effects of mesoporous and heterojunction structures in SnO2/SnS2 on the photocatalytic degradation activity under visible light irradiation. The results show that SnO2/SnS2 obtained by hydrothermal reaction at 180 °C presents a unique flower-like spherical structure with high crystallinity and a particle size of about 5 μm, a large mesoporous pore size of 12.33 nm provided abundant ion or molecular channels and a relatively high specific surface area of 50 m2·g− 1 provided abundant active sites. In addition, SnO2/SnS2 has low fluorescence intensity, indicating that the Type-II heterojunction structure formed promoted charge transfer, resulting in a higher separation efficiency of photo-generated charges (h+/e−). It is worth noting that SnO2/SnS2 has a strong light response at the wavelength of 200–800 nm, and degradation rate of SnO2/SnS2 was 1.7 times that of SnO2 and 1.5 times that of SnS2, after photocatalytic reaction time of 210 min, respectively. It is benefitting from that the Type-II heterojunction structure formed by the coupling of mesoporous SnO2 and SnS2 has a synergistic effect, which reduces the band gap and improves the photocatalytic activity. Furthermore, this study revealed that the reaction rate constant of SnO2/SnS2 photocatalytic degradation of sulfonamides increased with the increase of temperature, which belonged to the zero-order reaction with the apparent activation energy of (:1.201 times 10^{4})J·mol− 1. Finally, the photocatalytic stability and reusability of SnO2/SnS2 were further confirmed through 5 cycles of photocatalytic degradation experiments. This study provides new insights for the development of heterojunction photocatalysts with mesoporous structure, and provide new ideas for photocatalytic technology in antibiotic degradation.
Graphical abstract
成功构建了具有介孔结构和ii型异质结的SnO2/SnS2复合光催化剂，并以磺胺类抗生素为目标降解剂，探讨了SnO2/SnS2中介孔和异质结结构对可见光下光催化降解活性的影响。结果表明，在180℃水热条件下制备的SnO2/SnS2具有独特的花状球形结构，结晶度高，粒径约为5 μm， 12.33 nm的大介孔孔径提供了丰富的离子或分子通道，50 m2·g−1的相对高比表面积提供了丰富的活性位点。此外，SnO2/SnS2具有较低的荧光强度，说明ii型异质结结构形成了促进电荷转移的结构，使得光生电荷（h+/e−）的分离效率更高。值得注意的是，SnO2/SnS2在200-800 nm波长处具有较强的光响应，光催化反应时间为210 min后，SnO2/SnS2的降解率分别是SnO2的1.7倍和SnS2的1.5倍。得益于介孔SnO2与SnS2偶联形成的ii型异质结结构具有协同效应，减小了带隙，提高了光催化活性。研究还发现，SnO2/SnS2光催化降解磺胺类化合物的反应速率常数随着温度的升高而增大，属于零级反应，表观活化能为(:1.201 times 10^{4}) J·mol−1。最后，通过5个循环的光催化降解实验进一步证实了SnO2/SnS2的光催化稳定性和可重复使用性。本研究为开发具有介孔结构的异质结光催化剂提供了新的思路，并为光催化技术在抗生素降解中的应用提供了新的思路。图形摘要
{"title":"SnO2/SnS2 Heterojunction with Mesoporous Structure for Improved Photocatalytic Degradation of Sulfonamide Antibiotics","authors":"Zhanyu Li, Pengyu Li, Yike Fang, Bingxu Chen, Danfeng He, Wei Sun, Guohui Li, Yuanyuan Sun","doi":"10.1007/s10562-024-04883-9","DOIUrl":"10.1007/s10562-024-04883-9","url":null,"abstract":"<div><p>The SnO<sub>2</sub>/SnS<sub>2</sub> composite photocatalyst with mesoporous structure and Type-II heterojunction was successfully constructed, and sulfonamide antibiotics were used as the target degrader to explore the effects of mesoporous and heterojunction structures in SnO<sub>2</sub>/SnS<sub>2</sub> on the photocatalytic degradation activity under visible light irradiation. The results show that SnO<sub>2</sub>/SnS<sub>2</sub> obtained by hydrothermal reaction at 180 °C presents a unique flower-like spherical structure with high crystallinity and a particle size of about 5 μm, a large mesoporous pore size of 12.33 nm provided abundant ion or molecular channels and a relatively high specific surface area of 50 m<sup>2</sup><b>·</b>g<sup>− 1</sup> provided abundant active sites. In addition, SnO<sub>2</sub>/SnS<sub>2</sub> has low fluorescence intensity, indicating that the Type-II heterojunction structure formed promoted charge transfer, resulting in a higher separation efficiency of photo-generated charges (h<sup>+</sup>/e<sup>−</sup>). It is worth noting that SnO<sub>2</sub>/SnS<sub>2</sub> has a strong light response at the wavelength of 200–800 nm, and degradation rate of SnO<sub>2</sub>/SnS<sub>2</sub> was 1.7 times that of SnO<sub>2</sub> and 1.5 times that of SnS<sub>2</sub>, after photocatalytic reaction time of 210 min, respectively. It is benefitting from that the Type-II heterojunction structure formed by the coupling of mesoporous SnO<sub>2</sub> and SnS<sub>2</sub> has a synergistic effect, which reduces the band gap and improves the photocatalytic activity. Furthermore, this study revealed that the reaction rate constant of SnO<sub>2</sub>/SnS<sub>2</sub> photocatalytic degradation of sulfonamides increased with the increase of temperature, which belonged to the zero-order reaction with the apparent activation energy of <span>(:1.201 times 10^{4})</span>J·mol<sup>− 1</sup>. Finally, the photocatalytic stability and reusability of SnO<sub>2</sub>/SnS<sub>2</sub> were further confirmed through 5 cycles of photocatalytic degradation experiments. This study provides new insights for the development of heterojunction photocatalysts with mesoporous structure, and provide new ideas for photocatalytic technology in antibiotic degradation.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 2","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912930","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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