Wei Rao, Yifan Jiang, Qiong Liu, Junjun Zhang, Die He, Rong Chen
While high-valent copper intermediates are pivotal for efficient peroxydisulfate (PDS) activation, their generation and role in heterogeneous catalysis remain unclear. Herein, we demonstrate that a nonstoichiometric Cu0.84Bi2.08O4 catalyst enables the dark activation of PDS via a novel pathway dominated by a surface-bound Cu(III)-peroxo intermediate (≡Cu(III)-O−O−SO3). A suite of spectroscopic and chemical probes revealed that this Cu(III)-peroxo species, along with superoxide radicals (•O2−), acts as the primary oxidant, enabling the highly selective and rapid degradation of bisphenol A (BPA) and other phenolic pollutants. Furthermore, H2O2 generated from PDS hydrolysis synergistically participates in the reaction, accounting for the exceptionally high PDS utilization efficiency of the system. The system exhibits remarkable robustness, maintaining high activity over a wide pH range (4–11) and demonstrating strong resistance to interference from ions. This study elucidates a distinct Cu(III)-peroxo-mediated mechanism and offers a new strategy for designing highly selective catalysts for environmental remediation.
{"title":"Nonstoichiometric Copper Bismuth Oxide Catalyst Boosting Surface-Bound Cu(III)-Peroxo Intermediate for Selective Oxidation via Dark Peroxydisulfate Activation","authors":"Wei Rao, Yifan Jiang, Qiong Liu, Junjun Zhang, Die He, Rong Chen","doi":"10.1002/adsc.70307","DOIUrl":"https://doi.org/10.1002/adsc.70307","url":null,"abstract":"While high-valent copper intermediates are pivotal for efficient peroxydisulfate (PDS) activation, their generation and role in heterogeneous catalysis remain unclear. Herein, we demonstrate that a nonstoichiometric Cu<sub>0.84</sub>Bi<sub>2.08</sub>O<sub>4</sub> catalyst enables the dark activation of PDS via a novel pathway dominated by a surface-bound Cu(III)-peroxo intermediate (<b>≡</b>Cu(III)-O−O−SO<sub>3</sub>). A suite of spectroscopic and chemical probes revealed that this Cu(III)-peroxo species, along with superoxide radicals (•O<sub>2</sub><sup>−</sup>), acts as the primary oxidant, enabling the highly selective and rapid degradation of bisphenol A (BPA) and other phenolic pollutants. Furthermore, H<sub>2</sub>O<sub>2</sub> generated from PDS hydrolysis synergistically participates in the reaction, accounting for the exceptionally high PDS utilization efficiency of the system. The system exhibits remarkable robustness, maintaining high activity over a wide pH range (4–11) and demonstrating strong resistance to interference from ions. This study elucidates a distinct Cu(III)-peroxo-mediated mechanism and offers a new strategy for designing highly selective catalysts for environmental remediation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"348 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuping Wu, Xinyu Du, Yaoguo Wang, Zixin Feng, YunRu Ma, Yingying Fan, Li Niu
Constructing polymer photocatalysts that can concurrently accomplish charge transfer and mass transport to catalytic sites remains a formidable task. In this study, by cross-linking electron-rich polyphenol and electron-poor phenothiazine units, two hydrophilic and porous organic polymer photocatalysts characterized by densely packed donor–acceptor units are deliberately designed. The hydrophilic phenolic hydroxyl group in the donor moiety and the aperture channel neighboring the acceptor unit facilitate the capture of water and oxygen at the catalytic site. Meanwhile, the donor–acceptor columns serve as charge supply chains and numerous water oxidation and oxygen reduction centers. These photocatalysts are used for the photocatalytic synthesis of hydrogen peroxide from water and oxygen without the use of sacrificial reagents. Therein, the polymer containing tetramethyl groups shows high selectivity for the photogeneration of hydrogen peroxide, achieving a yield rate of 691.3 μmol g−1 h−1 (16.73 mM g−1) and an apparent quantum yield (AQY) of 11.9% under 630 nm irradiation. This organic polymer catalyst system exhibits considerable potential as a promising artificial photosynthesis system capable of realizing simultaneous charge transfer and mass transfer.
构建能够同时完成电荷转移和质量传递到催化位点的聚合物光催化剂仍然是一项艰巨的任务。在这项研究中，通过交联富电子多酚和贫电子吩噻嗪单元，故意设计了两种亲水性和多孔的有机聚合物光催化剂，其特征是密集排列的供体-受体单元。供体部分的亲水酚羟基和邻近受体单元的孔径通道有助于在催化位点捕获水和氧。同时，供体-受体柱作为电荷供应链和众多的水氧化和氧还原中心。这些光催化剂用于水和氧的光催化合成过氧化氢，而不使用牺牲试剂。其中，含四甲基的聚合物对过氧化氢的光生成表现出较高的选择性，在630 nm辐照下的产率为691.3 μmol g−1 h−1 (16.73 mM g−1)，表观量子产率（AQY）为11.9%。该有机聚合物催化剂体系作为一种有潜力的人工光合作用体系，能够同时实现电荷传递和质量传递。
{"title":"Organic Polymers Enabling Concurrent Charge and Mass Transfer for Photocatalytic Hydrogen Peroxide Synthesis","authors":"Yuping Wu, Xinyu Du, Yaoguo Wang, Zixin Feng, YunRu Ma, Yingying Fan, Li Niu","doi":"10.1002/adsc.70348","DOIUrl":"https://doi.org/10.1002/adsc.70348","url":null,"abstract":"Constructing polymer photocatalysts that can concurrently accomplish charge transfer and mass transport to catalytic sites remains a formidable task. In this study, by cross-linking electron-rich polyphenol and electron-poor phenothiazine units, two hydrophilic and porous organic polymer photocatalysts characterized by densely packed donor–acceptor units are deliberately designed. The hydrophilic phenolic hydroxyl group in the donor moiety and the aperture channel neighboring the acceptor unit facilitate the capture of water and oxygen at the catalytic site. Meanwhile, the donor–acceptor columns serve as charge supply chains and numerous water oxidation and oxygen reduction centers. These photocatalysts are used for the photocatalytic synthesis of hydrogen peroxide from water and oxygen without the use of sacrificial reagents. Therein, the polymer containing tetramethyl groups shows high selectivity for the photogeneration of hydrogen peroxide, achieving a yield rate of 691.3 μmol g<sup>−1</sup> h<sup>−1</sup> (16.73 mM g<sup>−1</sup>) and an apparent quantum yield (AQY) of 11.9% under 630 nm irradiation. This organic polymer catalyst system exhibits considerable potential as a promising artificial photosynthesis system capable of realizing simultaneous charge transfer and mass transfer.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"57 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319851","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rare-earth metal–organic frameworks (RE-MOFs) featuring tunable coordination environments and unique 4f electronic configurations hold great potential for photocatalytic applications. Nevertheless, their efficiency is often limited by rapid charge recombination. Herein, a series of RE-MOFs were synthesized via solvothermal reactions using 2′-amino-[1,1′:4′,1″-terphenyl]−3,3″,5,5″-tetracarboxylic acid (NH2-H4TPTC) as the organic linker and erbium/holmium (Er3+/Ho3+) as metal nodes and further integrated with CdS nanoparticles via a precipitation strategy to construct RE-MOF/CdS heterostructures. Comprehensive characterization verified the successful formation and stability of the composites. Under visible-light irradiation from a 300 W xenon lamp over 3 h, both Er-NH2-TPTC/CdS and Ho-NH2-TPTC/CdS exhibited significantly enhanced photocatalytic hydrogen evolution compared with pristine CdS. The optimized Ho-NH2-TPTC/CdS (20 wt%) composite achieved a hydrogen evolution rate of 11 408 μmol·g−1, representing an 8.6-fold enhancement over pristine CdS. Mechanistic analyses revealed that the intimate RE–MOF/CdS interface facilitates efficient charge separation and transfer, thereby suppressing electron–hole recombination. This study demonstrates a rational strategy for constructing high-performance RE-MOF-semiconductor heterostructures and provides new insight into the design of rare-earth-based photocatalysts for solar hydrogen production.
{"title":"Rare-Earth Metal–Organic Framework/CdS Heterostructures for Highly Efficient Photocatalytic Hydrogen Evolution","authors":"Si-Yuan Cheng, Yi Cheng, Chen-Xi Li, Yu-Shu Cai, Jun-Feng Qian, Zhong-Hua Sun, Ji-Ye Zhang, Qun Chen, Liang Wang, Zhi-Hui Zhang","doi":"10.1002/adsc.70357","DOIUrl":"https://doi.org/10.1002/adsc.70357","url":null,"abstract":"Rare-earth metal–organic frameworks (RE-MOFs) featuring tunable coordination environments and unique 4f electronic configurations hold great potential for photocatalytic applications. Nevertheless, their efficiency is often limited by rapid charge recombination. Herein, a series of RE-MOFs were synthesized via solvothermal reactions using 2′-amino-[1,1′:4′,1″-terphenyl]−3,3″,5,5″-tetracarboxylic acid (NH<sub>2</sub>-H<sub>4</sub>TPTC) as the organic linker and erbium/holmium (Er<sup>3+</sup>/Ho<sup>3+</sup>) as metal nodes and further integrated with CdS nanoparticles via a precipitation strategy to construct RE-MOF/CdS heterostructures. Comprehensive characterization verified the successful formation and stability of the composites. Under visible-light irradiation from a 300 W xenon lamp over 3 h, both Er-NH<sub>2</sub>-TPTC/CdS and Ho-NH<sub>2</sub>-TPTC/CdS exhibited significantly enhanced photocatalytic hydrogen evolution compared with pristine CdS. The optimized Ho-NH<sub>2</sub>-TPTC/CdS (20 wt%) composite achieved a hydrogen evolution rate of 11 408 μmol·g<sup>−1</sup>, representing an 8.6-fold enhancement over pristine CdS. Mechanistic analyses revealed that the intimate RE–MOF/CdS interface facilitates efficient charge separation and transfer, thereby suppressing electron–hole recombination. This study demonstrates a rational strategy for constructing high-performance RE-MOF-semiconductor heterostructures and provides new insight into the design of rare-earth-based photocatalysts for solar hydrogen production.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319896","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhengmei Wang, Xuan Wu, Xiaolong Hao, Qinghao Wang, Lirong Yao, Jincai Wu, Xiaobo Pan
Furfural (FAL), a key biomass-derived platform compound, upgrading to furfuryl alcohol (FOL) relies heavily on transition metal catalysts, which suffer from high cost, toxicity, and harsh reaction conditions. Herein, we developed a metal-free heterogeneous catalyst (PCOFs-BCF) by synthesizing quinoline-linked phosphorus-containing covalent organic frameworks (PCOFs), then postmodifying tris(pentafluorophenyl)borane (BCF) to construct frustrated Lewis pairs (FLPs). Phenylsilane as reducing agent and water as coreagent, PCOFs-BCF achieved excellent conversion and yield, outperforming homogeneous FLPs and phosphine-free analogs. Mechanistic studies confirmed that FLPs activate phenylsilane to generate hydrides for FAL carbonyl reduction, while water provides protons for silyl ether hydrolysis to FOL. This work offers a recyclable FLP catalyst strategy for sustainable biomass FAL valorization.
{"title":"Construction of Frustrated Lewis Pairs on Covalent Organic Framework for Water-Assisted Catalytic Hydrogenation of Furfural Compounds","authors":"Zhengmei Wang, Xuan Wu, Xiaolong Hao, Qinghao Wang, Lirong Yao, Jincai Wu, Xiaobo Pan","doi":"10.1002/adsc.70328","DOIUrl":"https://doi.org/10.1002/adsc.70328","url":null,"abstract":"Furfural (FAL), a key biomass-derived platform compound, upgrading to furfuryl alcohol (FOL) relies heavily on transition metal catalysts, which suffer from high cost, toxicity, and harsh reaction conditions. Herein, we developed a metal-free heterogeneous catalyst (PCOFs-BCF) by synthesizing quinoline-linked phosphorus-containing covalent organic frameworks (PCOFs), then postmodifying tris(pentafluorophenyl)borane (BCF) to construct frustrated Lewis pairs (FLPs). Phenylsilane as reducing agent and water as coreagent, PCOFs-BCF achieved excellent conversion and yield, outperforming homogeneous FLPs and phosphine-free analogs. Mechanistic studies confirmed that FLPs activate phenylsilane to generate hydrides for FAL carbonyl reduction, while water provides protons for silyl ether hydrolysis to FOL. This work offers a recyclable FLP catalyst strategy for sustainable biomass FAL valorization.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"98 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kamal Kant, Dhananjaya Kaldhi, Ahanthem Sonia, Jyoti, Priyadarshini Naik, Arup K. Kabi, Virender Singh, Chandi C. Malakar, Reda A. Haggam
We present a unified and operationally straightforward strategy for the direct synthesis of azide and aryltriazole derivatives under nitrite-free conditions. This dual catalytic platform encompasses two mechanistically distinct pathways: (i) a potassium iodide-catalyzed protocol involving the in situ generation of nitrous acid from hydroxylamine hydrochloride and tert-butyl hydroperoxide, mediated by catalytically generated iodine (I2), which facilitates the diazotization of primary amines followed by NN bond formation to furnish azide motifs; and (ii) an iron(III)-catalyzed transformation that bypasses conventional diazonium intermediates, promoting intramolecular cyclization of hydroxylamine-derived species to access aryltriazoles. Both approaches obviate the need for traditional nitrite salts or preformed azide reagents, offering a metal-efficient and environmentally benign alternative. The methodology demonstrates broad substrate scope across aromatic and aliphatic amines, affording structurally diverse nitrogen-rich products in yields of up to 93%. By eliminating reliance on hazardous nitrite-based reagents, this work provides a sustainable and versatile platform for the synthesis of valuable azide-containing scaffolds with broad synthetic applicability.
{"title":"Direct Conversion of Amines to Organic Azides Under Nitrite-Free Conditions Enabled by In Situ Nitrous Acid Formation","authors":"Kamal Kant, Dhananjaya Kaldhi, Ahanthem Sonia, Jyoti, Priyadarshini Naik, Arup K. Kabi, Virender Singh, Chandi C. Malakar, Reda A. Haggam","doi":"10.1002/adsc.70345","DOIUrl":"https://doi.org/10.1002/adsc.70345","url":null,"abstract":"We present a unified and operationally straightforward strategy for the direct synthesis of azide and aryltriazole derivatives under nitrite-free conditions. This dual catalytic platform encompasses two mechanistically distinct pathways: (i) a potassium iodide-catalyzed protocol involving the in situ generation of nitrous acid from hydroxylamine hydrochloride and <i>tert-</i>butyl hydroperoxide, mediated by catalytically generated iodine (I<sub>2</sub>), which facilitates the diazotization of primary amines followed by N<span></span>N bond formation to furnish azide motifs; and (ii) an iron(III)-catalyzed transformation that bypasses conventional diazonium intermediates, promoting intramolecular cyclization of hydroxylamine-derived species to access aryltriazoles. Both approaches obviate the need for traditional nitrite salts or preformed azide reagents, offering a metal-efficient and environmentally benign alternative. The methodology demonstrates broad substrate scope across aromatic and aliphatic amines, affording structurally diverse nitrogen-rich products in yields of up to 93%. By eliminating reliance on hazardous nitrite-based reagents, this work provides a sustainable and versatile platform for the synthesis of valuable azide-containing scaffolds with broad synthetic applicability.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"52 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Catalytic processes utilizing air as an environmentally benign oxidizing agent and acid catalysts offer significant advantages in converting renewable or sustainable carbohydrate feedstocks into high-value chemical compounds. Herein, a remarkably efficient and innovative Brønsted acid-catalyzed system has been developed, utilizing air as the sole oxidant, completely devoid of transition metals or costly oxidizing reagents. The system enables oxidative C−C/H activation and N-formamidation of amine and dextrose with notable efficiency synthesis of a diverse array of formamides while achieving impressive turnover numbers (TON = 91,455). Labeling studies have demonstrated that the carbon atom in the aldehyde group originates from the C1 position of dextrose, the hydrogen atoms are derived from the C−H bonds position within the dextrose skeleton, the H atom in the amide (NH) group originates from a hydroxyl group of dextrose, and the oxygen atom is derived from atmospheric O2. Mechanistic investigations have revealed that acidic conditions significantly promote the oxidation of dextrose by molecular oxygen.
{"title":"Insights Into the Carbohydrates Synthon in Brønsted Acid Catalyzed N-Formylation","authors":"Wenbin Zhang, Rui Liu, Xiulin Li, Ali Ramazani, Runhua Liao, Guoying Zhang","doi":"10.1002/adsc.70333","DOIUrl":"https://doi.org/10.1002/adsc.70333","url":null,"abstract":"Catalytic processes utilizing air as an environmentally benign oxidizing agent and acid catalysts offer significant advantages in converting renewable or sustainable carbohydrate feedstocks into high-value chemical compounds. Herein, a remarkably efficient and innovative Brønsted acid-catalyzed system has been developed, utilizing air as the sole oxidant, completely devoid of transition metals or costly oxidizing reagents. The system enables oxidative C−C/H activation and <i>N</i>-formamidation of amine and dextrose with notable efficiency synthesis of a diverse array of formamides while achieving impressive turnover numbers (TON = 91,455). Labeling studies have demonstrated that the carbon atom in the aldehyde group originates from the C1 position of dextrose, the hydrogen atoms are derived from the C−H bonds position within the dextrose skeleton, the H atom in the amide (NH) group originates from a hydroxyl group of dextrose, and the oxygen atom is derived from atmospheric O<sub>2</sub>. Mechanistic investigations have revealed that acidic conditions significantly promote the oxidation of dextrose by molecular oxygen.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"3 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The direct and selective modification of glycine derivatives has garnered significant attention interest in recent years, owing to the prevalence of the glycine motif in bioactive peptides. In this study, we present the first example of direct CC bond formation via carbonylation of glycine ester with 3-(2-Isocyanoethyl)indoles to furnish β-ketoamino ester derivatives. This transformation proceeds efficiently under visible-light irradiation using Rose Bengal B as an organic photosensitizer, exhibits broad functional group compatibility, and delivers the desired products in 60%–72% yields. Preliminary mechanistic investigations suggest that the reaction proceeds through a reductive quenching pathway, in which an in situ-generated iminium ion intermediate undergoes nucleophilic addition to afford the final products. Overall, this strategy provides a practical, efficient, and straightforward approach to the synthesis of β-ketoamino ester derivatives.
{"title":"Harnessing Photoredox Catalysis to Access β-Ketoamino Esters from 3-(2-Isocyanoethyl)indoles","authors":"Vadithya Ranga Rao, Chelukalapally Anil Kumar, Vadla Shiva Prasad, Dharavath Ravi, Silari MohanaKrishna, Madasu Gangaraju, Praveen Reddy Adiyala","doi":"10.1002/adsc.70334","DOIUrl":"https://doi.org/10.1002/adsc.70334","url":null,"abstract":"The direct and selective modification of glycine derivatives has garnered significant attention interest in recent years, owing to the prevalence of the glycine motif in bioactive peptides. In this study, we present the first example of direct C<span></span>C bond formation <i>via</i> carbonylation of glycine ester with 3-(2-Isocyanoethyl)indoles to furnish <i>β</i>-ketoamino ester derivatives. This transformation proceeds efficiently under visible-light irradiation using Rose Bengal B as an organic photosensitizer, exhibits broad functional group compatibility, and delivers the desired products in 60%–72% yields. Preliminary mechanistic investigations suggest that the reaction proceeds through a reductive quenching pathway, in which an in situ<i>-</i>generated iminium ion intermediate undergoes nucleophilic addition to afford the final products. Overall, this strategy provides a practical, efficient, and straightforward approach to the synthesis of <i>β</i>-ketoamino ester derivatives.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"24 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A visible-light-driven, photocatalyst-free 6π-photocyclization of N-substituted dieneamines has been developed. Various polysubstituted cyanodihydropyrroles and cyanopyrroles were constructed in good-to-excellent yields under nitrogen or air atmosphere. This novel strategy features formal hydroalkenylation, divergent synthesis, excellent regioselectivity, wide functional group tolerance, and operational convenience. Mechanistic studies suggest that both the 1,4-H shift of the diradical intermediate and the deprotonation/protonation processes may be involved in the transformation.
{"title":"\u0000Photocatalyst-Free, Visible Light-Driven 6π-Photocyclization: A Facile Access to Multisubstituted Cyanodihydropyrroles and Cyanopyrroles","authors":"Jie Yang, Jing Xie, Daohong Yu, Wenjun Luo, Jinbin Zhu, Lipeng Long, Haiqing Luo, Wei Guo, Zhongxia Wang, Zhengwang Chen","doi":"10.1002/adsc.70294","DOIUrl":"https://doi.org/10.1002/adsc.70294","url":null,"abstract":"A visible-light-driven, photocatalyst-free 6π-photocyclization of <i>N</i>-substituted dieneamines has been developed. Various polysubstituted cyanodihydropyrroles and cyanopyrroles were constructed in good-to-excellent yields under nitrogen or air atmosphere. This novel strategy features formal hydroalkenylation, divergent synthesis, excellent regioselectivity, wide functional group tolerance, and operational convenience. Mechanistic studies suggest that both the 1,4-H shift of the diradical intermediate and the deprotonation/protonation processes may be involved in the transformation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"291 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147287332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Getachew Alemu Tenkolu, Aikun Tang, Tao Cai, Qiang Ni, Han Zhang
Considering the explosive characteristics of hydrogen and the importance of preventing leakage, achieving controlled low-temperature combustion ensures both environmental safety and operational stability. Low-temperature catalytic combustion provides an effective solution to reduce hazardous pollutant formation during the hydrogen reaction. In this article, a spinel-based catalyst modified by partial substitution with transition metals (M) is prepared and doped with bimetallic Pt:Cu to enhance hydrogen catalytic combustion. The doped composite spinel Co1-xMxAl2O4 catalyst, where M represents Fe, Ti, and Mn, is synthesized using wet impregnation followed by a polyethylene glycol (PEG)-assisted sol–gel doping method to obtain a PtCu/Co0.8Fe0.2Al2O4 catalyst. Combining performance testing and material characterization, Fe-modified spinel exhibited a larger specific surface area of 31.63 m2/g compared to 30.46 m2/g, lowered activation energy from 57.8 to 46.9 kJ/mol, achieving a T90 at 349°C compared to 374.3°C for original CoAl2O4. Meanwhile, the bimetallic Pt 1%-Cu 4%/Co0.8Fe0.2Al2O4 catalyst exhibits excellent activity with T50 at 37.07°C and T90 at 43.34°C, attributed to a minimum activation energy of 32 kJ/mol. The synergistic effect at 4% and 5% Cu loadings is supported by high metal dispersion and structural stability of the Fe-modified spinel matrix, enabling room-temperature combustion initiation. This enhanced catalytic activity results from strong Pt–Cu bimetallic interactions, promoting efficient hydrogen dissociation while increasing oxygen vacancy formation and lattice oxygen mobility, as revealed by X-ray photoelectron spectroscopy, temperature-programed reduction, and thermogravimetric analysis. Overall, the enhanced low-temperature hydrogen combustion performance is comparable to standard precious metal catalysts, referencing the multimetallic effect on fuel utilization efficiency.
{"title":"Tailoring Bimetallic Pt–Cu Trace Doping on Composite Spinel for Enhanced Low-Temperature Hydrogen Catalytic Combustion Performance","authors":"Getachew Alemu Tenkolu, Aikun Tang, Tao Cai, Qiang Ni, Han Zhang","doi":"10.1002/adsc.70330","DOIUrl":"https://doi.org/10.1002/adsc.70330","url":null,"abstract":"Considering the explosive characteristics of hydrogen and the importance of preventing leakage, achieving controlled low-temperature combustion ensures both environmental safety and operational stability. Low-temperature catalytic combustion provides an effective solution to reduce hazardous pollutant formation during the hydrogen reaction. In this article, a spinel-based catalyst modified by partial substitution with transition metals (M) is prepared and doped with bimetallic Pt:Cu to enhance hydrogen catalytic combustion. The doped composite spinel Co<sub>1-x</sub>M<sub><i>x</i></sub>Al<sub>2</sub>O<sub>4</sub> catalyst, where M represents Fe, Ti, and Mn, is synthesized using wet impregnation followed by a polyethylene glycol (PEG)-assisted sol–gel doping method to obtain a PtCu/Co<sub>0.8</sub>Fe<sub>0.2</sub>Al<sub>2</sub>O<sub>4</sub> catalyst. Combining performance testing and material characterization, Fe-modified spinel exhibited a larger specific surface area of 31.63 m<sup>2</sup>/g compared to 30.46 m<sup>2</sup>/g, lowered activation energy from 57.8 to 46.9 kJ/mol, achieving a T<sub>90</sub> at 349°C compared to 374.3°C for original CoAl<sub>2</sub>O<sub>4</sub>. Meanwhile, the bimetallic Pt 1%-Cu 4%/Co<sub>0.8</sub>Fe<sub>0.2</sub>Al<sub>2</sub>O<sub>4</sub> catalyst exhibits excellent activity with T<sub>50</sub> at 37.07°C and T<sub>90</sub> at 43.34°C, attributed to a minimum activation energy of 32 kJ/mol. The synergistic effect at 4% and 5% Cu loadings is supported by high metal dispersion and structural stability of the Fe-modified spinel matrix, enabling room-temperature combustion initiation. This enhanced catalytic activity results from strong Pt–Cu bimetallic interactions, promoting efficient hydrogen dissociation while increasing oxygen vacancy formation and lattice oxygen mobility, as revealed by X-ray photoelectron spectroscopy, temperature-programed reduction, and thermogravimetric analysis. Overall, the enhanced low-temperature hydrogen combustion performance is comparable to standard precious metal catalysts, referencing the multimetallic effect on fuel utilization efficiency.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"14 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147292545","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
H. K. Meghana, S. Sujith, M. Harsha, G. Manjunatha Reddy, Naresh Nalajala, Ganapati V. Shanbhag
We selectively synthesized a less explored furan-2-ylmethylmethyl carbonate (FMMC), a potential green solvent and fuel additive via carboxymethylation of furfuryl alcohol with dimethyl carbonate. A defect-engineered UiO-66 MOF catalyst was employed for this transformation, and its activity was benchmarked against conventional catalysts such as H-ZSM-5, H-Beta, and Amberlyst-15. The nature of the active sites instrumental in obtaining high FMMC selectivity was emphasized by the variation in turnover numbers. The in situ approach of tailoring missing linker defects in the UiO-66 MOF was achieved with monocarboxylic acid modulators, formic acid and acetic acid. The catalysts were comprehensively characterized for the structural properties by PXRD, N2 sorption, and FESEM, and the intrinsic active sites were investigated with techniques such as EPR, FTIR, TGA, and acid–base titrations. The defective UiO-66 MOF demonstrated superior catalytic activity owing to the presence of a higher number of weak Brönsted acidic sites. The selective masking of Brönsted and Lewis acidic sites were studied by treating it with 2,6-lutidine and KSCN respectively and their effect on the catalytic activity was examined. A Central Composite Design (CCD) model was designed to obtain the high FMMC yield under optimized conditions. The catalyst gave 87.3% furfuryl alcohol conversion and 95.2% FMMC selectivity. The leaching and recyclability experiments showed that the catalyst was truly heterogeneous, and it was recyclable up to five consecutive cycles. The spent catalyst was thoroughly characterized to understand the stability and structural and intrinsic properties.
{"title":"Harnessing Defect-Engineered Zr-MOF Catalyst With Tailored Active Sites For Selective Carboxymethylation of Furfuryl Alcohol","authors":"H. K. Meghana, S. Sujith, M. Harsha, G. Manjunatha Reddy, Naresh Nalajala, Ganapati V. Shanbhag","doi":"10.1002/adsc.70319","DOIUrl":"https://doi.org/10.1002/adsc.70319","url":null,"abstract":"We selectively synthesized a less explored furan-2-ylmethylmethyl carbonate (FMMC), a potential green solvent and fuel additive via carboxymethylation of furfuryl alcohol with dimethyl carbonate. A defect-engineered UiO-66 MOF catalyst was employed for this transformation, and its activity was benchmarked against conventional catalysts such as H-ZSM-5, H-Beta, and Amberlyst-15. The nature of the active sites instrumental in obtaining high FMMC selectivity was emphasized by the variation in turnover numbers. The in situ approach of tailoring missing linker defects in the UiO-66 MOF was achieved with monocarboxylic acid modulators, formic acid and acetic acid. The catalysts were comprehensively characterized for the structural properties by PXRD, N<sub>2</sub> sorption, and FESEM, and the intrinsic active sites were investigated with techniques such as EPR, FTIR, TGA, and acid–base titrations. The defective UiO-66 MOF demonstrated superior catalytic activity owing to the presence of a higher number of weak Brönsted acidic sites. The selective masking of Brönsted and Lewis acidic sites were studied by treating it with 2,6-lutidine and KSCN respectively and their effect on the catalytic activity was examined. A Central Composite Design (CCD) model was designed to obtain the high FMMC yield under optimized conditions. The catalyst gave 87.3% furfuryl alcohol conversion and 95.2% FMMC selectivity. The leaching and recyclability experiments showed that the catalyst was truly heterogeneous, and it was recyclable up to five consecutive cycles. The spent catalyst was thoroughly characterized to understand the stability and structural and intrinsic properties.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"27 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147292543","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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