Pub Date : 2025-12-24DOI: 10.1007/s10562-025-05280-6
Wang Zhi-tao
{"title":"Retraction Note: Cycloaddition of Propargylic Amines and CO2 by Ni@Pd Nanoclusters Confined Within Metal–Organic Framework Cavities in Aqueous Solution","authors":"Wang Zhi-tao","doi":"10.1007/s10562-025-05280-6","DOIUrl":"10.1007/s10562-025-05280-6","url":null,"abstract":"","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"156 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145831191","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 : 2025-12-18DOI: 10.1007/s10562-025-05247-7
Wentao Zhu, Muhammad Asadullah Khan, Yao Sun, Daohong Liao, Liangji Xue, Fuzhou Wang, Ao Chen, Chen Tan
Industrial polyolefin processes are mainly based on heterogeneous catalytic systems. Shell higher olefin process (SHOP) type nickel catalysts represent one of the late-transition metal homogeneous catalysts for the industrial preparation of linear low-carbon α-olefins from ethylene. This work focuses on the heterogenization of homogeneous SHOP catalysts using hydrogen-bonding interactions or ionic anchoring strategies, which enhances catalytic activity and polymer molecular weight while maintaining narrow polydispersities. Three sodium-sulfonate functionalized SHOP nickel complexes were prepared, and their superior performance in ethylene polymerization compared to homogeneous catalysts was demonstrated, underscoring the potential of these heterogeneous catalysts in efficient production of highly crystalline linear α-olefinic solid polymers.
{"title":"Heterogeneous SHOP-Type Ni Catalyzed Ethylene Polymerization","authors":"Wentao Zhu, Muhammad Asadullah Khan, Yao Sun, Daohong Liao, Liangji Xue, Fuzhou Wang, Ao Chen, Chen Tan","doi":"10.1007/s10562-025-05247-7","DOIUrl":"10.1007/s10562-025-05247-7","url":null,"abstract":"<div><p>Industrial polyolefin processes are mainly based on heterogeneous catalytic systems. Shell higher olefin process (SHOP) type nickel catalysts represent one of the late-transition metal homogeneous catalysts for the industrial preparation of linear low-carbon α-olefins from ethylene. This work focuses on the heterogenization of homogeneous SHOP catalysts using hydrogen-bonding interactions or ionic anchoring strategies, which enhances catalytic activity and polymer molecular weight while maintaining narrow polydispersities. Three sodium-sulfonate functionalized SHOP nickel complexes were prepared, and their superior performance in ethylene polymerization compared to homogeneous catalysts was demonstrated, underscoring the potential of these heterogeneous catalysts in efficient production of highly crystalline linear α-olefinic solid polymers.</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":"156 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145778972","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 : 2025-12-18DOI: 10.1007/s10562-025-05238-8
Rustamkhon Kuryazov, Zaman Abdalhussein Ibadi Alaridhee, Dilafruz Kholmurodova, Abdulrahman A. Almehizia, Ahmed Aldulaimi, Rafid Kamal Jameel, Juma Bakirov, Yuldoshev Jushkinbek Erkaboy Ugli, Mukhayya Ruzieva, Elyor Berdimurodov, Karkaz Thalij
The advancement of these chemical transformations necessitates the optimization of conventional reaction conditions and the enhancement of catalytic system efficiency through the utilization of readily available, cost-effective raw materials that exhibit recyclability and multifunctionality, serving simultaneously as solvent, catalyst, and catalytic agent, in accordance with green chemistry principles. In this context, the present study reports the design and synthesis of [DHPZ][CuCl3]2 and [DHPZ][FeCl4]2 catalysts based on deep eutectic solvents incorporating inexpensive and abundant metals, namely copper and iron. Comprehensive characterization of these catalysts was performed using FT-IR, TGA, 1HNMR, 13CNMR, and cyclic voltammetry (CV) analyses. The catalytic performance was subsequently assessed in the electrocarboxylation reaction for the synthesis of 4-Phenyl-1,3-dioxolan-2-one derivatives 4(a-j) under optimized conditions, including ambient temperature, atmospheric pressure, an applied current of 10 mA, and a reaction duration of 1.5 h. This methodology afforded the target compounds in good to excellent yields, ranging from 89% to 97%. The synthesized derivatives were further confirmed by 1HNMR spectroscopy, CHN elemental analysis, and melting point determination.
{"title":"Design and Synthesis of a Novel Green [DHPZ][CuCl3]2 DES with Recyclable Functionality as Solvent, Electrolyte, Catalyst, and CO2 Capture Agent for the Electro-Organic Synthesis of 4-Phenyl-1,3-Dioxolan-2-One Derivatives","authors":"Rustamkhon Kuryazov, Zaman Abdalhussein Ibadi Alaridhee, Dilafruz Kholmurodova, Abdulrahman A. Almehizia, Ahmed Aldulaimi, Rafid Kamal Jameel, Juma Bakirov, Yuldoshev Jushkinbek Erkaboy Ugli, Mukhayya Ruzieva, Elyor Berdimurodov, Karkaz Thalij","doi":"10.1007/s10562-025-05238-8","DOIUrl":"10.1007/s10562-025-05238-8","url":null,"abstract":"<div><p>The advancement of these chemical transformations necessitates the optimization of conventional reaction conditions and the enhancement of catalytic system efficiency through the utilization of readily available, cost-effective raw materials that exhibit recyclability and multifunctionality, serving simultaneously as solvent, catalyst, and catalytic agent, in accordance with green chemistry principles. In this context, the present study reports the design and synthesis of [DHPZ][CuCl<sub>3</sub>]<sub>2</sub> and [DHPZ][FeCl<sub>4</sub>]<sub>2</sub> catalysts based on deep eutectic solvents incorporating inexpensive and abundant metals, namely copper and iron. Comprehensive characterization of these catalysts was performed using FT-IR, TGA, 1HNMR, 13CNMR, and cyclic voltammetry (CV) analyses. The catalytic performance was subsequently assessed in the electrocarboxylation reaction for the synthesis of 4-Phenyl-1,3-dioxolan-2-one derivatives <b>4(a-j)</b> under optimized conditions, including ambient temperature, atmospheric pressure, an applied current of 10 mA, and a reaction duration of 1.5 h. This methodology afforded the target compounds in good to excellent yields, ranging from 89% to 97%. The synthesized derivatives were further confirmed by 1HNMR spectroscopy, CHN elemental analysis, and melting point determination.</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":"156 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145779050","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 : 2025-12-18DOI: 10.1007/s10562-025-05268-2
B. N. Divya, P. Shiva Kumar, H. M. Veereshappa, S. Mahima, K. S. Manjunatha Kumara, Srinivasa Budagumpi, D. H. Nagaraju
The doping of Ru and Fe into β-MnO2 improves the conductivity which aids in better electrocatalytic OER performance. Synergetic effect of Ru/Fe on β-MnO2 framework is highly beneficial to balance the stabilizing structures. For OER in alkaline media, we have therefore synthesized β-MnO2 and doped Ru@β-MnO2, Fe@β-MnO2, and dual doped Ru-Fe@β-MnO2. The OER overpotentials were 550 mV, 310 mV, 290 mV, and 260 mV at a current density of 10 mA cm− 2, while the Tafel slope values in 1 M KOH were 126 mV dec− 1, 107 mV dec− 1, 100 mV dec− 1, and 86 mV dec− 1, respectively. When Fe@β-MnO2 and Ru@β-MnO2 are co-doped, the XPS shows that the binding energy shifts to a lower value, confirming the partial reduction of Mn4+ to Mn3+. However, when Ru-Fe@β-MnO2 is co-doped, the Mn 2p peaks return to higher binding energies, like the β-MnO2. The observed shifts in binding energies implies a dynamic equilibrium in the MnO2 lattice leads to electron donation. The Co-doping introduce additional electrons into the MnO2 lattice, reducing Mn4+ to Mn3+. This interplay suggests a self-regulating mechanism where the Mn oxidation state adjusts in response to the electronic effects of the dopants, maintaining the structural and electronic integrity of the MnO2 lattice. Further, this co-doped Ru-Fe@β-MnO2 nanoarrays demonstrated good long-term stability for 15 h, with no distinct changes observed in its chemical conditions.
Graphical Abstract
钌和铁掺杂在β-MnO2中，提高了β-MnO2的电导率，从而提高了β-MnO2的电催化OER性能。Ru/Fe对β-MnO2骨架的协同作用有利于平衡稳定结构。因此，对于碱性介质中的OER，我们合成了β-MnO2和掺杂Ru@β-MnO2， Fe@β-MnO2和双掺杂Ru-Fe@β-MnO2。当电流密度为10 mA cm−2时，OER过电位分别为550 mV、310 mV、290 mV和260 mV，而在1 M KOH中，Tafel斜率分别为126 mV dec−1、107 mV dec−1、100 mV dec−1和86 mV dec−1。当Fe@β-MnO2和Ru@β-MnO2共掺杂时，XPS显示结合能向较低的值移动，证实了Mn4+部分还原为Mn3+。然而，当Ru-Fe@β-MnO2共掺杂时，Mn 2p峰返回到更高的结合能，就像β-MnO2一样。观察到的结合能的变化表明，二氧化锰晶格中的动态平衡导致了电子赋能。共掺杂在MnO2晶格中引入了额外的电子，使Mn4+还原为Mn3+。这种相互作用表明了一种自我调节机制，其中Mn氧化态根据掺杂剂的电子效应进行调节，保持了MnO2晶格的结构和电子完整性。此外，共掺杂Ru-Fe@β-MnO2纳米阵列在15小时内表现出良好的长期稳定性，化学条件没有明显变化。图形抽象
{"title":"Self-regulating Electron Redistribution, by Ru and Fe Towards Optimal Electronic Structure of β-MnO2 for Oxygen Evolution Reaction in Alkaline Medium","authors":"B. N. Divya, P. Shiva Kumar, H. M. Veereshappa, S. Mahima, K. S. Manjunatha Kumara, Srinivasa Budagumpi, D. H. Nagaraju","doi":"10.1007/s10562-025-05268-2","DOIUrl":"10.1007/s10562-025-05268-2","url":null,"abstract":"<div><p>The doping of Ru and Fe into β-MnO<sub>2</sub> improves the conductivity which aids in better electrocatalytic OER performance. Synergetic effect of Ru/Fe on β-MnO<sub>2</sub> framework is highly beneficial to balance the stabilizing structures. For OER in alkaline media, we have therefore synthesized β-MnO<sub>2</sub> and doped Ru@β-MnO<sub>2</sub>, Fe@β-MnO<sub>2</sub>, and dual doped Ru-Fe@β-MnO<sub>2</sub>. The OER overpotentials were 550 mV, 310 mV, 290 mV, and 260 mV at a current density of 10 mA cm<sup>− 2</sup>, while the Tafel slope values in 1 M KOH were 126 mV dec<sup>− 1</sup>, 107 mV dec<sup>− 1</sup>, 100 mV dec<sup>− 1</sup>, and 86 mV dec<sup>− 1</sup>, respectively. When Fe@β-MnO<sub>2</sub> and Ru@β-MnO<sub>2</sub> are co-doped, the XPS shows that the binding energy shifts to a lower value, confirming the partial reduction of Mn<sup>4+</sup> to Mn<sup>3+</sup>. However, when Ru-Fe@β-MnO<sub>2</sub> is co-doped, the Mn 2p peaks return to higher binding energies, like the β-MnO<sub>2</sub>. The observed shifts in binding energies implies a dynamic equilibrium in the MnO<sub>2</sub> lattice leads to electron donation. The Co-doping introduce additional electrons into the MnO<sub>2</sub> lattice, reducing Mn<sup>4+</sup> to Mn<sup>3+</sup>. This interplay suggests a self-regulating mechanism where the Mn oxidation state adjusts in response to the electronic effects of the dopants, maintaining the structural and electronic integrity of the MnO<sub>2</sub> lattice. Further, this co-doped Ru-Fe@β-MnO<sub>2</sub> nanoarrays demonstrated good long-term stability for 15 h, with no distinct changes observed in its chemical conditions.</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":"156 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145778969","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 : 2025-12-18DOI: 10.1007/s10562-025-05272-6
Mei He, Duoduo Wei, Xiaogang Yin
Herein, we developed a Pd/UiO-66-NO catalyst for the reductive amination of benzaldehyde with aniline to synthesize N-benzylaniline. Through post-synthetic modification, salicylaldehyde was incorporated into the UiO-66-NH2 framework to construct a support (UiO-66-NO) featuring N, O-bidentate chelating sites, which enabled the stabilization of highly dispersed Pd nanoparticles. Characterization results confirmed the preserved framework integrity and demonstrated efficient secondary amine synthesis under mild conditions (60 °C, 3 h). The catalyst exhibited broad substrate scope with excellent functional group compatibility. Mechanistic studies revealed a two-step pathway involving amine-aldehyde condensation followed by hydrogenation of the imine intermediate. 1H NMR and GC kinetic analyses evidenced rapid imine formation and subsequent efficient reduction to the secondary amine. This study provides a new strategy for designing high-performance heterogeneous catalysts and opens up a viable pathway for the efficient synthesis of secondary amines.
{"title":"Stabilizing Pd Nanoparticles via N, O-Chelation in a MOF for General Reductive Amination","authors":"Mei He, Duoduo Wei, Xiaogang Yin","doi":"10.1007/s10562-025-05272-6","DOIUrl":"10.1007/s10562-025-05272-6","url":null,"abstract":"<div><p>Herein, we developed a Pd/UiO-66-NO catalyst for the reductive amination of benzaldehyde with aniline to synthesize <i>N</i>-benzylaniline. Through post-synthetic modification, salicylaldehyde was incorporated into the UiO-66-NH<sub>2</sub> framework to construct a support (UiO-66-NO) featuring N, O-bidentate chelating sites, which enabled the stabilization of highly dispersed Pd nanoparticles. Characterization results confirmed the preserved framework integrity and demonstrated efficient secondary amine synthesis under mild conditions (60 °C, 3 h). The catalyst exhibited broad substrate scope with excellent functional group compatibility. Mechanistic studies revealed a two-step pathway involving amine-aldehyde condensation followed by hydrogenation of the imine intermediate. <sup>1</sup>H NMR and GC kinetic analyses evidenced rapid imine formation and subsequent efficient reduction to the secondary amine. This study provides a new strategy for designing high-performance heterogeneous catalysts and opens up a viable pathway for the efficient synthesis of secondary amines.</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":"156 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145779049","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 : 2025-12-18DOI: 10.1007/s10562-025-05271-7
Alexey V. Ignatchenko, Reem Ibrahim, Jordan R. Kostera, Jordan D. Walker, Jared J. Jorolemon, Christian J. Leonardo
An invisible, reversible catalytic reaction called enolization occurs consistently when carboxylic acid vapors contact metal oxide surfaces, a pathway widely invoked in mechanistic proposals for decarboxylative ketonization but not sufficiently examined experimentally. While the CO₂H group responsible for adsorption readily forms surface carboxylates, the weaker α-C–H acidity becomes evident only through reversible H/D exchange. The formation of an enolized surface carboxylate enables its subsequent condensation with a second carboxylate, a transformation widely regarded as the rate-determining step in the decarboxylative ketonization mechanism relevant to oxygen removal in biofuel upgrading. In our kinetic study, the rate of approaching equilibrium was measured for H/D isotopic exchange on alpha-carbon of isobutyric acid used in various concentrations in a vapor phase mixture with D2O as well as for reversed D/H exchange between alpha-deuterated isobutyric acid and H2O upon contact with monoclinic zirconia and anatase titania catalysts. Faster rate for H/D vs. D/H exchange points to alpha-deprotonation, i.e., enolization, as the rate determining step of the exchange mechanism. The intrinsic rate of enolization was deduced using McKay equation for equilibrium reactions. Kinetic activation parameters were obtained through temperature dependence of the rate constant for both exchange directions, H/D and D/H. KOH doping on ZrO2 changes the geometry of the transition state leading to higher rates of enolization and increasing H/D kinetic isotope effect from 1.4 to 5.8. The opposite effect of KOH doping is observed on anatase TiO2 – enolization rates are slightly decreased, kH/kD remains relatively constant at 2.6–2.8 indicating that the nature of basic centers on TiO2 is unaffected. These results confirm C–C coupling, not enolization, being the rate limiting step of the decarboxylative ketonization mechanism.
{"title":"Kinetics of Carboxylic Acid Enolization on Metal Oxides in Vapor Phase","authors":"Alexey V. Ignatchenko, Reem Ibrahim, Jordan R. Kostera, Jordan D. Walker, Jared J. Jorolemon, Christian J. Leonardo","doi":"10.1007/s10562-025-05271-7","DOIUrl":"10.1007/s10562-025-05271-7","url":null,"abstract":"<div><p>An invisible, reversible catalytic reaction called enolization occurs consistently when carboxylic acid vapors contact metal oxide surfaces, a pathway widely invoked in mechanistic proposals for decarboxylative ketonization but not sufficiently examined experimentally. While the CO₂H group responsible for adsorption readily forms surface carboxylates, the weaker α-C–H acidity becomes evident only through reversible H/D exchange. The formation of an enolized surface carboxylate enables its subsequent condensation with a second carboxylate, a transformation widely regarded as the rate-determining step in the decarboxylative ketonization mechanism relevant to oxygen removal in biofuel upgrading. In our kinetic study, the rate of approaching equilibrium was measured for H/D isotopic exchange on alpha-carbon of isobutyric acid used in various concentrations in a vapor phase mixture with D<sub>2</sub>O as well as for reversed D/H exchange between alpha-deuterated isobutyric acid and H<sub>2</sub>O upon contact with monoclinic zirconia and anatase titania catalysts. Faster rate for H/D vs. D/H exchange points to alpha-deprotonation, i.e., enolization, as the rate determining step of the exchange mechanism. The intrinsic rate of enolization was deduced using McKay equation for equilibrium reactions. Kinetic activation parameters were obtained through temperature dependence of the rate constant for both exchange directions, H/D and D/H. KOH doping on ZrO<sub>2</sub> changes the geometry of the transition state leading to higher rates of enolization and increasing H/D kinetic isotope effect from 1.4 to 5.8. The opposite effect of KOH doping is observed on anatase TiO<sub>2</sub> – enolization rates are slightly decreased, k<sub>H</sub>/k<sub>D</sub> remains relatively constant at 2.6–2.8 indicating that the nature of basic centers on TiO<sub>2</sub> is unaffected. These results confirm C–C coupling, not enolization, being the rate limiting step of the decarboxylative ketonization mechanism.</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":"156 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145778973","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 : 2025-12-18DOI: 10.1007/s10562-025-05273-5
Hongkun Tian, Yuqi Hu, Hao Li
Diisobutyl ketone (DIBK), a high-value chemical with growing market demand, is currently produced as a by-product in methyl isobutyl ketone (MIBK) synthesis, leading to high costs and limited output. This study investigates the one-step synthesis of DIBK from acetone condensation and hydroconversion using Pd/Beta zeolite catalysts. A series of catalysts were prepared via impregnation and systematically characterized by XRD, BET, NH₃-TPD, Py-IR, and XPS. The effects of zeolite type, SiO₂/Al₂O₃ ratio, Pd loading, and reaction conditions on catalytic performance were thoroughly examined. Results demonstrate that Pd/Beta-25, possessing the highest acid site density, optimal Brønsted-to-Lewis acid ratio, and superior Pd dispersion, achieved the best performance: 98.4% acetone conversion and 64% DIBK selectivity under optimal conditions (210 °C, 3 MPa H₂, 9 h). The synergy between abundant acid sites (facilitating condensation) and well-dispersed Pd nanoparticles (enabling hydrogenation) is crucial for promoting the consecutive reaction pathway to DIBK. This work provides fundamental insights and an efficient catalytic system for direct DIBK production, highlighting the advantage of zeolite-based catalysts over conventional Pd/resin systems.
Graphical Abstract
二异丁基酮（DIBK）是一种市场需求不断增长的高价值化学品，目前作为甲基异丁基酮（MIBK）合成的副产物生产，导致成本高，产量有限。研究了丙酮缩合加氢转化一步法合成DIBK的Pd/ β沸石催化剂。采用浸渍法制备了一系列催化剂，并用XRD、BET、NH₃-TPD、Py-IR和XPS对其进行了系统表征。考察了分子筛类型、SiO₂/Al₂O₃比、Pd负载和反应条件对催化性能的影响。结果表明，在210℃、3 MPa H 2、9 H的最佳条件下，Pd/ β -25具有最高的酸位密度、最佳的Brønsted-to-Lewis酸比和优异的Pd分散性能，丙酮转化率为98.4%，DIBK选择性为64%。丰富的酸位点（促进缩合）和分散良好的钯纳米粒子（促进氢化）之间的协同作用对于促进连续反应途径到DIBK至关重要。这项工作为直接生产DIBK提供了基本的见解和有效的催化体系，突出了沸石基催化剂相对于传统Pd/树脂体系的优势。图形抽象
{"title":"Tuning the Acid-Metal Balance in Pd/Beta for Enhanced Catalytic Performance in Acetone Condensation and Hydroconversion","authors":"Hongkun Tian, Yuqi Hu, Hao Li","doi":"10.1007/s10562-025-05273-5","DOIUrl":"10.1007/s10562-025-05273-5","url":null,"abstract":"<div><p>Diisobutyl ketone (DIBK), a high-value chemical with growing market demand, is currently produced as a by-product in methyl isobutyl ketone (MIBK) synthesis, leading to high costs and limited output. This study investigates the one-step synthesis of DIBK from acetone condensation and hydroconversion using Pd/Beta zeolite catalysts. A series of catalysts were prepared via impregnation and systematically characterized by XRD, BET, NH₃-TPD, Py-IR, and XPS. The effects of zeolite type, SiO₂/Al₂O₃ ratio, Pd loading, and reaction conditions on catalytic performance were thoroughly examined. Results demonstrate that Pd/Beta-25, possessing the highest acid site density, optimal Brønsted-to-Lewis acid ratio, and superior Pd dispersion, achieved the best performance: 98.4% acetone conversion and 64% DIBK selectivity under optimal conditions (210 °C, 3 MPa H₂, 9 h). The synergy between abundant acid sites (facilitating condensation) and well-dispersed Pd nanoparticles (enabling hydrogenation) is crucial for promoting the consecutive reaction pathway to DIBK. This work provides fundamental insights and an efficient catalytic system for direct DIBK production, highlighting the advantage of zeolite-based catalysts over conventional Pd/resin systems.</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":"156 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145778971","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 : 2025-12-18DOI: 10.1007/s10562-025-05269-1
Jie Liu, Qingyan Chu, Guangliang Wang, Xiaoyang Zhang, Xiaowei Feng, Tengfei Wang, Tong Li, Ping Wang
The conventional nitration process, which relies on concentrated nitric acid as a reagent, presents significant challenges including high safety risks and substantial environmental burdens. To address these issues, this study developed a novel dual-base modified composite catalyst (TS-1@Ti-MWW-OH), which enables the efficient synthesis of 2-nitropropane via the ammoxidation/oxidation of acetone under mild conditions using ammonia and hydrogen peroxide. The core innovation of this work lies in the precise design of dual active sites with complementary functions, establishing a “synergistic relay” catalytic mechanism: the Ti4+ sites in Ti-MWW preferentially catalyze the conversion of acetone to acetone oxime, followed by the Ti4+ sites in TS-1 catalyzing the subsequent transformation of acetone oxime to 2-nitropropane. Through modification with 4-methoxypyridine/ethanolamine dual bases, the specific surface area and pore volume of the catalyst were significantly enhanced, thereby substantially improving reaction mass transfer efficiency and accessibility to active sites. Process simulation based on Aspen Plus V14 confirmed the potential for industrial scale-up of this route, achieving an annual production of 13000 tons of 2-nitropropane with a purity of no less than 99.99%, along with 760 tons of acetone oxime with a purity exceeding 99.8%. Furthermore, tray hydraulics analysis was employed to determine the main dimensions of key column equipment and their stable operating ranges within allowable flooding limits. This study, from the perspectives of both catalyst structural design and process engineering optimization, provides a promising new strategy for the green and sustainable production of nitroalkanes.
Graphical Abstract
传统的硝化工艺依赖于浓硝酸作为试剂，存在着巨大的安全风险和环境负担。为了解决这些问题，本研究开发了一种新型的双碱改性复合催化剂（TS-1@Ti-MWW-OH），该催化剂可以在温和的条件下使用氨和过氧化氢将丙酮氨氧化/氧化，从而高效合成2-硝基丙烷。本工作的核心创新点在于精确设计了功能互补的双活性位点，建立了“协同接力”催化机制：Ti-MWW中的Ti4+位点优先催化丙酮转化为丙酮肟，TS-1中的Ti4+位点催化后续丙酮肟转化为2-硝基丙烷。通过4-甲氧基吡啶/乙醇胺双碱改性，催化剂的比表面积和孔体积显著增强，从而大大提高了反应传质效率和活性位点的可及性。基于Aspen Plus V14的过程模拟证实了该路线的工业规模扩展潜力，实现了年产量13000吨纯度不低于99.99%的2-硝基丙烷，以及纯度超过99.8%的丙酮肟760吨。通过塔板水力学分析，确定了关键塔柱设备的主要尺寸及其在允许淹水范围内的稳定工作范围。本研究从催化剂结构设计和工艺优化两方面为硝基烷烃的绿色可持续生产提供了一条有前景的新策略。图形抽象
{"title":"Synergistic Catalysis of Composite Titanosilicate Zeolites for One-Step Ammoxidation of Acetone to 2-Nitropropane","authors":"Jie Liu, Qingyan Chu, Guangliang Wang, Xiaoyang Zhang, Xiaowei Feng, Tengfei Wang, Tong Li, Ping Wang","doi":"10.1007/s10562-025-05269-1","DOIUrl":"10.1007/s10562-025-05269-1","url":null,"abstract":"<div><p>The conventional nitration process, which relies on concentrated nitric acid as a reagent, presents significant challenges including high safety risks and substantial environmental burdens. To address these issues, this study developed a novel dual-base modified composite catalyst (TS-1@Ti-MWW-OH), which enables the efficient synthesis of 2-nitropropane via the ammoxidation/oxidation of acetone under mild conditions using ammonia and hydrogen peroxide. The core innovation of this work lies in the precise design of dual active sites with complementary functions, establishing a “synergistic relay” catalytic mechanism: the Ti<sup>4+</sup> sites in Ti-MWW preferentially catalyze the conversion of acetone to acetone oxime, followed by the Ti<sup>4+</sup> sites in TS-1 catalyzing the subsequent transformation of acetone oxime to 2-nitropropane. Through modification with 4-methoxypyridine/ethanolamine dual bases, the specific surface area and pore volume of the catalyst were significantly enhanced, thereby substantially improving reaction mass transfer efficiency and accessibility to active sites. Process simulation based on Aspen Plus V14 confirmed the potential for industrial scale-up of this route, achieving an annual production of 13000 tons of 2-nitropropane with a purity of no less than 99.99%, along with 760 tons of acetone oxime with a purity exceeding 99.8%. Furthermore, tray hydraulics analysis was employed to determine the main dimensions of key column equipment and their stable operating ranges within allowable flooding limits. This study, from the perspectives of both catalyst structural design and process engineering optimization, provides a promising new strategy for the green and sustainable production of nitroalkanes.</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":"156 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145778970","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 valorization of glycerol is a key research objective, and its carbonylation to glycerol carbonate represents a promising route. A major hurdle in this process is the development of efficient catalysts.This study systematically investigates the catalytic performance of various transition metal-based zeolitic imidazolate frameworks (ZIFs), including ZIF-8, ZIF-67, Cu-ZIF, Cu-ZIF-8, Cu-ZIF-67, and Co-ZIF-8, in the carbonylation of glycerol to glycerol carbonate. The results reveal that bimetallic ZIFs significantly enhance catalytic activity, among them, the Co-doped Pd/Co-ZIF-8-N catalyst exhibited the best performance, achieving a high glycerol carbonate yield of 92.97% and 96.37% selectivity, with a Pd loading of only 1%. Through characterization techniques such as Fourier Transform Infrared Spectroscopy (FT-IR), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), X-Ray Photoelectron Spectroscopy (XPS), and CO₂-Temperature Programmed Desorption (CO₂-TPD), we demonstrate that Co doping promotes the formation of carbon nanotubes, improves Pd dispersion, and modulates the acid–base properties of the material. Computational simulations further indicate that the combination of Co and Zn optimizes the natural charge distribution in the reaction transition state, facilitating electron transfer and thereby enhancing catalytic performance. Additionally, calcination temperature markedly influences the valence state and coordination environment of copper species, where the formation of a Cu–N₄ structure at high temperatures strengthens the synergistic effect with Pd. This work provides new mechanistic insights and material design strategies for the application of multimetallic ZIFs in carbonylation reactions.
{"title":"Efficient Glycerol Carbonylation over Multimetallic ZIF Catalysts: Synergy of Structure Regulation and Charge Optimization","authors":"Liyao Zhao, Zhihao Lv, Shuqi Qi, Pingbo Zhang, Jiawen Zhang, Mingming Fan","doi":"10.1007/s10562-025-05266-4","DOIUrl":"10.1007/s10562-025-05266-4","url":null,"abstract":"<div><p>The valorization of glycerol is a key research objective, and its carbonylation to glycerol carbonate represents a promising route. A major hurdle in this process is the development of efficient catalysts.This study systematically investigates the catalytic performance of various transition metal-based zeolitic imidazolate frameworks (ZIFs), including ZIF-8, ZIF-67, Cu-ZIF, Cu-ZIF-8, Cu-ZIF-67, and Co-ZIF-8, in the carbonylation of glycerol to glycerol carbonate. The results reveal that bimetallic ZIFs significantly enhance catalytic activity, among them, the Co-doped Pd/Co-ZIF-8-N catalyst exhibited the best performance, achieving a high glycerol carbonate yield of 92.97% and 96.37% selectivity, with a Pd loading of only 1%. Through characterization techniques such as Fourier Transform Infrared Spectroscopy (FT-IR), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), X-Ray Photoelectron Spectroscopy (XPS), and CO₂-Temperature Programmed Desorption (CO₂-TPD), we demonstrate that Co doping promotes the formation of carbon nanotubes, improves Pd dispersion, and modulates the acid–base properties of the material. Computational simulations further indicate that the combination of Co and Zn optimizes the natural charge distribution in the reaction transition state, facilitating electron transfer and thereby enhancing catalytic performance. Additionally, calcination temperature markedly influences the valence state and coordination environment of copper species, where the formation of a Cu–N₄ structure at high temperatures strengthens the synergistic effect with Pd. This work provides new mechanistic insights and material design strategies for the application of multimetallic ZIFs in carbonylation reactions.</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":"156 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145730327","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 development of multifunctional and sustainable catalysts for heterocycle construction remains critically important in modern organic chemistry. A novel Zr/P co-doped TiO2 nanocatalyst that was made via a Sol-gel chemical method and show how well it performs in the green, microwave-assisted production of azlactones. Zr and P co-doping creates oxygen vacancies, increases Lewis/Brønsted acidity, narrows the band gap, and greatly improves charge-carrier separation features directly responsible for the catalyst’s remarkable activity—in contrast to pristine TiO2, which has a wide band gap and rapid charge recombination. This material provides greater yields (89–96%), significantly shorter reaction durations (3–4 min), and superior recyclability when compared to previously reported TiO2 based or metal-oxide catalysts. Through quick dielectric heating, microwave irradiation speeds up reaction kinetics even more, creating a synergistic boost for azlactone synthesis that has never been seen before. Thus, this study presents a unique dual-strategy catalytic system that combines microwave activation and defect-engineered TiO2 nanophotocatalysis, providing a scalable, energy-efficient, and environmentally friendly pathway to pharmaceutically relevant azlactones.
{"title":"Zr/P Co-Doped TiO2 Nanonanocatalyst for Microwave-Assisted Green Synthesis of Bioactive Azlactones: Enhanced Catalytic Performance and Mechanistic Insights","authors":"Lakshmi Rekha Buddiga, Ganapathi Rao Gajula, Manuri Brahmayya, Ponnala Bhanuchander","doi":"10.1007/s10562-025-05267-3","DOIUrl":"10.1007/s10562-025-05267-3","url":null,"abstract":"<div><p>The development of multifunctional and sustainable catalysts for heterocycle construction remains critically important in modern organic chemistry. A novel Zr/P co-doped TiO<sub>2</sub> nanocatalyst that was made via a Sol-gel chemical method and show how well it performs in the green, microwave-assisted production of azlactones. Zr and P co-doping creates oxygen vacancies, increases Lewis/Brønsted acidity, narrows the band gap, and greatly improves charge-carrier separation features directly responsible for the catalyst’s remarkable activity—in contrast to pristine TiO<sub>2</sub>, which has a wide band gap and rapid charge recombination. This material provides greater yields (89–96%), significantly shorter reaction durations (3–4 min), and superior recyclability when compared to previously reported TiO<sub>2</sub> based or metal-oxide catalysts. Through quick dielectric heating, microwave irradiation speeds up reaction kinetics even more, creating a synergistic boost for azlactone synthesis that has never been seen before. Thus, this study presents a unique dual-strategy catalytic system that combines microwave activation and defect-engineered TiO<sub>2</sub> nanophotocatalysis, providing a scalable, energy-efficient, and environmentally friendly pathway to pharmaceutically relevant azlactones.</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":"156 1","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145730358","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号