Catalysis Science & Technology最新文献

{"title":"Unveiling the organocatalytic pathway to glycerol carbonate from glycerol and CO2: a comprehensive study using phase behavior, operando high-pressure FTIR, and DFT insights†","authors":"Taha Amine Chibane ,&nbsp;Raphaël Méreau ,&nbsp;Thierry Tassaing ,&nbsp;Karine De Oliveira Vigier","doi":"10.1039/d5cy00193e","DOIUrl":"10.1039/d5cy00193e","url":null,"abstract":"<div><div>The direct synthesis of glycerol carbonate from glycerol and CO₂, using acetonitrile as a dehydration agent and DBU as a catalyst, was investigated to identify the mechanism involved during this reaction. DFT modeling revealed that the most efficient pathway involves forming a C–O bond between CO₂ and glycerol's secondary alcohol. The catalyst reduces energy barriers across steps, particularly for the rate-limiting intramolecular ring closure, making the carbonyl substitution route more favorable than hydroxyl dehydration. However, acetonitrile's hydrolysis proved less effective as a dehydrating agent due to its higher energy barrier compared to direct carbonylation. While reaction parameters like CO₂ pressure and acetonitrile volume had minimal impact on yield, they influenced glycerol conversion. Higher pressure and larger acetonitrile volumes reduced glycerol conversion without changing the yield of glycerol carbonate. Elevated temperatures and prolonged reaction times promoted the formation of side products, primarily monoacetin. The reaction's complex phase behavior, driven by pressure and temperature, revealed that glycerol and acetonitrile become fully miscible only under specific conditions (155 °C, 45 bar). <em>In situ</em> FTIR and HPLC analyses identified kinetic profiles for glycerol carbonate, acetins, and acetamide, with ammonia and urea detected in the gas phase. Complementary DFT calculations confirmed that monoacetin formation predominantly arises from the reaction of glycerol with acetamide, a pathway characterized by the lowest energy barriers, aligning with experimental findings.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 16","pages":"Pages 4649-4660"},"PeriodicalIF":4.2,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810698","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ag2O-modified MnO2 enhanced electrocatalytic propylene epoxidation with water as the sole oxygen source†","authors":"Letian Yang ,&nbsp;Yuyang Ge ,&nbsp;Pengxin Ren ,&nbsp;Jujin Xue ,&nbsp;Yingjun Tian ,&nbsp;Jianbin Chen ,&nbsp;Wei Gao ,&nbsp;Liyue Pei ,&nbsp;Bingpeng Guo ,&nbsp;Yan Tian ,&nbsp;Yuehui Li ,&nbsp;Li Ma ,&nbsp;Siyuan Liu ,&nbsp;Zunqi Liu ,&nbsp;Baoying Li","doi":"10.1039/d5cy00421g","DOIUrl":"10.1039/d5cy00421g","url":null,"abstract":"<div><div>Propylene oxide, as a pivotal chemical raw material with an annual demand exceeding 20 million tons, faces challenges in traditional production processes such as high energy consumption, large carbon emissions, and severe environmental pollution. Electrocatalytic propylene epoxidation, utilizing renewable electricity instead of chemical oxidants and water as a clean oxygen source, is a green and safe synthesis strategy for propylene oxide. However, it is still necessary to solve the problem of low yield. In this work, we prepared a 0.5Ag₂O/MnO₂ catalyst and obtained a high yield of 13.4 g m⁻² h⁻¹, which displayed a 20-fold improvement compared to MnO₂ (0.6 g m⁻² h⁻¹). This was attributed to the abundant oxygen vacancies and active sites, which would weaken the interaction of Mn–O bonds and promote the activation of propylene.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 16","pages":"Pages 4759-4765"},"PeriodicalIF":4.2,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810696","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photocatalytic decarboxylative deuteration of lauric acid with heavy water for sustainable synthesis of deuterated alkanes†","authors":"Haifan Huang ,&nbsp;Zihan Lin ,&nbsp;Akira Yamamoto ,&nbsp;Yagna Bhoi Prakash ,&nbsp;Kexin Zou ,&nbsp;Shohichi Furukawa ,&nbsp;Ken-ichi Fujita ,&nbsp;Gunik Lee ,&nbsp;Jun Kumagai ,&nbsp;Hisao Yoshida","doi":"10.1039/d5cy00316d","DOIUrl":"10.1039/d5cy00316d","url":null,"abstract":"<div><div>As a simple model system for sustainable synthesis of deuterated alkanes, photocatalytic decarboxylative deuteration of lauric acid (dodecanoic acid) was explored employing heavy water (²H₂O, D₂O) as the deuterium source and titanium dioxide (TiO₂) photocatalysts loaded with metal cocatalysts (Au, Pt or Pd), without requiring any other reagents. The photocatalysts effectively facilitated the production of monodeuterated undecane ([²H₁]undecane, C₁₁H₂₃D). The alkyl radical degenerated from lauric acid through decarboxylation couples with the deuterium radical generated from heavy water, resulting in the formation of the deuterated undecane. Among the tested photocatalysts, a gold-loaded TiO₂ (Au/TiO₂) photocatalyst pre-dried before use achieved a 15.3% yield of deuterated undecane after 3 hours of photocatalytic reaction, with the deuteration ratio (<em>R</em>_d) in the obtained undecane reaching 85.1%. While extending the reaction time increased the overall yield, it led to a lower <em>R</em>_d. The <em>R</em>_d did not reach 100% since the alkyl radical intermediate also reacts with lauric acid or another alkyl radical to form non-deuterated undecane (C₁₁H₂₄) or docosane (C₂₂H₄₆), respectively as byproducts. The reaction mechanism of this photocatalytic system was elucidated using ESR measurement with radical trapping. This study offers a model methodology for the efficient synthesis of deuterated compounds, with potential applications in various fields such as pharmaceuticals.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 16","pages":"Pages 4637-4648"},"PeriodicalIF":4.2,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810697","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective and sustainable quinoline hydrogenation with a robust hierarchical catalyst framework†","authors":"Azina Rahmani ,&nbsp;Diego R. Javier-Jiménez ,&nbsp;Deborah Israel ,&nbsp;Brian Butkus ,&nbsp;Lei Zhai ,&nbsp;Parag Banerjee ,&nbsp;William E. Kaden ,&nbsp;Akihiro Kushima ,&nbsp;Titel Jurca","doi":"10.1039/d5cy00675a","DOIUrl":"10.1039/d5cy00675a","url":null,"abstract":"<div><div>A hierarchical heterogeneous palladium on nickel foam-based catalyst system (Al₂O₃–Pd–D/Ni) was demonstrated for the selective hydrogenation of quinoline and quinoline derivatives under low H₂ pressures, with green solvents (ethanol, ethanol water mixture). The catalyst framework features very low palladium loadings and is highly reusable under facile handling, requiring no filtration or other separation aids, and notably demonstrates no loss in reactivity or alteration of selectivity over multiple recycling trials. Theoretical calculations and X-ray photoelectron spectroscopy studies point to a fully-reduced Pd surface as the necessary active site for catalysis, arising from the <em>in situ</em> reduction of the PdO_<em>x</em> surface sites of the air-stable hierarchical material system.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 16","pages":"Pages 4632-4636"},"PeriodicalIF":4.2,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810695","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DFT investigation of mechanism, regioselectivity, and chemoselectivity in rhodium(iii)-catalyzed oxidative cyclization of chalcones with internal alkynes†","authors":"Simeng Qi ,&nbsp;Ran Fang ,&nbsp;Yanyun Dong ,&nbsp;Jiacheng Fan ,&nbsp;Alexander M. Kirillov ,&nbsp;Lizi Yang","doi":"10.1039/d5cy00229j","DOIUrl":"10.1039/d5cy00229j","url":null,"abstract":"<div><div>Density functional theory (DFT) was used to examine the mechanism, regioselectivity, and chemoselectivity in the rhodium(<span>iii</span>)-catalyzed oxidative cyclization of chalcones with internal alkynes. The computational findings indicate that the entire reaction comprises two fundamental catalytic cycles. Initially, the reaction undergoes the C–H activation, followed by migratory insertion, reductive elimination, and hydrolysis to form an enol, thereby completing the first catalytic cycle. Subsequently, the enol undergoes O–H deprotonation, migratory insertion, reductive elimination, hydrolysis, and retro-aldol reaction to generate the final product. In the case of asymmetric alkynes, distortion–interaction analysis indicates that the regioselectivity is influenced by steric effects during the alkyne insertion step, while the chemoselectivity for the Rh–C or Rh–O bonds is predominantly governed by spatial hindrance and electronic influence of the substrate. A linear fitting of charges in NPA (natural population analysis) for various substituents on different chalcones reveals that the charge of the starting material plays an important role in its ability to undergo a successful (4 + 1) cyclization. This study contributes to a deeper understanding of the fundamental reaction mechanisms and offers significant insights for the rational design of related catalytic processes.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 16","pages":"Pages 4766-4775"},"PeriodicalIF":4.2,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810735","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ligand-assisted nickel catalysis enabling N,N-dialkylation and cyclization of acyl hydrazides using aliphatic alcohols†","authors":"Ayanangshu Biswas ,&nbsp;Sourav Mandal ,&nbsp;Supriya Halder ,&nbsp;Bikramaditya Mandal ,&nbsp;Debashis Adhikari","doi":"10.1039/d5cy00433k","DOIUrl":"10.1039/d5cy00433k","url":null,"abstract":"<div><div>Herein, we describe a nickel-catalyzed <em>N</em>,<em>N</em>-dilakylation protocol for acyl hydrazides. A series of aliphatic alcohols and diols were successfully dehydrogenated and used for this challenging dialkylation as well as some cyclization reactions. The reaction is chemoselective, as many of the <em>N</em>,<em>N</em>-dialkylated products contain an olefinic motif, with the imine linkage selectively reduced while the olefinic one remains intact. The azo–hydrazo redox couple plays a crucial role in the hydrogenation of imines. The reaction proceeds <em>via</em> a radical pathway and in striking contrast to previous reports that involve metal hydrides.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 16","pages":"Pages 4776-4782"},"PeriodicalIF":4.2,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mapping the catalytic landscape of triphenylborane (BPh3)-catalyzed CO2-epoxide coupling to carbonates: an in silico approach to solve substrate-dependent selectivity†","authors":"Nikunj Kumar ,&nbsp;Puneet Gupta","doi":"10.1039/d5cy00281h","DOIUrl":"10.1039/d5cy00281h","url":null,"abstract":"<div><div>The catalytic coupling of CO₂ and epoxides is a promising approach for carbon valorization, enabling the synthesis of cyclic-carbonates (CCs) and poly-carbonates (PCs). However, controlling product selectivity remains a challenge. Triphenylborane (BPh₃) has emerged as a promising metal-free catalyst, yet the origins of its substrate-dependent selectivity remain unclear. While BPh₃ selectively forms CCs with propylene oxide (PO), it exclusively produces PCs with cyclohexene oxide (CHO), highlighting distinct reactivity. To understand this selectivity, we conducted a comprehensive density functional theory (DFT) study, mapping the catalytic landscape of BPh₃-mediated CO₂-epoxide coupling and comparing it with triethylborane (BEt₃) catalysis, which lacks such selectivity. Our calculations reveal that epoxide ring opening is the rate-determining step, consistent with experimental studies. Additionally, high CO₂ concentrations can form an inactive species that inhibits epoxide activation, explaining the experimentally observed inverse rate dependence on CO₂ concentration. Our distortion/interaction analysis (DIA) and non-covalent interaction (NCI) analysis show that in BPh₃-catalyzed CO₂ and PO coupling, weaker intermolecular interactions in the epoxide addition step disfavour PC formation, favoring CC formation. Conversely, for CO₂ and CHO coupling, the high distortion energy in the ring-closing step makes CC formation unfavourable, leading to PC as the dominant product. In contrast, BEt₃ catalysis stabilizes PC formation across both epoxides, eliminating selectivity. This study sketches the catalytic landscape of BPh₃-catalyzed CO₂-epoxide coupling, revealing how boron substitution governs selectivity and offers insights for designing boron-based catalysts for selective CO₂ utilization.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 16","pages":"Pages 4661-4671"},"PeriodicalIF":4.2,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Diphenyl carbonate synthesis from CO2 over a ZnCeZrOX ternary solid solution: synergistic catalysis using oxygen vacancies and Lewis acid sites†","authors":"Mengke Xing ,&nbsp;Tianli Hui ,&nbsp;Rui Zhang ,&nbsp;Tao Zheng ,&nbsp;Zhichang Liu ,&nbsp;Haiyan Liu ,&nbsp;Chunming Xu ,&nbsp;Xianghai Meng","doi":"10.1039/d5cy00348b","DOIUrl":"10.1039/d5cy00348b","url":null,"abstract":"<div><div>The direct synthesis of diphenyl carbonate (DPC) from CO₂ and phenol has attracted much attention as it can realize CO₂ utilization and can avoid phosgene usage in the traditional production process. Nevertheless, the achievement of high DPC yields is hindered by the difficult activation of CO₂. Herein, a dual metal incorporated ZnCeZrO_<em>X</em> catalyst was synthesized, and the synergistic catalysis mechanism between oxygen vacancies and Lewis acid sites was systematically demonstrated. Raman and EPR analyses revealed that the simultaneous introduction of Zn and Ce effectively promoted the formation of abundant oxygen vacancies, thereby enhancing the adsorption and activation of CO₂. NH₃-TPD and Py-IR characterizations demonstrated that dual doping of Zn and Ce modulated Lewis acidity, benefiting the adsorption of phenol and intermediates. Compared with ZnZrO_<em>X</em> and CeZrO_<em>X</em>, the ZnCeZrO_<em>X</em> catalyst demonstrated superior catalytic performance, achieving a phenol conversion of 47.6% and a DPC selectivity of 82.5%. DFT and <em>in situ</em> FTIR analyses indicated that oxygen vacancies activated CO₂ to form b-CO₃²⁻ species, while Lewis acid sites adsorbed phenol to facilitate the dissociation of the O_phenol–H bond, synergistically generating DPC. This study demonstrates synergistic catalysis using oxygen vacancies and Lewis acid sites, opening a novel avenue for DPC synthesis.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 16","pages":"Pages 4872-4884"},"PeriodicalIF":4.2,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810744","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"On the enhanced photocatalytic activity of N-doped carbon dots†","authors":"Hector Daniel Almeida Gonzalez ,&nbsp;Gabriel Rafael Guerrero Porras ,&nbsp;Hervé Vezin ,&nbsp;Lisandra Morales Alvarez ,&nbsp;Angel Luis Corcho Valdés ,&nbsp;L. Julieth Bravo Martínez ,&nbsp;Alicia M. Díaz-García ,&nbsp;David González-Martínez ,&nbsp;Jose M. Moran-Mirabal ,&nbsp;Clarissa Murru ,&nbsp;Johnny Deschamps ,&nbsp;Claudia Iriarte-Mesa ,&nbsp;Qixiang Jiang ,&nbsp;Freddy Kleitz ,&nbsp;Luis Felipe Desdin-Garcia ,&nbsp;Manuel Antuch","doi":"10.1039/d5cy00457h","DOIUrl":"10.1039/d5cy00457h","url":null,"abstract":"<div><div>Carbon nanostructures (dots) have emerged as a novel and sustainable alternative for the photocatalytic degradation of water pollutants. This work presents the synthesis of multidoped carbon nanomaterials (CNs) using a microwave-assisted method. Overall, four types of carbon nanostructures were obtained: (i) nitrogen-doped CNs (N-CDs), (ii) nitrogen and sulfur co-doped CNs (N,S-CNs), (iii) nitrogen and phosphorus co-doped CNs (N,P-CNs), and (iv) nitrogen, sulfur, and phosphorus multi-doped CNs (N,S,P-CNs). The characterization of these nanoparticles was performed <em>via</em> Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), enabling the identification of stretching modes corresponding to CO, C–N, and N–H functional groups. Additionally, UV-vis and fluorescence spectroscopies allowed the detection of n–π* and π–π* absorption bands at ∼325 and 400 nm, along with light emission at 438 nm. High-resolution transmission electron microscopy (TEM) characterization confirmed structural and morphological differences between the nanomaterials, which exhibited sizes ranging from 1 to 100 nm, depending on the chemical composition of the starting precursors. Finally, the photocatalytic activity of the CNs towards the degradation of toluidine blue was assessed, considering the effects of morphology, composition, and both catalyst and dye concentration on photodegradation. Such a catalytic process followed pseudo-first-order kinetics, where N-CDs exhibited the highest potential for toluidine blue degradation. Our results highlight that the photocatalytic activity of carbon nanomaterials is a multifactorial process essentially driven by the formation of OH radicals, where doping and particle morphology also play a combined role in photocatalysis. This work opens a route for understanding the chemical composition and structure of photocatalytic nanocarbons and their application to the degradation of organic pollutants in water, thus offering a sustainable alternative for wastewater treatment.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 16","pages":"Pages 4713-4726"},"PeriodicalIF":4.2,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810731","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nickel-aluminosilicate catalysts for ethylene oligomerization: recent scientific progress","authors":"Vasile Hulea","doi":"10.1039/d5cy00372e","DOIUrl":"10.1039/d5cy00372e","url":null,"abstract":"<div><div>Significant scientific effort has been made during the last decades to develop heterogeneous catalysts and processes for ethylene oligomerization. Among the reported catalysts, Ni-aluminosilicates are regarded as the most promising candidates. This paper reviews the recent advancements in ethylene conversion catalyzed by Ni-aluminosilicates. The main fundamental and practical aspects on this topic, including types of catalysts depending on the support, active nickel sites, oligomerization mechanism and kinetics and catalyst deactivation, are examined. The multi-reaction catalytic processes in which oligomerization is the key step have been also discussed.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 16","pages":"Pages 4612-4631"},"PeriodicalIF":4.2,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144810714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}