化学•材料最新文献

{"title":"Intricacies of Carbon Dot Photoluminescence for Emerging Applications: A Review.","authors":"Nilanjana Nandi, Priyanka Sarkar, Neha Barnwal, Kalyanasis Sahu","doi":"10.1002/asia.202401470","DOIUrl":"https://doi.org/10.1002/asia.202401470","url":null,"abstract":"<p><p>Discovered in 2004, carbon dots (CDs) have already traversed a long journey, generating many promising research directions. Its cheapness, ease of synthesis, high water-solubility, tunable emission, and excellent biocompatibility make it a single-point solution to many problems, and tremendous efforts were invested into understanding the structure-property-function relationship, which eases the engineering of the CD properties suitable for a desired application. From the usual random choice of precursors or carbon materials as a starting point in the early days, more systematic approaches are now available for choosing proper starting materials and appropriate experimental conditions (solvent medium, reaction temperature, reaction duration, pH, etc) to customize its photoluminescence. The presence of impurities has a crucial role in the outcome and applicability of photoluminescence. Recently, a significant focus has been on the long-wavelength emissive CDs, particularly in the red to near-infrared (NIR) regions, for better penetration into live cells and to circumvent autofluorescence problems. Proper design can harvest phosphorescence from CDs. Many excellent reviews are available, focusing on different facets of CD prospects. Hence, we will only highlight the importance of the optical properties of CDs. We will mention some of the new works that have appeared in the last five years.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401470"},"PeriodicalIF":3.5,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187622","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":"Unveiling the Overlooked Inhibitory Effects of Carbon Dioxide on Photochemical Nitrate Decomposition over Photoactive Mineral Dust","authors":"Xin Zhang, Hong Wang, Shujun Liu, Miao Feng, Yanxia Wang, Meijia Jiang, Fan Dong","doi":"10.1021/acs.est.4c11591","DOIUrl":"https://doi.org/10.1021/acs.est.4c11591","url":null,"abstract":"Carbon emissions lead to an increased greenhouse gas concentration, which, in turn, affects air quality by altering the global climate. Despite its importance, the direct relationship between carbon emissions and the atmospheric reactive nitrogen cycle has been poorly understood. This study provides an in-depth investigation of the effects of CO₂ on the photochemical transformation of nitrates on mineral dust. The results show that CO₂ inhibits the photochemical transformation of nitrate under simulated solar irradiation. Specifically, the NO_<i>x</i> production rate from nitrate photolysis with CO₂ was significantly reduced to 1.17 × 10^–10 mol·s^–1, representing a decrease of 57.8%, compared to that without CO₂ (2.77 × 10^–10 mol·s^–1). This inhibition effect can be primarily ascribed to electron competition and the formation of carbonate/bicarbonate intermediates. Quenching experiments and electron paramagnetic resonance spectroscopy unveiled the crucial role of photogenerated electrons in nitrate photolysis, showing its significant competition with photochemical CO₂ conversion. Additionally, carbonate/bicarbonate intermediates formed during photochemical CO₂ conversion enhance the nitrate stability on mineral dust surfaces, thus, reducing their decomposition rate. This study unveils an overlooked atmospheric process of greenhouse gas participating in the reactive nitrogen cycle, highlighting the unignorable synergistic effects of carbon emissions and air pollution in photochemical reactions.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"88 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cyclic Osmate Esters from 1,2- and 1,3-Diols and α-Hydroxy Acids for X-ray Analysis","authors":"Jordan C. Thompson, Ngoc H. Le, Jace Pluemer, Ruby Chen, Charles J. Dooley, III, Joseph W. Ziller, Scott D. Rychnovsky","doi":"10.1021/acs.joc.4c03119","DOIUrl":"https://doi.org/10.1021/acs.joc.4c03119","url":null,"abstract":"We previously demonstrated that osmium tetroxide and TMEDA generate stable crystalline adducts with alkenes that facilitate X-ray analysis and structure assignments. Alternatively, osmate esters can be prepared from diols, potassium osmate, and TMEDA·2TsOH in a nonoxidative condensation reaction. This new approach provides a convenient route to form stable, crystalline osmate(VI) esters for X-ray analysis. Because it is redox neutral, it works with a variety of diol substrates, including 1,3-diols, that cannot be prepared from alkenes. α-Hydroxy acids also form stable osmate esters in reasonable yields and readily crystallize. An alternative ligand screen was performed to assess the improved crystallinity from substituted TMEDA analogues. The enhanced crystallinity of osmate esters and the incorporation of a heavy atom make a reliable determination of structure and absolute configuration routine.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192381","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}

{"title":"Amides Enable Room-Temperature CO2 Conversion: Simple Organic Molecules Challenging Metal Catalysts","authors":"Chen Jin, Lin Zhang, En-Hui Xing, Peng-Fei Mu, En-Qing Gao","doi":"10.1021/acs.joc.5c00056","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00056","url":null,"abstract":"The conversion of carbon dioxide (CO₂) into valuable chemicals has been intensively pursued for sustainable chemistry. It is highly desirable to achieve the conversion under ambient conditions using organocatalysts instead of precious or pollutive metal catalysts. Herein, we disclose a new class of organocatalysts for direct C(sp)–H carboxylation with CO₂. Amide molecules such as <i>N-</i>methylacetamide and valerolactam behave as efficient bifunctional catalysts to promote the conversion of aromatic alkynes to propiolic acids. In particular, the simple organic catalysts enable the reaction to occur at room temperature, which has been achieved only with complex transition metal catalysts prior to this report. In the presence of the optimal base of Cs₂CO₃, the adjacent nitrogen and oxygen sites of the amide group concurrently activate CO₂ and C(sp)–H and position them in favor of C–C coupling, affording a high catalytic activity on par with those of transition metal catalysts. The work sheds new light on the catalytic chemistry of CO₂ and also illustrates the great potential of discovering new organocatalysts from simple molecules.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192382","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}

{"title":"Photooxidation of Dipyrrinones: Reaction with Singlet Oxygen and Characterization of Reaction Intermediates","authors":"Dominik Madea, Júlia Peňáková, Jaya Mehara, Rikuo Akisaka, Marek Martínek, Jana Roithová, Petr Klán","doi":"10.1021/acs.joc.4c02954","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02954","url":null,"abstract":"Bilirubin (BR) is a water-insoluble product of heme catabolism in mammals. Elevated blood concentrations of BR, especially in the neonatal period, are treated with blue-green light phototherapy. The major mechanism of BR elimination during phototherapy is photoisomerization, while a minor, less studied mechanism of degradation is oxidation. In this work, we studied the oxidation of the bilirubin model tetramethyl-dipyrrinone (<i>Z</i>-<b>13</b>) by singlet oxygen in methanol using UV–vis and ESI-MS spectroscopy, resulting in propentdyopents as the main oxidation products. We also identified two additional intermediates that were formed during the reaction (hydroperoxide <b>21a</b> and imine <b>17</b>). The structure of the hydroperoxide was confirmed by helium-tagging IR spectroscopy. Such reaction intermediates formed during the oxidation of BR or bilirubin models have not been described so far. We believe that this work can be used as a first step in studying the complex oxidation mechanism of BR during phototherapy.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"129 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192480","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}

{"title":"High-Performance CsPbBr3 Quantum Dot/ZTO Heterojunction Phototransistor with Enhanced Stability and Responsivity","authors":"Min Guo, Jia Li, Xingyu Zhang, Guozhen Bai, Xinmu Chen, Xinlu Teng, Zhidong Lou, Yanbing Hou, Feng Teng, Yufeng Hu","doi":"10.1021/acs.jpclett.4c03538","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03538","url":null,"abstract":"Although all inorganic metal halide perovskite quantum dots (QDs) have shown great potential in photodetectors, many reported devices still suffer from low responsivity due to poor mobility and high defect densities. To overcome these challenges, heterojunction structures that separate electron and hole pathways have emerged as a promising approach to improve the responsivity by reducing radiative recombination. Two-dimensional materials such as graphene and MoS₂ have been integrated with perovskites to enhance performance; however, these materials often lead to high dark-state currents, which hinder the on/off ratios in photodetectors. Hence, identifying alternative functional materials that can complement perovskite QDs while minimizing these drawbacks is critical. Amorphous metal oxide semiconductors, such as zinc tin oxide (ZTO), have attracted attention as high-performance channel materials in thin-film transistors (TFTs) due to their high field-effect mobility, thermal stability, and ability to be processed at low temperatures over large areas. However, ZTO suffers from persistent photoconductivity (PPC) caused by oxygen vacancies, which leads to slow response times and prolonged conductivity after light exposure, thereby limiting its effectiveness in optoelectronic devices. In this work, we demonstrate a high-performance phototransistor using a planar heterojunction structure composed of CsPbBr₃ quantum dots and ZTO via a simple solution-processing method. This device exhibits a responsivity of over 10³ A/W, a specific detectivity of 7.0 × 10¹⁴ Jones, and an on/off ratio of 5 × 10⁴ under 390 nm light illumination with an intensity of 0.03 mW/cm². The combination of ZTO and CsPbBr₃ QDs offers significant improvements over devices that lack either layer, showcasing superior performance compared to that of most perovskite photodetectors.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"40 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192511","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}

{"title":"Machine-learning-assisted catalytic performance predictions of binary alloy catalysts for glucose hydrogenation","authors":"Zhecheng Fang ,&nbsp;Sifan Wang ,&nbsp;Haoan Fan ,&nbsp;Xuezhi Zhao ,&nbsp;Huiping Ji ,&nbsp;Bolong Li ,&nbsp;Zhenyu Zhang ,&nbsp;Jianghao Wang ,&nbsp;Kaige Wang ,&nbsp;Weiyu Song ,&nbsp;Reinout Meijboom ,&nbsp;Jie Fu","doi":"10.1016/j.apcata.2024.120086","DOIUrl":"10.1016/j.apcata.2024.120086","url":null,"abstract":"<div><div>Sorbitol production involves glucose hydrogenation, which requires co-adsorption of glucose and hydrogen on the catalyst surface for high catalytic performance. Binary alloy catalysts can modulate substrate adsorption to achieve better catalytic performance than Raney Ni. Herein, we established a pioneering DFT/ML approach to investigate the adsorption energies of glucose (ΔE_GCHO) and H atoms (ΔE_H) on 1155 binary alloy catalysts. The Light Gradient Boosting Machine (LGBM) algorithm proved the most effective ML model, predicting ΔE_GCHO and ΔE_H with R² values of 0.785 and 0.636, respectively. Microkinetic simulation demonstrated a correlation between catalytic activity and adsorption energy, revealing high-performance catalyst screening criteria as ΔE_GCHO = −1.45 to −0.65 eV and ΔE_H = −0.55–0.00 eV. Nine possible binary alloy catalysts with high predicted activity were identified, with Pd₃Mg performing best. The present study highlights the potential of the DFT/ML-assisted approach in the development of efficient glucose hydrogenation binary alloy catalysts.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120086"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135075","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}

{"title":"Selective hydrogenation of α, β-unsaturated aldehydes/ketones via photocatalytic and electrocatalytic techniques: A review","authors":"Shunli Shi,&nbsp;Jiaxuan Yang,&nbsp;Ying Li,&nbsp;Yahui Zhu,&nbsp;Weiming Xiao,&nbsp;Shunmin Ding,&nbsp;Shuhua Wang,&nbsp;Chao Chen","doi":"10.1016/j.apcata.2024.120063","DOIUrl":"10.1016/j.apcata.2024.120063","url":null,"abstract":"<div><div>The selective hydrogenation of α, β-unsaturated aldehydes/ketones, while preserving other functional groups within the molecule, is of paramount importance in synthetic chemistry for the precise modulation of product structures and properties. This is particularly crucial in the synthesis of complex and high-value organic molecules. As sustainability concerns intensify, the development of catalytic technologies that adhere to green chemistry principles has become an urgent imperative. These advancements not only address the rising demand for chemicals but also respond to the global call to mitigate unsustainable practices. This review focuses on the selective hydrogenation of α, β-unsaturated aldehydes/ketones, highlighting significant progress and breakthroughs in photocatalysis and electrocatalysis within the non-traditional thermal catalysis framework over the past decade. It provides an in-depth analysis of the characteristics and design principles of catalysts, catalytic systems, performance metrics, and the mechanistic pathways involved. Moreover, this review examines the factors influencing the selective hydrogenation of C<img>C/C<img>O bonds, pinpointing potential focal points for the development of green and sustainable hydrogenation systems for these compounds. Through elucidating these advancements, the review aims to offer valuable insights for further innovations in green and sustainable synthetic chemistry.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120063"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135090","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}

{"title":"Understanding Diels–Alder conversion of 2,5-Dimethylfuran and acrylic acid to para-Xylene over beta zeolites","authors":"Jie Huang ,&nbsp;Bing Yan ,&nbsp;Zhansheng Wang ,&nbsp;Xu Chen ,&nbsp;Zonghui Liu ,&nbsp;Bing Xue","doi":"10.1016/j.apcata.2024.120067","DOIUrl":"10.1016/j.apcata.2024.120067","url":null,"abstract":"<div><div>Conversion of 2,5-Dimethylfuran (DMF) and Acrylic Acid by Diels–Alder cycloaddition reaction over the Beta zeolites has demonstrated potential for producing renewable <em>para</em>-Xylene (PX). However, the reaction process and the structure-activity correlation were not fully characterized. In this work, Beta zeolites were used to catalyze the Diels–Alder reaction of DMF. The structural characterization, selective poisoning experiments, in-situ FTIR spectra measurements, and kinetic analysis were performed. The results illustrated that the reaction to form PX proceeds by cycloaddition and subsequent decarboxylation over Lewis (L) acid sites, and finally dehydration over Brønsted (B) acid sites. 2,5-dimethylbenzoic acid could not produce PX by decarboxylation over Beta zeolites. The FTIR spectra measurements showed that the B acid sites were incorporated into the reaction network. There were strong diffusion limitations in the H-Beta catalyst during the reaction. When diffusion limitations were eliminated by producing mesopores, the reaction was kinetically limited by the dehydration step.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120067"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135246","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}

{"title":"Heterogeneous bismuth catalyst for the selective hydrogenation of nitroarenes to arylamines using molecular hydrogen","authors":"Raju Kumar ,&nbsp;Baint Singh ,&nbsp;Achala Rana ,&nbsp;Manvender Yadav ,&nbsp;Jyotishman Kaishyop ,&nbsp;Tuhin Surva Khan ,&nbsp;Rajesh Kumar ,&nbsp;Ganesh Naik ,&nbsp;Anand Narani","doi":"10.1016/j.apcata.2024.120080","DOIUrl":"10.1016/j.apcata.2024.120080","url":null,"abstract":"<div><div>Bismuth is renowned for its exceptional safety, highlighted by numerous examples demonstrating its low toxicity. Considering this, we present a novel, active, and reusable heterogeneous bismuth catalyst (Bi-NC/γ-Al₂O₃) for chemoselective hydrogenation of nitroarenes to aryl amines using molecular hydrogen. The Bi-NC/γ-Al₂O₃ catalyst was synthesized through a simple impregnation method followed by pyrolysis at 700°C, for 2 h under a nitrogen atmosphere. The physicochemical properties of fresh and spent Bi-NC/γ-Al₂O₃ catalysts were comprehensively characterized by powder X-ray diffraction (P-XRD), X-ray photoelectron spectroscopy (XPS), High-resolution transmission electron microscopy (HR-TEM), N₂ adsorption-desorption, H₂-temperature programmed reduction (H₂-TPR), NH₃-temperature programmed desorption (NH₃-TPD), and thermogravimetric analysis (TGA). The bismuth content in the Bi-NC/γ-Al₂O₃ catalyst was estimated by inductively coupled plasma optical emission spectroscopy (ICP-OES). The catalyst demonstrated exceptional performance and selectivity in reducing a wide variety of nitroarenes to their corresponding aryl amines, achieving good to excellent yields (36 examples). Furthermore, the Bi-NC/γ-Al₂O₃ catalyst was applied to the selective hydrogenation of nitro groups in three commercially available drugs. Additionally, five pharmaceutical intermediates, including linezolid, Norfloxacin, Carbamazepine, paracetamol, and tizanidine, were synthesized up to a ∼1 g scale with a quantitative yield, showcasing the catalyst activity and selectivity. Further, the reaction mechanism was elucidated by tracking the intermediates (through GC-FID &amp; GC-MS) and employing Density Functional Theory (DFT). Notably, the Bi-NC/γ-Al₂O₃ catalyst is stable, recovered, and reused for four cycles without losing significant activity and selectivity.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120080"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135255","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}