ChemSusChem最新文献_第4页

Hydrogen Sensing via Heterolytic H2 Activation at Room Temperature by Atomic Layer Deposited Ceria. 原子层沉积铈室温下异裂H2活化的氢传感。

IF 7.5 2区化学

ChemSusChem Pub Date : 2025-01-17 DOI: 10.1002/cssc.202402342

Carlos Morales, Rudi Tschammer, Emilia Pożarowska, Julia Kosto, Ignacio J Villar-Garcia, Virginia Pérez-Dieste, Marco Favaro, David E Starr, Paulina Kapuścik, Michał Mazur, Damian Wojcieszak, Jarosław Domaradzki, Carlos Alvarado, Christian Wenger, Karsten Henkel, Jan Ingo Flege

{"title":"Hydrogen Sensing via Heterolytic H2 Activation at Room Temperature by Atomic Layer Deposited Ceria.","authors":"Carlos Morales, Rudi Tschammer, Emilia Pożarowska, Julia Kosto, Ignacio J Villar-Garcia, Virginia Pérez-Dieste, Marco Favaro, David E Starr, Paulina Kapuścik, Michał Mazur, Damian Wojcieszak, Jarosław Domaradzki, Carlos Alvarado, Christian Wenger, Karsten Henkel, Jan Ingo Flege","doi":"10.1002/cssc.202402342","DOIUrl":"https://doi.org/10.1002/cssc.202402342","url":null,"abstract":"Ultrathin atomic layer deposited ceria films (< 20 nm) are capable of H2 heterolytic activation at room temperature, undergoing a significant reduction regardless of the absolute pressure, as measured under in-situ conditions by near ambient pressure X-ray photoelectron spectroscopy. ALD-ceria can gradually reduce as a function of H2 concentration under H2/O2 environments, especially for diluted mixtures below 10%. At room temperature, this reduction is limited to the surface region, where the hydroxylation of the ceria surface induces a charge transfer towards the ceria matrix, reducing Ce4+ cations to Ce3+. Thus, ALD-ceria replicates the expected sensing mechanism of metal oxides at low temperatures without using any noble metal decorating the oxide surface to enhance H2 dissociation. The intrinsic defects of the ALD deposit seem to play a crucial role since the post-annealing process capable of healing these defects leads to decreased film reactivity. The sensing behavior was successfully demonstrated in sensor test structures by resistance changes towards low concentrations of H2 at low operating temperatures without using noble metals. These promising results call for combining ALD-ceria with more conductive metal oxides, taking advantage of the charge transfer at the interface and thus modifying the depletion layer formed at the heterojunction.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402342"},"PeriodicalIF":7.5,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996966","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}

引用次数: 0

Preparative Isolation of N-Glycans from Natural Sources Mediated by a Deglycosylating Heterogeneous Biocatalyst in Flow. 非均相生物催化剂介导的天然n -聚糖制备分离。

IF 7.5 2区化学

ChemSusChem Pub Date : 2025-01-16 DOI: 10.1002/cssc.202402346

Sonia Serna, Natalia Comino, Niels C Reichardt, Fernando López-Gallego

{"title":"Preparative Isolation of N-Glycans from Natural Sources Mediated by a Deglycosylating Heterogeneous Biocatalyst in Flow.","authors":"Sonia Serna, Natalia Comino, Niels C Reichardt, Fernando López-Gallego","doi":"10.1002/cssc.202402346","DOIUrl":"10.1002/cssc.202402346","url":null,"abstract":"Efficient methods for isolating N-glycans are essential to understanding the functions and characteristics of the entire N-glycome. Enzymatic release using PNGaseF is the most effective approach for releasing mammalian N-glycans for analytical purposes. However, the use of PNGaseF for preparative N-glycan isolation is precluded due to the enzyme's cost and limited stability. In this work, we develop a PNGaseF heterogeneous biocatalyst for the preparative isolation of N-glycans from natural sources. By controlling the immobilization conditions, 100-51 % of offered PNGaseF is immobilized on aldehyde-functionalized agarose porous microbeads through distinct protein orientations, achieving different performances. The enzyme orientation through the N-terminus provides the best activity/operational stability balance, being 20 % more efficient than that randomly oriented. This active and stable heterogeneous biocatalyst eases its application in a packed bed reactor (PBR) for continuous release of free N-glycans from a model glycoprotein. This PBR processes 1 g of ovalbumin from chicken egg white to isolate 95 % of its N-glycans upon operating the PBR for 7 days. Finally, by tuning the flow rate, we can control the profile of N-glycans isolated due to different enzyme kinetics for the deglycosylation reactions. In-line methodologies to isolate N-glycans open new paths for more sustainable protocols to prepare relevant glycans.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402346"},"PeriodicalIF":7.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996977","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}

引用次数: 0

Enzymatic Treatment of Lignin in Alkaline Homogeneous Systems: A Review on Alkaliphilic Laccases. 木质素在碱性均相体系中的酶处理：亲碱漆酶的研究进展。

IF 7.5 2区化学

ChemSusChem Pub Date : 2025-01-16 DOI: 10.1002/cssc.202402377

Lou Delugeau, Stéphane Grelier, Frédéric Peruch

引用次数: 0

Adjusting the Ratio of Oxidation States in a CuO@Cu₂O for the Optimization of Electrocatalytic CO₂ Conversion to Ethylene. 调整CuO@Cu2O中氧化态的比例以优化电催化CO2转化为乙烯。

IF 7.5 2区化学

ChemSusChem Pub Date : 2025-01-16 DOI: 10.1002/cssc.202401963

Jun Lu, Yanhan Ren, Liang Wang, Lie Zou, Jing Liang, Xiaolong Liang, Yan Gao, Fei Li, Junfeng Gao, Andreas Terfort, Jinxuan Liu

{"title":"Adjusting the Ratio of Oxidation States in a CuO@Cu2O for the Optimization of Electrocatalytic CO2 Conversion to Ethylene.","authors":"Jun Lu, Yanhan Ren, Liang Wang, Lie Zou, Jing Liang, Xiaolong Liang, Yan Gao, Fei Li, Junfeng Gao, Andreas Terfort, Jinxuan Liu","doi":"10.1002/cssc.202401963","DOIUrl":"10.1002/cssc.202401963","url":null,"abstract":"Understanding the impact of surface copper valence states on the distribution of electrochemical carbon dioxide products is critical. Herein, CuO@Cu2O with a Cu2+/Cu+ interface was fabricated using wet chemical etching approach. The hollow shape offered a large region for gas adsorption, while the interfacial mixed chemical state of Cu2+/Cu+ with tunable control ratio raised the local density of CHO* and accelerated the carbon-carbon coupling reaction. The H-cell test results demonstrate that, as result of this precise structural design, the Faraday efficiency of ethylene is enhanced from 15.2 % to 43.5 %, and the service life is increased 4 times. In addition, its selectivity is almost 50 % and its partial current density in MEA is 93.2 mA cm-2. In situ Raman and DFT data demonstrate that the Cu2+/Cu+ interface effect enhances the concentration of COCHO intermediates and lowers the energy barrier for the conversion of CO* to COCHO* intermediates.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401963"},"PeriodicalIF":7.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996945","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}

引用次数: 0

Effect of the Electrolyte on the Oxygen Reduction Reaction with a MOF Embedded Co-Porphyrin. 电解质对PCN-224（Co）氧还原反应的影响

IF 7.5 2区化学

ChemSusChem Pub Date : 2025-01-16 DOI: 10.1002/cssc.202402295

Dana Rademaker, Stefania Tanase, Dennis G H Hetterscheid

{"title":"Effect of the Electrolyte on the Oxygen Reduction Reaction with a MOF Embedded Co-Porphyrin.","authors":"Dana Rademaker, Stefania Tanase, Dennis G H Hetterscheid","doi":"10.1002/cssc.202402295","DOIUrl":"10.1002/cssc.202402295","url":null,"abstract":"Electrocatalysis in metal-organic frameworks is an interplay between the diffusion of charges, the intrinsic catalytic rate, and the mass-transport of reactants through the pores. Here a systematic study is carried out to investigate the role of the electrolyte nature and concentration on the oxygen reduction reaction (ORR) with the PCN-224(Co) MOF in aqueous electrolyte. It was found that the ORR activity is slightly influenced by the nature of the ions in solution, providing that the ionic strength is high enough to minimize the resistivity during the measurement. The ORR activity was found to be 1.3-1.5 times lower in lithium acetate compared to sodium acetate, while the ORR activity in cesium acetate was 1.3-1.6 times higher compared to the activity in sodium acetate. Moreover, there was no dependency found of the ORR catalysis on the size of the anion, buffer concentration, or oxygen concentration. These findings suggest that ORR catalysis in PCN-224(Co) is limited by the intrinsic ORR rate at the active site rather than charge transport through the porous structure or substrate transport in the pores. Therefore, optimization of ORR catalysis with this MOF might be achieved by the optimization of the electronics at the cobalt active site.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402295"},"PeriodicalIF":7.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996962","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}

引用次数: 0

Pulsed-Current Operation Enhances H₂O₂ Production on a Boron-Doped Diamond Mesh Anode in a Zero-Gap PEM Electrolyzer. 脉冲电流操作提高了零间隙PEM电解槽中掺硼金刚石网状阳极的H2O2产量。

IF 7.5 2区化学

ChemSusChem Pub Date : 2025-01-16 DOI: 10.1002/cssc.202401947

Adam Vass, Maximilian Göltz, Hanadi Ghanem, Stefan Rosiwal, Tanja Franken, Regina Palkovits, Guido Mul, Mihalis N Tsampas, Georgios Katsoukis, Marco Altomare

{"title":"Pulsed-Current Operation Enhances H2O2 Production on a Boron-Doped Diamond Mesh Anode in a Zero-Gap PEM Electrolyzer.","authors":"Adam Vass, Maximilian Göltz, Hanadi Ghanem, Stefan Rosiwal, Tanja Franken, Regina Palkovits, Guido Mul, Mihalis N Tsampas, Georgios Katsoukis, Marco Altomare","doi":"10.1002/cssc.202401947","DOIUrl":"https://doi.org/10.1002/cssc.202401947","url":null,"abstract":"A niobium (Nb) mesh electrode was coated with boron-doped diamond (BDD) using chemical vapor deposition in a custom-built hot-filament reactor. The BDD-functionalized mesh was tested in a zero-gap electrolysis configuration and evaluated for the anodic formation of H2O2 by selective oxidation of water, including the analysis of the effects on Faradaic efficiency towards H2O2 (FEH2O2) induced by pulsed electrolysis. A low electrolyte flow rate (V⋅anolyte) was found to result in a relatively high concentration of H2O2 in single-pass electrolysis experiments. Regarding pulsed electrolysis, we show an optimal ratio of on-time to off-time to obtain the highest concentration of H2O2. Off-times that are \"too short\" result in decreased FEH2O2, whereas \"too long\" off-times dilute the product in the electrolyte stream. Using our electrolyzer setup with an anodic pulse of 2 s with 4 s intervals, and a V⋅anolyte of 0.75 cm3 min-1, resulted in the best performance. This adjustment increased the FEH2O2 by 70 % compared to constant current electrolysis, at industrially relevant current densities (150 mA cm-2). Fine tuning of BDD morphology, flow patterns, and anolyte composition might further increase the performance of zero-gap electrolyzers in pulsed operation modes.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401947"},"PeriodicalIF":7.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996979","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}

引用次数: 0

Valorization of Humins by Cyclic Levulinic Acid Production Using Polyoxometalates and Formic Acid. 用多金属氧酸盐和甲酸生产环乙酰丙酸对人类素的催化作用。

IF 7.5 2区化学

ChemSusChem Pub Date : 2025-01-15 DOI: 10.1002/cssc.202401973

André Wassenberg, Tobias Esser, Maximilian J Poller, Dorothea Voß, Jakob Albert

{"title":"Valorization of Humins by Cyclic Levulinic Acid Production Using Polyoxometalates and Formic Acid.","authors":"André Wassenberg, Tobias Esser, Maximilian J Poller, Dorothea Voß, Jakob Albert","doi":"10.1002/cssc.202401973","DOIUrl":"10.1002/cssc.202401973","url":null,"abstract":"At a time when increasing attention is paid to sustainability in chemistry, levulinic acid (LA) is one of the most important platform chemicals for the goal of overcoming our dependence on fossil raw materials. However, a so far limiting obstacle on the way to efficient LA production from biomass is the formation of undesirable humin byproducts. In this work, a new catalytic route for the effective utilization of these humin byproducts, enabling a cyclic synthesis of LA using formic acid (FA) as organocatalyst is proposed. Selective catalytic oxidation (SCO) of humins using the H5PV2Mo10O40 (HPA-2) polyoxometalate (POM) catalyst produces FA that can be isolated from the aqueous reaction mixture by using nanofiltration membranes accompanied by a complete catalyst recycling (>99 %). After concentration of FA by distillation, the latter can be used as organocatalyst for LA production from sugars, whereby the formed humins can in turn be separated and used as substrates for further FA production via SCO to close the catalytic cycle. By using FA as a green and sustainable acidic organocatalyst, relatively high yields of LA (up to 42 mol %) could be achieved. In the future this can potentially lead to the creation of a closed cycle for an environmentally friendly and efficient production of green LA without undesired humin formation.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202401973"},"PeriodicalIF":7.5,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142982287","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}

引用次数: 0

Engineering Cascade Bio-solar Cells Inspired by the Z-Scheme of Oxygenic Photosynthesis: Layered Chlorophyll and Bacterio-chlorophyll Derivatives. 受氧光合作用z方案启发的工程级联生物太阳能电池：层状叶绿素和细菌-叶绿素衍生物。

IF 7.5 2区化学

ChemSusChem Pub Date : 2025-01-15 DOI: 10.1002/cssc.202402588

Shengnan Duan, Teng Gu, Chiasa Uragami, Shin-Ichi Sasaki, Yuanqi Zhou, Ruohan Tao, Xianju Zhou, Chunbao Feng, Hitoshi Tamiaki, Xiao-Feng Wang, Zeyun Xiao, Hideki Hashimoto

{"title":"Engineering Cascade Bio-solar Cells Inspired by the Z-Scheme of Oxygenic Photosynthesis: Layered Chlorophyll and Bacterio-chlorophyll Derivatives.","authors":"Shengnan Duan, Teng Gu, Chiasa Uragami, Shin-Ichi Sasaki, Yuanqi Zhou, Ruohan Tao, Xianju Zhou, Chunbao Feng, Hitoshi Tamiaki, Xiao-Feng Wang, Zeyun Xiao, Hideki Hashimoto","doi":"10.1002/cssc.202402588","DOIUrl":"https://doi.org/10.1002/cssc.202402588","url":null,"abstract":"The natural Z-scheme of oxygenic photosynthesis efficiently drives electron transfer from photosystem II (PSII) to photosystem I (PSI) via an electron transport chain, despite the lower energy levels of PSII. Inspired by this sophisticated mechanism, we present a layered cascade bio-solar cell (CBSC) that emulates the Z-scheme. In this design, chlorophyll derivatives (Chl) act as PSI analogs, while bacteriochlorophyll derivatives (BChl) serve as PSII analogs in the active layer. The resulting photocurrent, prominently detected in the near-infrared region, is validated through external quantum efficiency measurements. Sub-nanosecond transient absorption spectroscopy reveals a prolonged charge transfer (CT) state from BChl to Chl (Chl-/BChl+ species) compared to the reverse direction (Chl+/BChl- species). This asymmetry highlights a dominant electron flow from BChl (PSII analog) to Chl (PSI analog) under simultaneous excitation, effectively replicating the natural Z-scheme electron transfer. These findings represent a significant advance in the design of bio-inspired solar cells, paving the way for artificial photosynthesis systems and offering profound insights into improving photovoltaic theory and efficiency.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402588"},"PeriodicalIF":7.5,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142982274","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}

引用次数: 0

The Impact of Ligand Structure and Reaction Temperature on Ethenolysis of Fatty Acid Methyl Esters Catalyzed by Spirocyclic Alkyl Amino Carbene Ru Complexes. 配体结构和反应温度对螺旋环烷基氨基羰基络合物催化脂肪酸甲酯醇解反应的影响。

IF 7.5 2区化学

ChemSusChem Pub Date : 2025-01-15 DOI: 10.1002/cssc.202402190

Anna V Afanaseva, Alexander A Vinogradov, Alexey A Vinogradov, Mikhail E Minyaev, Dmitry A Pyatakov, Alexander N Tavtorkin, Vladimir V Bagrov, Pavel V Ivchenko, Ilya E Nifant'ev

{"title":"The Impact of Ligand Structure and Reaction Temperature on Ethenolysis of Fatty Acid Methyl Esters Catalyzed by Spirocyclic Alkyl Amino Carbene Ru Complexes.","authors":"Anna V Afanaseva, Alexander A Vinogradov, Alexey A Vinogradov, Mikhail E Minyaev, Dmitry A Pyatakov, Alexander N Tavtorkin, Vladimir V Bagrov, Pavel V Ivchenko, Ilya E Nifant'ev","doi":"10.1002/cssc.202402190","DOIUrl":"10.1002/cssc.202402190","url":null,"abstract":"Spirocyclic alkyl amino carbene (SCAAC) Ru complexes demonstrate outstanding activity and selectivity in ethenolysis of methyl oleate (MO) or fatty acid methyl esters (FAMEs), and 5,6-dimethoxyindane derivative was the most active catalyst to date. For the further catalyst design, we proposed modifying the spirocyclic fragment by fusion of saturated carbo- or heterocycle, linked to the 5,6-positions of indane or 6,7- positions of tetralin. Another suggested way of the modification of SCAAC complex was the insertion of chromane fragment to the carbene ligand. Using an alternative approach to SCAAC ligand precursors, based on hydroformylation of indenes, dihydronaphthalenes and their analogs, new SCAAC complexes were synthesized, their cis-configuration was confirmed by XRD. Comparative study of new and known selected complexes in ethenolysis of FAMEs (84 wt% MO) revealed that each of SCAAC catalysts has a temperature optimum of activity. At 60 °C 0.5 ppm of the complex containing 1,2,3,4,5,6,7,8-octahydroanthracene spirocyclic fragment provided 56 % conversion of FAMEs with TON=1.1⋅106; 0.25 ppm of this complex in ethenolysis of high-purity MO demonstrated the TON ~2⋅106, leading among the catalysts under study. In ethenolysis of FAMEs chromane derivative showed TON of 4-6⋅105 and unprecedented temperature-independent 99.7-99.9 % selectivity at 15-60 °C.","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402190"},"PeriodicalIF":7.5,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142982283","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}

引用次数: 0

Chemical and Enzymatic Mechanosynthesis of Organocatalytic Peptide Materials Based on Proline and Phenylalanine. 基于脯氨酸和苯丙氨酸的有机催化多肽材料的化学和酶的机械合成。

IF 7.5 2区化学

ChemSusChem Pub Date : 2025-01-15 DOI: 10.1002/cssc.202402446

Alexandra Rios-Echeverri, Carlos E Puerto Galvis, Karen J Ardila-Fierro, José G Hernández

引用次数: 0