Pub Date : 2026-05-26Epub Date: 2026-05-01DOI: 10.1039/d6cy00211k
Lei Yang , Yulin Wang , Qingyun Wang , Feng Lin , Liang Lv
Rational vacancy engineering endows semiconductors with exotic chemical and physical properties, particularly in photocatalysis. Herein, we report a KBr-mediated bulk vacancy repolymerization strategy for the structural engineering of polymeric carbon nitride (PCN), obtaining a modified catalyst (KCN) with optimized physicochemical properties. Structural characterizations reveal that KBr mediation not only heals bulk vacancies and reconstructs layered stacking but also introduces surface cyano groups and K+ ions into the framework, providing a favorable dynamic driving force for the photocatalytic oxygen reduction process. Therefore, KCN exhibits a remarkable H2O2 evolution rate of 5488 μmol g−1 h−1 (λ > 420 nm), which is about 140 fold higher than pristine PCN. This work provides a promising avenue for designing high-performance photocatalysts.
{"title":"Structural healing of deficient carbon nitride for efficient H2O2 photosynthesis","authors":"Lei Yang , Yulin Wang , Qingyun Wang , Feng Lin , Liang Lv","doi":"10.1039/d6cy00211k","DOIUrl":"10.1039/d6cy00211k","url":null,"abstract":"<div><div>Rational vacancy engineering endows semiconductors with exotic chemical and physical properties, particularly in photocatalysis. Herein, we report a KBr-mediated bulk vacancy repolymerization strategy for the structural engineering of polymeric carbon nitride (PCN), obtaining a modified catalyst (KCN) with optimized physicochemical properties. Structural characterizations reveal that KBr mediation not only heals bulk vacancies and reconstructs layered stacking but also introduces surface cyano groups and K<sup>+</sup> ions into the framework, providing a favorable dynamic driving force for the photocatalytic oxygen reduction process. Therefore, KCN exhibits a remarkable H<sub>2</sub>O<sub>2</sub> evolution rate of 5488 μmol g<sup>−1</sup> h<sup>−1</sup> (<em>λ</em> > 420 nm), which is about 140 fold higher than pristine PCN. This work provides a promising avenue for designing high-performance photocatalysts.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 10","pages":"Pages 3502-3507"},"PeriodicalIF":4.0,"publicationDate":"2026-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011631","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}
Pub Date : 2026-05-26Epub Date: 2026-04-02DOI: 10.1039/d5cy01557j
D. N. Maaskant , P. T. Prins , N. S. Genz , B. M. Weckhuysen , M. Monai
To improve catalytic performance, it is important to control the state of the active phase of catalysts (e.g., metallic, oxidic, or carbide). However, conventional pretreatments (e.g., heating) often cause unwanted side-effects, like sintering and active phase encapsulation. Here, we propose UV light illumination as an alternative approach to tune the active phase under reaction conditions. We showcase this possibility using a Co/TiO2 catalyst for CO2 hydrogenation. UV light illumination resulted in an increase in the percentage of reduced Co (i.e., 93 vs. 97% metallic cobalt for dark vs. light), as revealed by X-ray absorption spectroscopy. Furthermore, using operando Fourier transform infrared spectroscopy under CO2 hydrogenation conditions, we observed a light-induced change in surface coverage of different species, such as CO*, (bi)carbonates and formates. When switching between dark and light conditions, a reversible increase in activity was observed, accompanied by a decrease in the IR absorption bands of formates and CO*. We propose that the reduction of cobalt is due to a charge transfer mechanism from the conduction band of the titania support to the conduction band of the cobalt metal (oxide) nanoparticles. On the other hand, we attribute CO desorption to a metal-to-ligand charge transfer, from the d-band of the cobalt metal (oxide) nanoparticles to the adsorbed CO molecules. While UV light illumination is more commonly used to enhance catalytic performance, we demonstrate its application to tune the active phase of the catalyst, offering advantages over conventional methods that suffer from undesired effects, like metal (oxide) nanoparticle sintering.
为了提高催化性能，控制催化剂（如金属、氧化物或碳化物）的活性相状态是很重要的。然而，传统的预处理（如加热）通常会引起不必要的副作用，如烧结和活性相封装。在这里，我们提出紫外光照明作为一种替代方法来调整反应条件下的活性相。我们使用Co/TiO2催化剂进行CO2加氢，展示了这种可能性。正如x射线吸收光谱所显示的那样，紫外光照射导致还原Co的百分比增加（即，在暗与光下，金属钴的百分比为93% vs. 97%）。此外，在CO2加氢条件下，利用operando傅立叶变换红外光谱，我们观察到不同物种（如CO*， （bi）碳酸盐和甲酸盐）的表面覆盖发生了光诱导变化。当在黑暗和光照条件之间切换时，观察到活性的可逆增加，同时甲酸酯和CO*的红外吸收带减少。我们提出钴的还原是由于电荷从钛载体的导带转移到钴金属（氧化物）纳米颗粒的导带。另一方面，我们将CO的解吸归因于金属到配体的电荷转移，从钴金属（氧化物）纳米颗粒的d波段到被吸附的CO分子。虽然紫外光照明更常用于提高催化性能，但我们展示了它在调整催化剂活性相方面的应用，相比于传统方法（如金属（氧化物）纳米颗粒烧结）带来的不良影响，它具有优势。
{"title":"Tuning the active phase and surface chemistry of a CO2 hydrogenation Co/TiO2 catalyst with UV light","authors":"D. N. Maaskant , P. T. Prins , N. S. Genz , B. M. Weckhuysen , M. Monai","doi":"10.1039/d5cy01557j","DOIUrl":"10.1039/d5cy01557j","url":null,"abstract":"<div><div>To improve catalytic performance, it is important to control the state of the active phase of catalysts (<em>e.g.</em>, metallic, oxidic, or carbide). However, conventional pretreatments (<em>e.g.</em>, heating) often cause unwanted side-effects, like sintering and active phase encapsulation. Here, we propose UV light illumination as an alternative approach to tune the active phase under reaction conditions. We showcase this possibility using a Co/TiO<sub>2</sub> catalyst for CO<sub>2</sub> hydrogenation. UV light illumination resulted in an increase in the percentage of reduced Co (<em>i.e.</em>, 93 <em>vs.</em> 97% metallic cobalt for dark <em>vs.</em> light), as revealed by X-ray absorption spectroscopy. Furthermore, using operando Fourier transform infrared spectroscopy under CO<sub>2</sub> hydrogenation conditions, we observed a light-induced change in surface coverage of different species, such as CO*, (bi)carbonates and formates. When switching between dark and light conditions, a reversible increase in activity was observed, accompanied by a decrease in the IR absorption bands of formates and CO*. We propose that the reduction of cobalt is due to a charge transfer mechanism from the conduction band of the titania support to the conduction band of the cobalt metal (oxide) nanoparticles. On the other hand, we attribute CO desorption to a metal-to-ligand charge transfer, from the d-band of the cobalt metal (oxide) nanoparticles to the adsorbed CO molecules. While UV light illumination is more commonly used to enhance catalytic performance, we demonstrate its application to tune the active phase of the catalyst, offering advantages over conventional methods that suffer from undesired effects, like metal (oxide) nanoparticle sintering.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 10","pages":"Pages 3508-3519"},"PeriodicalIF":4.0,"publicationDate":"2026-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011632","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}
The one-pot reductive N-formylation of nitro substrates using CO2 as a renewable C1 feedstock is a sustainable and practical route to access formamides, key intermediates in pharmaceuticals and bioactive molecules. We report an efficient strategy for the reductive N-formylation of nitro compounds with CO2 and phenylsilane enabled by a single-site cobalt(ii) hydride catalyst immobilized within a zirconium-based UiO-67 metal–organic framework. The confined environment of UiO-67 facilitates tandem nitro group reduction and CO2 incorporation within a single catalytic platform, delivering formamides in excellent yields. The catalytic system displays a broad substrate scope, tolerating aromatic and aliphatic nitro compounds bearing electron-donating, electron-withdrawing, halogen and heteroaromatic substituents. UiO-67-CoH demonstrates good stability and recyclability, retaining its crystalline framework while achieving nearly 99% conversion of nitro substrates and delivering up to 94% yield of the corresponding formamides. Detailed mechanistic insights obtained from control experiments, spectroscopic analysis, kinetic studies and DFT calculations reveal the role of the MOF in stabilizing reactive cobalt hydride species and suppressing deactivation pathways. Overall, this study establishes UiO-67-CoH as a robust and versatile platform for CO2 valorization and underscores the broader potential of MOFs in designing earth-abundant single-site catalysts for sustainable transformations to produce value-added fine chemicals.
{"title":"CO2-mediated direct N-formylation of nitro compounds by a metal–organic framework node-supported cobalt(ii) catalyst","authors":"Swapnaneel Sarmah , Chhaya Thadhani , Aditya Kumar , Kuntal Manna","doi":"10.1039/d5cy01380a","DOIUrl":"10.1039/d5cy01380a","url":null,"abstract":"<div><div>The one-pot reductive <em>N</em>-formylation of nitro substrates using CO<sub>2</sub> as a renewable C1 feedstock is a sustainable and practical route to access formamides, key intermediates in pharmaceuticals and bioactive molecules. We report an efficient strategy for the reductive <em>N</em>-formylation of nitro compounds with CO<sub>2</sub> and phenylsilane enabled by a single-site cobalt(<span>ii</span>) hydride catalyst immobilized within a zirconium-based UiO-67 metal–organic framework. The confined environment of UiO-67 facilitates tandem nitro group reduction and CO<sub>2</sub> incorporation within a single catalytic platform, delivering formamides in excellent yields. The catalytic system displays a broad substrate scope, tolerating aromatic and aliphatic nitro compounds bearing electron-donating, electron-withdrawing, halogen and heteroaromatic substituents. UiO-67-CoH demonstrates good stability and recyclability, retaining its crystalline framework while achieving nearly 99% conversion of nitro substrates and delivering up to 94% yield of the corresponding formamides. Detailed mechanistic insights obtained from control experiments, spectroscopic analysis, kinetic studies and DFT calculations reveal the role of the MOF in stabilizing reactive cobalt hydride species and suppressing deactivation pathways. Overall, this study establishes UiO-67-CoH as a robust and versatile platform for CO<sub>2</sub> valorization and underscores the broader potential of MOFs in designing earth-abundant single-site catalysts for sustainable transformations to produce value-added fine chemicals.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 10","pages":"Pages 3559-3571"},"PeriodicalIF":4.0,"publicationDate":"2026-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011638","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}
Pub Date : 2026-05-26Epub Date: 2026-04-10DOI: 10.1039/d6cy00244g
Mudi Wu , Mingwu Tan
Plastic waste is accumulating in our environment, causing severe threats to the ecosystem and human health. Conventional recycling methods often suffer from low efficiency and limited product value, hindering their extensive application. By comparison, microwave catalytic pyrolysis of plastic waste is a promising route due to its rapid and uniform heating, high energy efficiency, and superior product selectivity. Here we review recent progress in applying microwave catalytic pyrolysis for plastic waste upcycling from the perspective of type, function, and synthesis strategies of catalysts. This review introduces the fundamental principles of microwave heating in the catalytic pyrolysis process, and the conversion pathway of plastic waste over different catalysts, emphasizing the relationship between catalyst properties and product selectivity. The high economic viability of this technology provides huge potential for its industrial application. Finally, challenges, including catalyst stability, mechanism study, and the gap between lab and real-world scenarios, are also critically discussed. Overall, microwave catalysis shows significant potential for plastic waste upcycling.
{"title":"Recent progress for microwave catalytic pyrolysis of plastic waste to valuable chemicals","authors":"Mudi Wu , Mingwu Tan","doi":"10.1039/d6cy00244g","DOIUrl":"10.1039/d6cy00244g","url":null,"abstract":"<div><div>Plastic waste is accumulating in our environment, causing severe threats to the ecosystem and human health. Conventional recycling methods often suffer from low efficiency and limited product value, hindering their extensive application. By comparison, microwave catalytic pyrolysis of plastic waste is a promising route due to its rapid and uniform heating, high energy efficiency, and superior product selectivity. Here we review recent progress in applying microwave catalytic pyrolysis for plastic waste upcycling from the perspective of type, function, and synthesis strategies of catalysts. This review introduces the fundamental principles of microwave heating in the catalytic pyrolysis process, and the conversion pathway of plastic waste over different catalysts, emphasizing the relationship between catalyst properties and product selectivity. The high economic viability of this technology provides huge potential for its industrial application. Finally, challenges, including catalyst stability, mechanism study, and the gap between lab and real-world scenarios, are also critically discussed. Overall, microwave catalysis shows significant potential for plastic waste upcycling.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 10","pages":"Pages 3444-3463"},"PeriodicalIF":4.0,"publicationDate":"2026-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011629","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}
The electrochemical synthesis of hydrogen peroxide (H2O2) in neutral media is highly desirable for practical applications but suffers from sluggish kinetics due to insufficient proton availability. Here, we report a strategy to overcome this limitation by engineering the local reaction microenvironment of ZnO catalysts. We construct tuneable Lewis acidic sites by grafting CeO2 nanoparticles onto ZnO nanorods, creating a ZnO–Cex composite. This Ce-derived interface polarizes water molecules, functioning as an efficient hydroxyl pump to establish a localized alkaline microenvironment that facilitates the two-electron oxygen reduction pathway. In situ spectroscopic tracking of reaction intermediates reveals that optimal Ce modification significantly accelerates the protonation of *OOH to *HOOH. The ZnO–Ce0.2 catalyst achieves a faradaic efficiency of approximately 97% and a high H2O2 production rate of 54.29 mol gcat−1 h−1 at 0.6 A cm−2 in a neutral electrolyte with pure O2. Notably, this performance is successfully extended to operation under ambient air, where the catalyst maintains exceptional activity and selectivity. This work demonstrates that tailoring interfacial Lewis acidity to modulate the local pH is a potent strategy for advancing sustainable H2O2 electrosynthesis.
在中性介质中电化学合成过氧化氢（H2O2）在实际应用中是非常理想的，但由于质子可用性不足，动力学缓慢。在这里，我们报告了一种通过设计ZnO催化剂的局部反应微环境来克服这一限制的策略。我们通过将CeO2纳米颗粒接枝到ZnO纳米棒上，构建了可调谐的Lewis酸位点，从而制备了ZnO - cex复合材料。这种ce衍生的界面使水分子极化，作为一个有效的羟基泵，建立一个局部碱性微环境，促进双电子氧还原途径。反应中间体的原位光谱跟踪表明，最佳的Ce修饰显著加速了*OOH到*HOOH的质子化。ZnO-Ce0.2催化剂在含纯O2的中性电解液中，在0.6 a cm−2条件下，法拉第效率约为97%，H2O2产率高达54.29 mol gcat−1 h−1。值得注意的是，这种性能成功地扩展到环境空气下的操作，在这种情况下，催化剂保持了出色的活性和选择性。这项工作表明，调整界面刘易斯酸度来调节局部pH值是促进可持续H2O2电合成的有效策略。
{"title":"Modulating local pH environment in ZnO–Cex catalysts for efficient neutral H2O2 electrosynthesis","authors":"Yuxiang Zhang , Zibo Geng , Hao Zheng , Yue Lu , Xinyu Shan , Xinxian Zhu , Shan Ding","doi":"10.1039/d6cy00230g","DOIUrl":"10.1039/d6cy00230g","url":null,"abstract":"<div><div>The electrochemical synthesis of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) in neutral media is highly desirable for practical applications but suffers from sluggish kinetics due to insufficient proton availability. Here, we report a strategy to overcome this limitation by engineering the local reaction microenvironment of ZnO catalysts. We construct tuneable Lewis acidic sites by grafting CeO<sub>2</sub> nanoparticles onto ZnO nanorods, creating a ZnO–Ce<sub><em>x</em></sub> composite. This Ce-derived interface polarizes water molecules, functioning as an efficient hydroxyl pump to establish a localized alkaline microenvironment that facilitates the two-electron oxygen reduction pathway. <em>In situ</em> spectroscopic tracking of reaction intermediates reveals that optimal Ce modification significantly accelerates the protonation of *OOH to *HOOH. The ZnO–Ce<sub>0.2</sub> catalyst achieves a faradaic efficiency of approximately 97% and a high H<sub>2</sub>O<sub>2</sub> production rate of 54.29 mol g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup> at 0.6 A cm<sup>−2</sup> in a neutral electrolyte with pure O<sub>2</sub>. Notably, this performance is successfully extended to operation under ambient air, where the catalyst maintains exceptional activity and selectivity. This work demonstrates that tailoring interfacial Lewis acidity to modulate the local pH is a potent strategy for advancing sustainable H<sub>2</sub>O<sub>2</sub> electrosynthesis.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 10","pages":"Pages 3633-3638"},"PeriodicalIF":4.0,"publicationDate":"2026-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011672","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}
Catalytic dehydration of alcohols remains a challenge in organic synthesis, and olefin products are important synthetic precursors because of their high reactivity. Platinum-group-metal-on-carbon catalysts (such as Ru/C and Pd/C) are commercially available and widely utilized as heterogeneous, green, and sustainable catalysts in various organic reactions. However, examples of their application to the catalytic dehydration of alcohols have not been reported. Herein, we demonstrate the Ru/C-catalyzed dehydration of tertiary (tert) alcohols in toluene under thermal conditions. Ru/C also potentially exhibits oxidative activity. Therefore, a tandem reaction involving the Ru/C-catalyzed dehydration of tert-benzylic alcohols, a Diels–Alder reaction, and subsequent oxygen oxidation was developed to afford highly functionalized aromatic products. Additionally, a one-pot synthesis of biaryls from 1-arylcyclohexanols as tert-alcohol substrates was successfully developed via Pd/C-catalyzed dehydration and subsequent dehydrogenation in H2O. These green and sustainable synthetic approaches based on novel heterogeneous dehydration methodologies are valuable for the construction of diverse functional materials.
{"title":"Platinum-group-metal-on-carbon catalyzed dehydration of tertiary alcohols and its application to the one-pot synthesis of aromatics","authors":"Shuki Oyama , Yuto Suganuma , Rina Adachi , Shuji Akai , Yoshinari Sawama","doi":"10.1039/d6cy00165c","DOIUrl":"10.1039/d6cy00165c","url":null,"abstract":"<div><div>Catalytic dehydration of alcohols remains a challenge in organic synthesis, and olefin products are important synthetic precursors because of their high reactivity. Platinum-group-metal-on-carbon catalysts (such as Ru/C and Pd/C) are commercially available and widely utilized as heterogeneous, green, and sustainable catalysts in various organic reactions. However, examples of their application to the catalytic dehydration of alcohols have not been reported. Herein, we demonstrate the Ru/C-catalyzed dehydration of tertiary (<em>tert</em>) alcohols in toluene under thermal conditions. Ru/C also potentially exhibits oxidative activity. Therefore, a tandem reaction involving the Ru/C-catalyzed dehydration of <em>tert</em>-benzylic alcohols, a Diels–Alder reaction, and subsequent oxygen oxidation was developed to afford highly functionalized aromatic products. Additionally, a one-pot synthesis of biaryls from 1-arylcyclohexanols as <em>tert</em>-alcohol substrates was successfully developed <em>via</em> Pd/C-catalyzed dehydration and subsequent dehydrogenation in H<sub>2</sub>O. These green and sustainable synthetic approaches based on novel heterogeneous dehydration methodologies are valuable for the construction of diverse functional materials.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 10","pages":"Pages 3536-3541"},"PeriodicalIF":4.0,"publicationDate":"2026-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011635","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}
Pub Date : 2026-05-26Epub Date: 2026-04-30DOI: 10.1039/d6cy00123h
Delai Wang , Guoyu Lin , Hai-Qun Xu , Zihao Zhai , Chang Mei , Xiang Chen , Guangshun Wu , Zheng Cao , Zhen Jin , Shilong Xu , Di Wang , Lei Wang , Weiwei Dong , Xiaoran Niu , Yi Ding
Proton exchange membrane fuel cells (PEMFCs) are promising for mobile and renewable energy storage due to their high efficiency and zero-carbon emissions. However, the slow kinetics of the oxygen reduction reaction (ORR) at the cathode remains a significant challenge. In this work, we successfully synthesized an L10-PtZn intermetallic compound (IMC) with a core–shell structure using a thiourea molecule-assisted strategy based on strong metal–support interactions with Pt–S bonding. The as-prepared PtZn-IMC catalyst exhibited significantly enhanced oxygen reduction reaction (ORR) performance, achieving a mass activity (MA) of 1.50 A mgPt−1, approximately six-fold higher than that achieved by commercial Pt/C nanoparticles. Moreover, the catalyst demonstrated remarkable stability, retaining 93% of MA in rotating disk electrode (RDE) tests and showing only a 7.9% peak power density loss in membrane electrode assembly (MEA) measurements. Density functional theory (DFT) calculations reveal that the ordered PtZn structure lowered the Pt d-band center, improving the ORR kinetics and structural stability. This work demonstrates the potential of core–shell structure PtZn-IMC as an efficient and stable catalyst for PEMFC applications.
质子交换膜燃料电池（pemfc）由于其高效率和零碳排放，在移动和可再生能源存储方面前景广阔。然而，阴极氧还原反应（ORR）的缓慢动力学仍然是一个重大的挑战。在这项工作中，我们利用硫脲分子辅助策略，基于与Pt-S键的强金属支持相互作用，成功合成了具有核壳结构的L10-PtZn金属间化合物（IMC）。制备的PtZn-IMC催化剂表现出显著增强的氧还原反应（ORR）性能，达到1.50 a mgPt−1的质量活性（MA），比商用Pt/C纳米颗粒高约6倍。此外，该催化剂表现出了显著的稳定性，在旋转圆盘电极（RDE）测试中保留了93%的MA，在膜电极组装（MEA）测试中仅显示出7.9%的峰值功率密度损失。密度泛函理论（DFT）计算表明，有序的PtZn结构降低了Pt d带中心，提高了ORR动力学和结构稳定性。这项工作证明了核壳结构PtZn-IMC作为一种高效稳定的PEMFC催化剂的潜力。
{"title":"Sulfur-confinement synthesis of an L10-PtZn intermetallic catalyst for enhanced oxygen reduction","authors":"Delai Wang , Guoyu Lin , Hai-Qun Xu , Zihao Zhai , Chang Mei , Xiang Chen , Guangshun Wu , Zheng Cao , Zhen Jin , Shilong Xu , Di Wang , Lei Wang , Weiwei Dong , Xiaoran Niu , Yi Ding","doi":"10.1039/d6cy00123h","DOIUrl":"10.1039/d6cy00123h","url":null,"abstract":"<div><div>Proton exchange membrane fuel cells (PEMFCs) are promising for mobile and renewable energy storage due to their high efficiency and zero-carbon emissions. However, the slow kinetics of the oxygen reduction reaction (ORR) at the cathode remains a significant challenge. In this work, we successfully synthesized an L1<sub>0</sub>-PtZn intermetallic compound (IMC) with a core–shell structure using a thiourea molecule-assisted strategy based on strong metal–support interactions with Pt–S bonding. The as-prepared PtZn-IMC catalyst exhibited significantly enhanced oxygen reduction reaction (ORR) performance, achieving a mass activity (MA) of 1.50 A mg<sub>Pt</sub><sup>−1</sup>, approximately six-fold higher than that achieved by commercial Pt/C nanoparticles. Moreover, the catalyst demonstrated remarkable stability, retaining 93% of MA in rotating disk electrode (RDE) tests and showing only a 7.9% peak power density loss in membrane electrode assembly (MEA) measurements. Density functional theory (DFT) calculations reveal that the ordered PtZn structure lowered the Pt d-band center, improving the ORR kinetics and structural stability. This work demonstrates the potential of core–shell structure PtZn-IMC as an efficient and stable catalyst for PEMFC applications.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 10","pages":"Pages 3542-3550"},"PeriodicalIF":4.0,"publicationDate":"2026-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011636","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}
Pub Date : 2026-05-26Epub Date: 2026-04-16DOI: 10.1039/d6cy00216a
Lukas Popp , Patrick Schühle
Biomass-derived hydrogen is frequently contaminated with CO and CO2, which limits its direct utilization in downstream applications. Cyclic hydrogenation/dehydrogenation of liquid organic hydrogen carriers (LOHCs) such as benzyltoluene (BT) provides a pathway to simultaneously store hydrogen and purify such “low-grade” hydrogen feeds. In this context, Ni-based catalysts are particularly attractive because they can hydrogenate aromatic systems under CO-containing atmospheres while representing a relatively cheap alternative to noble metal catalysts. Here, we systematically investigate BT hydrogenation over a commercial Ni/Al2O3/SiO2 catalyst under process-relevant LOHC conditions (T = 170–230 °C, p = 10–50 bar) in the presence of CO (0–6%) and demonstrate that BT conversion remains feasible even at high CO levels, while the hydrogenation rate decreases due to competitive CO adsorption. Time-resolved analysis of both gas- and liquid-phase compositions further reveals CO methanation during BT hydrogenation, indicating that both reactions proceed in parallel while competing for active sites. By varying temperature and total pressure, the balance between BT hydrogenation and methanation can be steered, with 230 °C and 50 bar identified as the most favorable conditions for efficient BT hydrogenation under CO presence. In addition, introducing CO2 at biomass-typical concentrations (30 vol%) shows that it likewise adsorbs competitively on Ni and is also converted to methane. Collectively, these results highlight Ni-based catalysts as a robust catalyst for mixed-gas hydrogenation and LOHC-enabled purification/storage of biogenic hydrogen, while underscoring an inherent trade-off between competitive (co-)methanation, that consumes a fraction of hydrogen as CH4 that cannot be recovered upon LOHC dehydrogenation, yet constitutes an energy-dense coproduct stream that may be valorized.
生物质衍生的氢经常被CO和CO2污染，这限制了其在下游应用中的直接利用。苯基甲苯（BT）等液态有机氢载体（lohc）的循环加氢/脱氢为同时储存氢和净化这种“低品位”氢原料提供了一条途径。在这种情况下，镍基催化剂特别有吸引力，因为它们可以在含co的气氛下使芳香体系氢化，同时代表了贵金属催化剂的相对便宜的替代品。在这里，我们系统地研究了在与工艺相关的LOHC条件下（T = 170-230°C, p = 10-50 bar），在CO（0-6%）存在下，BT在商业Ni/Al2O3/SiO2催化剂上的加氢，并证明了即使在高CO水平下，BT转化仍然是可行的，而由于CO的竞争性吸附，加氢速率降低。气相和液相组成的时间分辨分析进一步揭示了BT加氢过程中的CO甲烷化，表明两个反应并行进行，同时竞争活性位点。通过改变温度和总压，可以控制BT加氢和甲烷化之间的平衡，其中230℃和50 bar是CO存在下BT加氢的最有利条件。此外，以生物质典型浓度（30 vol%）引入二氧化碳表明，它同样具有竞争性地吸附Ni，并转化为甲烷。总的来说，这些结果强调了镍基催化剂作为混合气体加氢和LOHC支持的生物氢净化/储存的强大催化剂，同时强调了竞争性（共）甲烷化之间的内在权衡，甲烷化消耗一部分氢作为CH4，不能在LOHC脱氢中回收，但构成了一个能量密集的副产物流。
{"title":"Nickel catalysts in the hydrogenation of benzyltoluene using impure hydrogen streams","authors":"Lukas Popp , Patrick Schühle","doi":"10.1039/d6cy00216a","DOIUrl":"10.1039/d6cy00216a","url":null,"abstract":"<div><div>Biomass-derived hydrogen is frequently contaminated with CO and CO<sub>2</sub>, which limits its direct utilization in downstream applications. Cyclic hydrogenation/dehydrogenation of liquid organic hydrogen carriers (LOHCs) such as benzyltoluene (BT) provides a pathway to simultaneously store hydrogen and purify such “low-grade” hydrogen feeds. In this context, Ni-based catalysts are particularly attractive because they can hydrogenate aromatic systems under CO-containing atmospheres while representing a relatively cheap alternative to noble metal catalysts. Here, we systematically investigate BT hydrogenation over a commercial Ni/Al<sub>2</sub>O<sub>3</sub>/SiO<sub>2</sub> catalyst under process-relevant LOHC conditions (<em>T</em> = 170–230 °C, <em>p</em> = 10–50 bar) in the presence of CO (0–6%) and demonstrate that BT conversion remains feasible even at high CO levels, while the hydrogenation rate decreases due to competitive CO adsorption. Time-resolved analysis of both gas- and liquid-phase compositions further reveals CO methanation during BT hydrogenation, indicating that both reactions proceed in parallel while competing for active sites. By varying temperature and total pressure, the balance between BT hydrogenation and methanation can be steered, with 230 °C and 50 bar identified as the most favorable conditions for efficient BT hydrogenation under CO presence. In addition, introducing CO<sub>2</sub> at biomass-typical concentrations (30 vol%) shows that it likewise adsorbs competitively on Ni and is also converted to methane. Collectively, these results highlight Ni-based catalysts as a robust catalyst for mixed-gas hydrogenation and LOHC-enabled purification/storage of biogenic hydrogen, while underscoring an inherent trade-off between competitive (co-)methanation, that consumes a fraction of hydrogen as CH<sub>4</sub> that cannot be recovered upon LOHC dehydrogenation, yet constitutes an energy-dense coproduct stream that may be valorized.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 10","pages":"Pages 3609-3620"},"PeriodicalIF":4.0,"publicationDate":"2026-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011670","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}
In this contribution, we report the design of Cu nanoparticles encapsulated within both hierarchical and conventional MFI frameworks for the dehydrogenation of ethanol to acetaldehyde. The encapsulated catalysts were successfully synthesized via a hydrothermal method, using tetrabutylammonium hydroxide (TBAOH) and tetrapropylammonium hydroxide (TPAOH) as structure-directing agents (SDAs) for hierarchical and conventional frameworks, respectively. Characterization results showed that the hierarchical silicalite-1 zeolite (Cu@hieS-1) exhibited the simultaneous presence of mesopores and uniform Cu nanoparticles (∼2.3 nm), with high Cu dispersion (82.6%), thereby significantly improving active-site accessibility and reducing diffusion path lengths, eventually enhancing catalytic efficiency. Catalytic testing demonstrated that Cu@hieS-1 achieved 96% ethanol conversion and 82% acetaldehyde yield at 400 °C, outperforming conventional zeolites (15% ethanol conversion and 12% acetaldehyde yield). The reason for the improved catalytic activity over Cu@hieS-1 compared to the conventional ones relates to the fact that Cu@hieS-1 contains a higher proportion of Cu+ species compared with the others, eventually leading to promoting acetaldehyde formation. Additionally, hierarchical zeolites exhibited enhanced catalytic stability, maintaining ∼80% conversion and 82% acetaldehyde yield. This work illustrates the benefits of the encapsulated catalyst in optimizing catalytic performances for sustainable acetaldehyde production.
{"title":"Cu encapsulated in hierarchical MFI zeolites for ethanol dehydrogenation to acetaldehyde","authors":"Kachaporn Saenluang , Narasiri Maineawklang , Anittha Prasertsab , Tawan Sooknoi , Søren Kegnæs , Chularat Wattanakit","doi":"10.1039/d6cy00074f","DOIUrl":"10.1039/d6cy00074f","url":null,"abstract":"<div><div>In this contribution, we report the design of Cu nanoparticles encapsulated within both hierarchical and conventional MFI frameworks for the dehydrogenation of ethanol to acetaldehyde. The encapsulated catalysts were successfully synthesized <em>via</em> a hydrothermal method, using tetrabutylammonium hydroxide (TBAOH) and tetrapropylammonium hydroxide (TPAOH) as structure-directing agents (SDAs) for hierarchical and conventional frameworks, respectively. Characterization results showed that the hierarchical silicalite-1 zeolite (Cu@hieS-1) exhibited the simultaneous presence of mesopores and uniform Cu nanoparticles (∼2.3 nm), with high Cu dispersion (82.6%), thereby significantly improving active-site accessibility and reducing diffusion path lengths, eventually enhancing catalytic efficiency. Catalytic testing demonstrated that Cu@hieS-1 achieved 96% ethanol conversion and 82% acetaldehyde yield at 400 °C, outperforming conventional zeolites (15% ethanol conversion and 12% acetaldehyde yield). The reason for the improved catalytic activity over Cu@hieS-1 compared to the conventional ones relates to the fact that Cu@hieS-1 contains a higher proportion of Cu<sup>+</sup> species compared with the others, eventually leading to promoting acetaldehyde formation. Additionally, hierarchical zeolites exhibited enhanced catalytic stability, maintaining ∼80% conversion and 82% acetaldehyde yield. This work illustrates the benefits of the encapsulated catalyst in optimizing catalytic performances for sustainable acetaldehyde production.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 10","pages":"Pages 3621-3632"},"PeriodicalIF":4.0,"publicationDate":"2026-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011671","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}
Pub Date : 2026-05-26Epub Date: 2026-04-08DOI: 10.1039/d5cy01563d
Jiaqi Zhuang , Han Zhang , Yujing You , Mengyang Yuan , Guoquan Zhou , Liwei Zhao , Zhiqiang Jiang
To address the energy crisis and global warming, utilizing solar energy for photocatalytic reduction of CO2 into fuels represents an ideal solution. This study addresses the core issue of low charge separation efficiency in traditional graphitic carbon nitride (g-C3N4) photocatalysts by successfully synthesizing sulfur (S) and gallium (Ga) co-doped bundled carbon nitride (SBCN-Ga) using a “solvothermal–copolymerization–impregnation” strategy. Characterization and theoretical calculations reveal that the synergistic effect of S and Ga constructs an efficient donor–acceptor (D–A) structure within the material, inducing a strong electron push–pull effect from “Ga–N sites” to “C–N triazine rings”. This significantly promotes the separation and migration of photogenerated charges and broadens the light response range to the near-infrared region. The obtained SBCN-Ga catalyst achieved a high CO yield of up to 638 μmol g−1 h−1 in the photocatalytic CO2 reduction reaction, 49 times higher than that of pristine g-C3N4 and exhibited excellent stability. This work provides a new strategy for designing high-performance photocatalysts by tuning the electron push–pull effect.
{"title":"Efficient full-spectrum-light-driven photocatalytic CO2 reduction boosted by synergetic electronic interactions in S–Ga codoped carbon nitride","authors":"Jiaqi Zhuang , Han Zhang , Yujing You , Mengyang Yuan , Guoquan Zhou , Liwei Zhao , Zhiqiang Jiang","doi":"10.1039/d5cy01563d","DOIUrl":"10.1039/d5cy01563d","url":null,"abstract":"<div><div>To address the energy crisis and global warming, utilizing solar energy for photocatalytic reduction of CO<sub>2</sub> into fuels represents an ideal solution. This study addresses the core issue of low charge separation efficiency in traditional graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) photocatalysts by successfully synthesizing sulfur (S) and gallium (Ga) co-doped bundled carbon nitride (SBCN-Ga) using a “solvothermal–copolymerization–impregnation” strategy. Characterization and theoretical calculations reveal that the synergistic effect of S and Ga constructs an efficient donor–acceptor (D–A) structure within the material, inducing a strong electron push–pull effect from “Ga–N sites” to “C–N triazine rings”. This significantly promotes the separation and migration of photogenerated charges and broadens the light response range to the near-infrared region. The obtained SBCN-Ga catalyst achieved a high CO yield of up to 638 μmol g<sup>−1</sup> h<sup>−1</sup> in the photocatalytic CO<sub>2</sub> reduction reaction, 49 times higher than that of pristine g-C<sub>3</sub>N<sub>4</sub> and exhibited excellent stability. This work provides a new strategy for designing high-performance photocatalysts by tuning the electron push–pull effect.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 10","pages":"Pages 3587-3597"},"PeriodicalIF":4.0,"publicationDate":"2026-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148011668","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}
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