Pub Date : 2026-06-08Epub Date: 2026-04-28DOI: 10.1039/d6cy00127k
Yufeng Zhao , Haozhi Wang , Keyi Zhou , Daoping He , Xi Chen
Electrochemical nitrate reduction to ammonia (NO3RR) represents a promising approach for wastewater treatment while simultaneously offering an alternative to the Haber–Bosch synthesis process. However, current research on metal-free carbon-based catalysts remains limited in scope, exhibits relatively low catalytic performance, and predominantly relies on carbon precursors derived from non-renewable resources. To address these challenges, this study employs chitin and shrimp shells as a precursor to synthesize sulfur–nitrogen co-doped carbon (SNC) catalysts via thiourea doping. At −0.95 V (vs. RHE), the optimized catalyst achieves a faradaic efficiency of 97.6% and an ammonia yield rate of 21 012 μg h−1 mg−1. Characterizations such as high-resolution transmission electron microscopy (HRTEM), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) have been conducted to elucidate the catalyst structure.
{"title":"Synergistic N, S doping in chitin-derived carbon catalysts for efficient nitrate-to-ammonia electroreduction","authors":"Yufeng Zhao , Haozhi Wang , Keyi Zhou , Daoping He , Xi Chen","doi":"10.1039/d6cy00127k","DOIUrl":"10.1039/d6cy00127k","url":null,"abstract":"<div><div>Electrochemical nitrate reduction to ammonia (NO<sub>3</sub>RR) represents a promising approach for wastewater treatment while simultaneously offering an alternative to the Haber–Bosch synthesis process. However, current research on metal-free carbon-based catalysts remains limited in scope, exhibits relatively low catalytic performance, and predominantly relies on carbon precursors derived from non-renewable resources. To address these challenges, this study employs chitin and shrimp shells as a precursor to synthesize sulfur–nitrogen co-doped carbon (SNC) catalysts <em>via</em> thiourea doping. At −0.95 V (<em>vs.</em> RHE), the optimized catalyst achieves a faradaic efficiency of 97.6% and an ammonia yield rate of 21 012 μg h<sup>−1</sup> mg<sup>−1</sup>. Characterizations such as high-resolution transmission electron microscopy (HRTEM), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and <em>in situ</em> attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) have been conducted to elucidate the catalyst structure.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 11","pages":"Pages 3808-3818"},"PeriodicalIF":4.2,"publicationDate":"2026-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148196172","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 : 2026-06-08Epub Date: 2026-04-23DOI: 10.1039/d6cy00137h
Magdalena Jabłońska , Haythem Benamor
In recent years, the demand for climate-smart policies has become a global imperative. While the primary focus has traditionally been on reducing carbon footprints, nitrous oxide (N2O), a non-carbon greenhouse gas, also has a substantial impact on climate change and warrants greater attention in mitigation efforts. In this mini-review, firstly, we focus our attention on N2O formation and its destruction potential to the environment and human health, through its emission from natural and anthropogenic sources. N2O is an inevitable by-product of adipic and nitric acid production processes. Thus, we presented the variety of post-treatment methods (commonly known as ‘end-of-pipe’ solutions) that were developed and implemented in the chemical and energy industries to control N2O emissions. We focused on hydrotalcite-derived mixed metal oxides and Cu-containing zeolites as the most widely applied groups of catalysts in decomposition of N2O (deN2O), pointing out the existing gaps in research. Finally, we provided general conclusions together with a discussion about promising research directions.
{"title":"Advances in decomposition of N2O from nitric acid plants and current status over selected copper-containing catalysts","authors":"Magdalena Jabłońska , Haythem Benamor","doi":"10.1039/d6cy00137h","DOIUrl":"10.1039/d6cy00137h","url":null,"abstract":"<div><div>In recent years, the demand for climate-smart policies has become a global imperative. While the primary focus has traditionally been on reducing carbon footprints, nitrous oxide (N<sub>2</sub>O), a non-carbon greenhouse gas, also has a substantial impact on climate change and warrants greater attention in mitigation efforts. In this mini-review, firstly, we focus our attention on N<sub>2</sub>O formation and its destruction potential to the environment and human health, through its emission from natural and anthropogenic sources. N<sub>2</sub>O is an inevitable by-product of adipic and nitric acid production processes. Thus, we presented the variety of post-treatment methods (commonly known as ‘end-of-pipe’ solutions) that were developed and implemented in the chemical and energy industries to control N<sub>2</sub>O emissions. We focused on hydrotalcite-derived mixed metal oxides and Cu-containing zeolites as the most widely applied groups of catalysts in decomposition of N<sub>2</sub>O (deN<sub>2</sub>O), pointing out the existing gaps in research. Finally, we provided general conclusions together with a discussion about promising research directions.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 11","pages":"Pages 3703-3719"},"PeriodicalIF":4.2,"publicationDate":"2026-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148196164","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 study, we elucidate the formation mechanism of by-products especially N2O during NO purification using H2 as a reductant on alumina-supported Pt, Pd, and Rh catalysts by looking into the catalytic reaction dynamics and NO adsorption/desorption properties, as well as chemical state change of catalysts, with assistance of advanced characterization techniques including the NO pulse method, in situ temperature/atmosphere controlled FT-IR and XPS analysis. It was found that the surface NO adsorption/desorption properties and surface oxygen species of PGM catalysts result in significantly distinguished by-product formation behavior. Lower formation of N2O and NH3 was confirmed on the Rh/Al2O3 catalyst rather than the Pd and Pt cases, whose phenomenon is attributed to the high stability of the Rh–NO+ chemical bond formed. Additionally, Rh–O bonding tends to be more stable than that of Pt and Pd, also contributing to the suppression of NO dissociation and subsequent by-product formation. These findings provide valuable insights into the design and development of advanced catalysts aimed at minimizing the emission of greenhouse gases such as N2O.
在本研究中，我们借助先进的表征技术，包括NO脉冲法、原位温度/气氛控制FT-IR和XPS分析，通过研究催化反应动力学、NO吸附/解吸性能以及催化剂的化学状态变化，阐明了H2作为还原剂在氧化铝负载Pt、Pd和Rh催化剂上净化NO的副产物特别是N2O的形成机理。研究发现，PGM催化剂的表面NO吸附/解吸特性和表面氧的种类决定了其副产物形成行为的显著差异。在Rh/Al2O3催化剂上，N2O和NH3的生成比Pd和Pt催化剂低，这是由于形成的Rh - no +化学键具有较高的稳定性。此外，Rh-O键比Pt和Pd键更稳定，也有助于抑制NO解离和随后的副产物形成。这些发现为设计和开发旨在减少温室气体（如N2O）排放的先进催化剂提供了有价值的见解。
{"title":"Insights into the selective reduction of NO over Al2O3-supported Pt, Rh, and Pd catalysts","authors":"Shunsuke Oishi , Hiromi Togashi , Koki Aono , Ryoichi Ogawa , Yunzi Xin , Takashi Shirai","doi":"10.1039/d6cy00094k","DOIUrl":"10.1039/d6cy00094k","url":null,"abstract":"<div><div>In this study, we elucidate the formation mechanism of by-products especially N<sub>2</sub>O during NO purification using H<sub>2</sub> as a reductant on alumina-supported Pt, Pd, and Rh catalysts by looking into the catalytic reaction dynamics and NO adsorption/desorption properties, as well as chemical state change of catalysts, with assistance of advanced characterization techniques including the NO pulse method, <em>in situ</em> temperature/atmosphere controlled FT-IR and XPS analysis. It was found that the surface NO adsorption/desorption properties and surface oxygen species of PGM catalysts result in significantly distinguished by-product formation behavior. Lower formation of N<sub>2</sub>O and NH<sub>3</sub> was confirmed on the Rh/Al<sub>2</sub>O<sub>3</sub> catalyst rather than the Pd and Pt cases, whose phenomenon is attributed to the high stability of the Rh–NO<sup>+</sup> chemical bond formed. Additionally, Rh–O bonding tends to be more stable than that of Pt and Pd, also contributing to the suppression of NO dissociation and subsequent by-product formation. These findings provide valuable insights into the design and development of advanced catalysts aimed at minimizing the emission of greenhouse gases such as N<sub>2</sub>O.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 11","pages":"Pages 3760-3767"},"PeriodicalIF":4.2,"publicationDate":"2026-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148196167","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 : 2026-06-08Epub Date: 2026-04-20DOI: 10.1039/d6cy00361c
Adrián Moreno González , Sarah L. McOnie , Eleonora Fava , Stephen P. Thomas
Catalytic hydrogen isotope exchange (HIE) enables atom-economical deuterium incorporation into pharmacologically relevant molecules, typically with precious metal catalysts. The drive for increased sustainability and decreased environmental impact and physiological toxicity has piqued interest in the use of base-metals for catalytic HIE. The manganese complex [dmpe2MnH3] was applied as a catalyst to the HIE of furan and thiophene derivatives using D2 as the deuterium source, however this system was incompatible with N-containing heterocycles. Development and application of the manganese hydride complex [dppbzMn(CO)3H] showed comparable reactivity to that of [dmpe2MnH3] for furan and thiophene derivatives, and enabled application to N-containing heteroarenes and carboarenes with increased functional group tolerance.
{"title":"Manganese-catalysed HIE of arenes and heteroarenes","authors":"Adrián Moreno González , Sarah L. McOnie , Eleonora Fava , Stephen P. Thomas","doi":"10.1039/d6cy00361c","DOIUrl":"10.1039/d6cy00361c","url":null,"abstract":"<div><div>Catalytic hydrogen isotope exchange (HIE) enables atom-economical deuterium incorporation into pharmacologically relevant molecules, typically with precious metal catalysts. The drive for increased sustainability and decreased environmental impact and physiological toxicity has piqued interest in the use of base-metals for catalytic HIE. The manganese complex [dmpe<sub>2</sub>MnH<sub>3</sub>] was applied as a catalyst to the HIE of furan and thiophene derivatives using D<sub>2</sub> as the deuterium source, however this system was incompatible with N-containing heterocycles. Development and application of the manganese hydride complex [dppbzMn(CO)<sub>3</sub>H] showed comparable reactivity to that of [dmpe<sub>2</sub>MnH<sub>3</sub>] for furan and thiophene derivatives, and enabled application to N-containing heteroarenes and carboarenes with increased functional group tolerance.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 11","pages":"Pages 3784-3790"},"PeriodicalIF":4.2,"publicationDate":"2026-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148196169","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 : 2026-06-08Epub Date: 2026-04-23DOI: 10.1039/d6cy00148c
Zhen Yan , Leyang Qi , Jicong Yan , Qi Zhang , Fuping Tian , Xiang Wang
The catalytic upcycling of polystyrene (PS) waste into valuable aromatic chemicals can mitigate plastic pollution and reduce dependence on fossil-derived aromatics; however, its hydroconversion into mono-aromatics remains challenging due to the intrinsic stability of the C–C bonds in the polymer backbone and the competitive hydrogenation of aromatic rings under hydrogen atmospheres. Herein, we report a solvent-free catalytic strategy for the efficient upcycling of PS into mono-aromatics over a bifunctional Ni/NbOx catalyst. Under relatively mild conditions, i.e. 260 °C and 3 MPa H2, a 1 wt% Ni/NbOx catalyst achieves complete PS conversion within 3 h without a solvent, delivering a liquid yield above 90% and a mono-aromatics selectivity of 60.7%, corresponding to a mono-aromatics formation rate of 2.02 gmono-aromatics gcat−1 h−1. Comparison with a physical mixture of Ni + NbOx indicates that the close contact between Ni and NbOx in Ni/NbOx enhances hydrogen spillover, thus resulting in a higher activity for the hydrocracking of polystyrene into mono-aromatics. The Ni/NbOx catalyst exhibits good recyclability and applicability to real-world and mixed plastic wastes, providing a cost-effective and scalable catalytic approach for the sustainable upgrading of polystyrene waste into valuable aromatic chemicals.
{"title":"Solvent-free recycling of polystyrene waste into valuable mono-aromatics over a Ni/NbOx catalyst","authors":"Zhen Yan , Leyang Qi , Jicong Yan , Qi Zhang , Fuping Tian , Xiang Wang","doi":"10.1039/d6cy00148c","DOIUrl":"10.1039/d6cy00148c","url":null,"abstract":"<div><div>The catalytic upcycling of polystyrene (PS) waste into valuable aromatic chemicals can mitigate plastic pollution and reduce dependence on fossil-derived aromatics; however, its hydroconversion into mono-aromatics remains challenging due to the intrinsic stability of the C–C bonds in the polymer backbone and the competitive hydrogenation of aromatic rings under hydrogen atmospheres. Herein, we report a solvent-free catalytic strategy for the efficient upcycling of PS into mono-aromatics over a bifunctional Ni/NbO<sub><em>x</em></sub> catalyst. Under relatively mild conditions, <em>i.e.</em> 260 °C and 3 MPa H<sub>2</sub>, a 1 wt% Ni/NbO<sub><em>x</em></sub> catalyst achieves complete PS conversion within 3 h without a solvent, delivering a liquid yield above 90% and a mono-aromatics selectivity of 60.7%, corresponding to a mono-aromatics formation rate of 2.02 g<sub>mono-aromatics</sub> g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup>. Comparison with a physical mixture of Ni + NbO<sub><em>x</em></sub> indicates that the close contact between Ni and NbO<sub><em>x</em></sub> in Ni/NbO<sub><em>x</em></sub> enhances hydrogen spillover, thus resulting in a higher activity for the hydrocracking of polystyrene into mono-aromatics. The Ni/NbO<sub><em>x</em></sub> catalyst exhibits good recyclability and applicability to real-world and mixed plastic wastes, providing a cost-effective and scalable catalytic approach for the sustainable upgrading of polystyrene waste into valuable aromatic chemicals.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 11","pages":"Pages 3881-3888"},"PeriodicalIF":4.2,"publicationDate":"2026-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148196190","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 : 2026-06-08Epub Date: 2026-05-15DOI: 10.1039/d5cy01574j
Gopal Tembe
Since the discovery of selective oligomerization of ethylene to its trimer, namely hexene-1, in the mid-60s, it has stimulated continued research activity on unique catalyst systems in industries and academic institutions. The successful commercialization of a chromium-based catalyst for producing hexene-1 by Chevron-Phillips Chemical Company was first demonstrated in 2003 by establishing a plant in the Middle East and, more recently, expanding its capacity in the US. Although a few other industries have made progress in developing hexene-1 technology based on catalysts involving chromium compounds, the actual identity of the active species responsible for ethylene trimerization remains elusive. It is pertinent to note that compared to the conventional linear alpha olefin processes for 1-hexene production via non-selective ethylene oligomerization, the on-purpose ethylene trimerization process is favored owing to its high atom efficiency and reduced downstream separation costs. It is evident that despite publications in this area, there appears to be a lack of complete theoretical understanding of the factors influencing the catalytic performance of these chromium-based systems, leading to a trial-and-error approach as the main strategy in catalyst development. In this article, the intriguing but challenging aspects of structural studies carried out so far on the chromium precursors employed in commercial processes are compiled. The earlier chromium precursor complexes employed in the catalyst systems developed by Phillips Petroleum Company and the currently used chromium(iii) carboxylate precursor in the Chevron-Philips technology (CPC) have also been compared based on patented and published research. The available literature information has helped provide definitive mechanistic insights into the landmark CPC ethylene trimerization system, which combines studies involving experimental investigations of unresolved issues in addition to exclusive theoretical calculations on the Cr(iii)2-ethylhexanoate/2,5-dimethylpyrrole/alkylaluminum-based model system.
{"title":"Insights into the structural studies of chromium precursors in the Phillips ethylene trimerization catalyst system: a mini review","authors":"Gopal Tembe","doi":"10.1039/d5cy01574j","DOIUrl":"10.1039/d5cy01574j","url":null,"abstract":"<div><div>Since the discovery of selective oligomerization of ethylene to its trimer, namely hexene-1, in the mid-60s, it has stimulated continued research activity on unique catalyst systems in industries and academic institutions. The successful commercialization of a chromium-based catalyst for producing hexene-1 by Chevron-Phillips Chemical Company was first demonstrated in 2003 by establishing a plant in the Middle East and, more recently, expanding its capacity in the US. Although a few other industries have made progress in developing hexene-1 technology based on catalysts involving chromium compounds, the actual identity of the active species responsible for ethylene trimerization remains elusive. It is pertinent to note that compared to the conventional linear alpha olefin processes for 1-hexene production <em>via</em> non-selective ethylene oligomerization, the on-purpose ethylene trimerization process is favored owing to its high atom efficiency and reduced downstream separation costs. It is evident that despite publications in this area, there appears to be a lack of complete theoretical understanding of the factors influencing the catalytic performance of these chromium-based systems, leading to a trial-and-error approach as the main strategy in catalyst development. In this article, the intriguing but challenging aspects of structural studies carried out so far on the chromium precursors employed in commercial processes are compiled. The earlier chromium precursor complexes employed in the catalyst systems developed by Phillips Petroleum Company and the currently used chromium(<span>iii</span>) carboxylate precursor in the Chevron-Philips technology (CPC) have also been compared based on patented and published research. The available literature information has helped provide definitive mechanistic insights into the landmark CPC ethylene trimerization system, which combines studies involving experimental investigations of unresolved issues in addition to exclusive theoretical calculations on the Cr(<span>iii</span>)2-ethylhexanoate/2,5-dimethylpyrrole/alkylaluminum-based model system.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 11","pages":"Pages 3743-3759"},"PeriodicalIF":4.2,"publicationDate":"2026-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148196166","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 role of highly uniform, diverse experimental data in catalyst informatics is examined using an oxidative coupling of methane dataset measured by a single researcher under consistent devices and conditions. Broad compositional coverage and minimized experimental variability enable machine learning to capture composition–performance relationships using simple one-hot encoding. Inverse analysis of the compositional space identifies promising catalysts for experimental validation. These results demonstrate that carefully curated, well-distributed datasets, even if relatively small, enable machine learning to effectively capture composition–performance relationships.
{"title":"Importance of consistent and well-dispersed catalyst datasets for machine learning in oxidative coupling of methane","authors":"Hinata Sudo , Yoshiki Hasukawa , Rensuke Koiwai , Fernando Garcia-Escobar , Shun Nishimura , Lauren Takahashi , Keisuke Takahashi","doi":"10.1039/d6cy00228e","DOIUrl":"10.1039/d6cy00228e","url":null,"abstract":"<div><div>The role of highly uniform, diverse experimental data in catalyst informatics is examined using an oxidative coupling of methane dataset measured by a single researcher under consistent devices and conditions. Broad compositional coverage and minimized experimental variability enable machine learning to capture composition–performance relationships using simple one-hot encoding. Inverse analysis of the compositional space identifies promising catalysts for experimental validation. These results demonstrate that carefully curated, well-distributed datasets, even if relatively small, enable machine learning to effectively capture composition–performance relationships.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 11","pages":"Pages 3791-3798"},"PeriodicalIF":4.2,"publicationDate":"2026-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148196170","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 : 2026-06-08Epub Date: 2026-05-14DOI: 10.1039/d6cy00020g
Jiming Wang , Min Ji , Min Wang
Photo-thermo-chemical dry reforming of methane (PTC-DRM) presents advantages over thermocatalytic DRM by storing solar and thermal energy as chemical energy, yet maintaining high efficiency and stability remains a challenge. Herein, we report an efficient PTC-DRM process on Ni–Co–Ce–Al catalysts and investigate the synergistic effect of Ni and Co on reaction performance. Characterization results revealed that the introduction of Co increases the concentration of acidic sites on the Ni-based catalyst surface. An appropriate number of acidic sites facilitates the DRM reaction. Co-incorporated catalysts demonstrate excellent light responsiveness, and generate more energetic hot charge carriers under light irradiation. Density functional theory (DFT) calculations confirm that the interfacial electronic structure of the Ni–Co–Ce–Al catalyst facilitates spontaneous electron transfer from CeO2 to NiCo bimetallic quantum dots (QDs), which is mediated by the built-in electric field at the metal–semiconductor interface—attributed to the inherent work function difference between CeO2 (5.45 eV) and NiCo alloys (4.93 eV). The incorporation of an optimal amount of Co significantly improves the catalytic performance, with the Ni0.9–Co0.1–Ce–Al catalyst exhibiting the highest thermal and photocatalytic activity. At 650 °C, the conversions of CH4 and CO2 increased from 55.8% and 60.1% under dark conditions to 65.1% and 67.9% under light irradiation, respectively. Accordingly, the yields of H2 and CO increased from 21.4 and 26.5 μmol min−1 g−1 to 23.6 and 27.7 μmol min−1 g−1. This study demonstrates that the synergy between bimetallic components coupled with photothermal integration can effectively enhance DRM efficiency and coke resistance, providing a valuable catalyst design strategy for solar-driven conversion of carbon resources.
光-热化学甲烷干式重整（PTC-DRM）将太阳能和热能作为化学能储存，具有热催化式重整的优势，但保持高效和稳定性仍是一个挑战。在此，我们报道了一个高效的PTC-DRM工艺在Ni - Co - ce - al催化剂上，并研究了Ni和Co对反应性能的协同效应。表征结果表明，Co的引入增加了ni基催化剂表面酸性位点的浓度。适当数量的酸性位点有利于DRM反应。共掺入催化剂表现出优异的光响应性，在光照射下能产生更多的高能热电荷载流子。密度泛函理论（DFT）计算证实，由于CeO2 （5.45 eV）和NiCo合金（4.93 eV）的固有功函数差异，Ni-Co-Ce-Al催化剂的界面电子结构促进了电子从CeO2自发转移到NiCo双金属量子点（QDs），这是由金属-半导体界面上的内置电场介导的。当Co的加入量达到最佳时，催化性能得到显著提高，Ni0.9-Co0.1-Ce-Al催化剂表现出最高的热催化和光催化活性。650℃时，CH4和CO2的转化率分别从黑暗条件下的55.8%和60.1%提高到光照条件下的65.1%和67.9%。H2和CO的产率分别由21.4和26.5 μmol min−1 g−1提高到23.6和27.7 μmol min−1 g−1。本研究表明，双金属组分之间的协同作用加上光热集成可以有效提高DRM效率和抗焦性，为太阳能驱动碳资源转化提供了有价值的催化剂设计策略。
{"title":"Photo-assisted methane dry reforming over Ni–Co–CeO2–Al2O3 catalysts with enhanced activity: synergistic effect of Ni and Co","authors":"Jiming Wang , Min Ji , Min Wang","doi":"10.1039/d6cy00020g","DOIUrl":"10.1039/d6cy00020g","url":null,"abstract":"<div><div>Photo-thermo-chemical dry reforming of methane (PTC-DRM) presents advantages over thermocatalytic DRM by storing solar and thermal energy as chemical energy, yet maintaining high efficiency and stability remains a challenge. Herein, we report an efficient PTC-DRM process on Ni–Co–Ce–Al catalysts and investigate the synergistic effect of Ni and Co on reaction performance. Characterization results revealed that the introduction of Co increases the concentration of acidic sites on the Ni-based catalyst surface. An appropriate number of acidic sites facilitates the DRM reaction. Co-incorporated catalysts demonstrate excellent light responsiveness, and generate more energetic hot charge carriers under light irradiation. Density functional theory (DFT) calculations confirm that the interfacial electronic structure of the Ni–Co–Ce–Al catalyst facilitates spontaneous electron transfer from CeO<sub>2</sub> to NiCo bimetallic quantum dots (QDs), which is mediated by the built-in electric field at the metal–semiconductor interface—attributed to the inherent work function difference between CeO<sub>2</sub> (5.45 eV) and NiCo alloys (4.93 eV). The incorporation of an optimal amount of Co significantly improves the catalytic performance, with the Ni<sub>0.9</sub>–Co<sub>0.1</sub>–Ce–Al catalyst exhibiting the highest thermal and photocatalytic activity. At 650 °C, the conversions of CH<sub>4</sub> and CO<sub>2</sub> increased from 55.8% and 60.1% under dark conditions to 65.1% and 67.9% under light irradiation, respectively. Accordingly, the yields of H<sub>2</sub> and CO increased from 21.4 and 26.5 μmol min<sup>−1</sup> g<sup>−1</sup> to 23.6 and 27.7 μmol min<sup>−1</sup> g<sup>−1</sup>. This study demonstrates that the synergy between bimetallic components coupled with photothermal integration can effectively enhance DRM efficiency and coke resistance, providing a valuable catalyst design strategy for solar-driven conversion of carbon resources.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 11","pages":"Pages 3819-3829"},"PeriodicalIF":4.2,"publicationDate":"2026-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148196174","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 : 2026-06-08Epub Date: 2026-04-24DOI: 10.1039/d6cy00183a
Felicia Zaar , Alvaro Posada-Borbón , Henrik Grönbeck
Liquid organic hydrogen carriers (LOHCs) enable storage and transport of H2 using existing liquid fuel infrastructure, through reversible catalytic hydrogenation and dehydrogenation of organic molecules. A viable, commercially deployed LOHC system is the methylcyclohexane (C7H14)/toluene (C7H8) system. However, Pt-based catalysts, which are used for both hydrogenation of C7H8 and dehydrogenation of C7H14, also promote unwanted C–C bond scission, leading to demethylation and LOHC degradation. One route to prevent C–C bond scission over Pt catalysts is to mildly poison the catalyst with sulfur. Using density functional theory (DFT) calculations and mean-field microkinetic modeling, we show that the presence of sulfur, besides suppressing demethylation, also improves the C7H14 dehydrogenation activity. The enhanced performance is a result of sulfur destabilizing neighboring co-adsorbates, which promotes C7H8 desorption. The computational results for dehydrogenation over Pt surfaces reproduce experimental trends for alumina-supported Pt nanoparticles, suggesting that controlled, moderate sulfur poisoning is a universal means to improve the overall performance of Pt catalysts for LOHC dehydrogenation.
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1,2,3-Triazoles constitute a prominent class of nitrogen-rich heterocycles with remarkable chemical stability and wide-ranging applications. Since the development of the copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction, the facile synthesis of 1,4-disubstituted 1,2,3-triazoles has become routine; however, selective access to the complementary 1,5-disubstituted regioisomers remained a long-standing synthetic challenge. This limitation was effectively addressed through the introduction of ruthenium-catalyzed azide–alkyne cycloaddition (RuAAC), which enabled the direct and regioselective formation of 1,5-disubstituted 1,2,3-triazoles. The present review provides a comprehensive and critical overview of synthetic strategies developed for achieving 1,5-regioselectivity in 1,2,3-triazoles, with a primary focus on metal-catalyzed azide–alkyne cycloaddition reactions. The evolution of ruthenium-based catalytic systems is discussed in detail, encompassing Cp*Ru complexes, non-Cp ruthenium catalysts, mixed-ligand systems, heterogeneous and recyclable Ru-catalysts, and the mechanistic insights governing regioselectivity. In addition to ruthenium catalysis, the roles of alternative transition metals, such as nickel, iron, and zinc, in promoting 1,5-regioselective triazole formation are systematically examined. Furthermore, emerging strategies involving alkali and alkaline earth metals, as well as base-mediated synthesis, are highlighted as sustainable and economically attractive alternatives. By integrating diverse catalytic platforms, mechanistic perspectives, and synthetic methodologies, this review provides a unified and up-to-date account of the advances in 1,5-regioselective 1,2,3-triazole synthesis, serving as a valuable resource for researchers engaged in heterocyclic chemistry, catalysis, and drug discovery.
{"title":"1,5-Regioselectivity in 1,2,3-triazoles from metal-catalyzed azide–alkyne cycloadditions: synthetic strategies and catalytic scope","authors":"Kunj B. Mishra , Priyanka Chaudhary , Utkarsh Sharma , Adesh Kumar Singh , Priyanka Parashar , Yogendra Kumar , Vishal Goswami","doi":"10.1039/d5cy01607j","DOIUrl":"10.1039/d5cy01607j","url":null,"abstract":"<div><div>1,2,3-Triazoles constitute a prominent class of nitrogen-rich heterocycles with remarkable chemical stability and wide-ranging applications. Since the development of the copper(<span>i</span>)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction, the facile synthesis of 1,4-disubstituted 1,2,3-triazoles has become routine; however, selective access to the complementary 1,5-disubstituted regioisomers remained a long-standing synthetic challenge. This limitation was effectively addressed through the introduction of ruthenium-catalyzed azide–alkyne cycloaddition (RuAAC), which enabled the direct and regioselective formation of 1,5-disubstituted 1,2,3-triazoles. The present review provides a comprehensive and critical overview of synthetic strategies developed for achieving 1,5-regioselectivity in 1,2,3-triazoles, with a primary focus on metal-catalyzed azide–alkyne cycloaddition reactions. The evolution of ruthenium-based catalytic systems is discussed in detail, encompassing Cp*Ru complexes, non-Cp ruthenium catalysts, mixed-ligand systems, heterogeneous and recyclable Ru-catalysts, and the mechanistic insights governing regioselectivity. In addition to ruthenium catalysis, the roles of alternative transition metals, such as nickel, iron, and zinc, in promoting 1,5-regioselective triazole formation are systematically examined. Furthermore, emerging strategies involving alkali and alkaline earth metals, as well as base-mediated synthesis, are highlighted as sustainable and economically attractive alternatives. By integrating diverse catalytic platforms, mechanistic perspectives, and synthetic methodologies, this review provides a unified and up-to-date account of the advances in 1,5-regioselective 1,2,3-triazole synthesis, serving as a valuable resource for researchers engaged in heterocyclic chemistry, catalysis, and drug discovery.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"16 11","pages":"Pages 3668-3702"},"PeriodicalIF":4.2,"publicationDate":"2026-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148196090","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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