Duozhen Chai, C.-J. Wang, Jinzhen Liu, Dongfeng Cao, Kaixuan Guo, Yuankun Wang, Ye Yuan, Francis Verpoort
The cyclization of propargyl alcohols with CO2 represents a highly significant method for the utilization of CO2. The resulting cyclic carbonates possesses high chemical value and hold great potential for applications in battery electrolytes, polymer precursors, and pharmaceutical intermediates. However, most existing reports on this cyclization have been limited to simple propargyl alcohol substrates that are substituted with inert alkyl, cycloalkyl, and phenyl groups. For functionalized propargyl alcohols, such as alkyne-1,2-diols, only a single report has been documented thus far. In this study, we have developed an innovative catalytic system comprising cost-effective copper salts and environmentally friendly ionic liquids (CuCl/1-ethyl-3-methylimidazolium acetate) for the cyclization of alkyne-1,2-diols with CO2. Compared to the previously reported AgF/bulky monophosphine ligand (BrettPhos) system, our system is free of traditional volatile solvents, phosphine ligands, and additives. Notably, this is the first reported Cu(I)-catalyzed system for this cyclization, offering significant advantages in terms of cost-effectiveness and reduced toxicity compared to silver salts. Moreover, the use of ionic liquids ensures considerable recyclability, further enhancing the sustainability and practicality of this approach.
{"title":"CuCl/Ionic Liquid Catalyzed Cascade Transformation of CO2 and Alkyne-1,2-Diols: Synthesis of Keto-Functionalized Cyclic Carbonates","authors":"Duozhen Chai, C.-J. Wang, Jinzhen Liu, Dongfeng Cao, Kaixuan Guo, Yuankun Wang, Ye Yuan, Francis Verpoort","doi":"10.3390/catal15030279","DOIUrl":"https://doi.org/10.3390/catal15030279","url":null,"abstract":"The cyclization of propargyl alcohols with CO2 represents a highly significant method for the utilization of CO2. The resulting cyclic carbonates possesses high chemical value and hold great potential for applications in battery electrolytes, polymer precursors, and pharmaceutical intermediates. However, most existing reports on this cyclization have been limited to simple propargyl alcohol substrates that are substituted with inert alkyl, cycloalkyl, and phenyl groups. For functionalized propargyl alcohols, such as alkyne-1,2-diols, only a single report has been documented thus far. In this study, we have developed an innovative catalytic system comprising cost-effective copper salts and environmentally friendly ionic liquids (CuCl/1-ethyl-3-methylimidazolium acetate) for the cyclization of alkyne-1,2-diols with CO2. Compared to the previously reported AgF/bulky monophosphine ligand (BrettPhos) system, our system is free of traditional volatile solvents, phosphine ligands, and additives. Notably, this is the first reported Cu(I)-catalyzed system for this cyclization, offering significant advantages in terms of cost-effectiveness and reduced toxicity compared to silver salts. Moreover, the use of ionic liquids ensures considerable recyclability, further enhancing the sustainability and practicality of this approach.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 3","pages":"279-279"},"PeriodicalIF":0.0,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/3/279/pdf?version=1742203458","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333819","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Noble metals are still in high demand for exhaust control catalysts in mobile sources. Designing highly efficient and less costly catalysts for soot purification from engine emissions is a challenge. Herein, the Ni-Co spinel oxide catalyst made of earth-abundant elements was synthesized by a precipitation method. Based on the test results of powder X-ray diffraction (XRD), N2 adsorption–desorption experiments, the temperature-programmed oxidation of soot (soot-TPO), the temperature-programmed oxidation of NO (NO-TPO), the temperature-programmed reduction in H2 (H2-TPR), and the advantages of Ni-Co synergistic catalysts relative to pure NiO and Co3O4 oxides were systematically investigated. The NiCo2O4 catalyst exhibits excellent catalytic performance and stability during soot oxidation compared with NiO and Co3O4 catalysts, i.e., its T10, T50, T90 and SCO2m are 316, 356, 388 °C and 99.95%, respectively. The mechanism of the Ni-Co synergy effect for boosting soot oxidation on the spinel oxide catalyst is proposed according to the experimental results of in situ diffuse reflectance infrared Fourier transform spectra (in situ DRIFTS) and the theoretical knowledge of coordination chemistry of metal–NO. This study lays a good foundation for exhaust purification by non-noble metal catalysts for pollution control and sustainable environmental practices.
{"title":"Pore-Rich Ni-Co Spinel Oxides for Treating Soot Oxidation in Engine Exhausts","authors":"Linsheng Xu, Kaixuan Chen, Yuanfeng Li, Yaxiao Ma, Baolong Cui, Jing Xiong, Yuechang Wei","doi":"10.3390/catal15030267","DOIUrl":"https://doi.org/10.3390/catal15030267","url":null,"abstract":"Noble metals are still in high demand for exhaust control catalysts in mobile sources. Designing highly efficient and less costly catalysts for soot purification from engine emissions is a challenge. Herein, the Ni-Co spinel oxide catalyst made of earth-abundant elements was synthesized by a precipitation method. Based on the test results of powder X-ray diffraction (XRD), N2 adsorption–desorption experiments, the temperature-programmed oxidation of soot (soot-TPO), the temperature-programmed oxidation of NO (NO-TPO), the temperature-programmed reduction in H2 (H2-TPR), and the advantages of Ni-Co synergistic catalysts relative to pure NiO and Co3O4 oxides were systematically investigated. The NiCo2O4 catalyst exhibits excellent catalytic performance and stability during soot oxidation compared with NiO and Co3O4 catalysts, i.e., its T10, T50, T90 and SCO2m are 316, 356, 388 °C and 99.95%, respectively. The mechanism of the Ni-Co synergy effect for boosting soot oxidation on the spinel oxide catalyst is proposed according to the experimental results of in situ diffuse reflectance infrared Fourier transform spectra (in situ DRIFTS) and the theoretical knowledge of coordination chemistry of metal–NO. This study lays a good foundation for exhaust purification by non-noble metal catalysts for pollution control and sustainable environmental practices.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 3","pages":"267-267"},"PeriodicalIF":0.0,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/3/267/pdf?version=1741790711","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331548","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this article, Pt-SnxOy hybrid nanoparticles encaged in porous silica nanospheres (Pt-SnxOy@PSNs) were prepared by using 1-dodecanethiol (C12-SH) as a coordination agent to confine Pt and Sn ions in a microemulsion system, which is formed by cetyltrimethylammonium bromide (CTAB) and C12-SH as co-surfactants in water. Compared with Pt@PSNs, when different molar ratios of SnxOy were introduced into Pt@PSNs to form Pt-SnxOy@PSNs, the catalytic efficiency of 4-nitrophenol (4-NP) reduction with NaBH4 can be significantly enhanced. At molar ratios of 4-NP/Pt of 150/1, the 4-NP conversion reached 100% over Pt-SnxOy@PSNs with Pt/Sn molar ratios of 1/0.75 in 8 min. This catalytic performance showed a slight decrease after six reaction cycles. This enhanced catalytic efficiency can be ascribed to the synergistic effect between Pt and SnxOy, and the protection of porous silica nanostructures can effectively improve the stability of the catalyst.
{"title":"Enhanced Catalytic Reduction of 4-Nitrophenol over Porous Silica Nanospheres Encapsulating Pt-SnxOy Hybrid Nanoparticles","authors":"Kaijie Li, Qin Wang, Qifan Zhao, Hongbo Yu, Hongfeng Yin","doi":"10.3390/catal15030263","DOIUrl":"https://doi.org/10.3390/catal15030263","url":null,"abstract":"In this article, Pt-SnxOy hybrid nanoparticles encaged in porous silica nanospheres (Pt-SnxOy@PSNs) were prepared by using 1-dodecanethiol (C12-SH) as a coordination agent to confine Pt and Sn ions in a microemulsion system, which is formed by cetyltrimethylammonium bromide (CTAB) and C12-SH as co-surfactants in water. Compared with Pt@PSNs, when different molar ratios of SnxOy were introduced into Pt@PSNs to form Pt-SnxOy@PSNs, the catalytic efficiency of 4-nitrophenol (4-NP) reduction with NaBH4 can be significantly enhanced. At molar ratios of 4-NP/Pt of 150/1, the 4-NP conversion reached 100% over Pt-SnxOy@PSNs with Pt/Sn molar ratios of 1/0.75 in 8 min. This catalytic performance showed a slight decrease after six reaction cycles. This enhanced catalytic efficiency can be ascribed to the synergistic effect between Pt and SnxOy, and the protection of porous silica nanostructures can effectively improve the stability of the catalyst.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 3","pages":"263-263"},"PeriodicalIF":0.0,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/3/263/pdf?version=1741670477","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332853","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cleavage of C-C bonds is crucial for hydrogen production via aqueous phase reforming of biomass-derived oxygenates. In this study, the hydrogen production performance and C-C bond cleavage capacity of Ni-W/AC catalysts with varying W/Ni ratios are evaluated using ethylene glycol as a model compound. A series of APR experiments conducted suggests that Ni-0.2W/AC catalyst exhibits the highest C1/C2+ ratio of 15.87 and achieves a hydrogen yield of 47.76%. The enhanced Ni-W bimetallic interactions, which significantly improve the efficiency of C-C bond cleavage and increase catalyst activity by promoting active site dispersion, are confirmed by detailed characterization techniques. Further analysis of product distribution provides insights into the reaction pathways of ethylene glycol and the reaction mechanism for ethanol during aqueous phase reforming. All the results indicate that this catalytic reforming method effectively facilitates C-C bond cleavage and hydrogen production, contributing to a better understanding of APR mechanisms for biomass-derived oxygenates.
{"title":"Efficient Hydrogen Production by Aqueous Phase Reforming of Ethylene Glycol over Ni-W Catalysts with Enhanced C-C Bond Cleavage Activity","authors":"Ling Xie, Zilong Huang, Y. H. Zhan, Jiahao Huang, Chao Wang, Riyang Shu, Junyao Wang, Libin Lei, Jianping Liu, Zhipeng Tian, Ying Chen","doi":"10.3390/catal15030258","DOIUrl":"https://doi.org/10.3390/catal15030258","url":null,"abstract":"Cleavage of C-C bonds is crucial for hydrogen production via aqueous phase reforming of biomass-derived oxygenates. In this study, the hydrogen production performance and C-C bond cleavage capacity of Ni-W/AC catalysts with varying W/Ni ratios are evaluated using ethylene glycol as a model compound. A series of APR experiments conducted suggests that Ni-0.2W/AC catalyst exhibits the highest C1/C2+ ratio of 15.87 and achieves a hydrogen yield of 47.76%. The enhanced Ni-W bimetallic interactions, which significantly improve the efficiency of C-C bond cleavage and increase catalyst activity by promoting active site dispersion, are confirmed by detailed characterization techniques. Further analysis of product distribution provides insights into the reaction pathways of ethylene glycol and the reaction mechanism for ethanol during aqueous phase reforming. All the results indicate that this catalytic reforming method effectively facilitates C-C bond cleavage and hydrogen production, contributing to a better understanding of APR mechanisms for biomass-derived oxygenates.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 3","pages":"258-258"},"PeriodicalIF":0.0,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/3/258/pdf?version=1741341824","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331488","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
To overcome the limitations of conventional catalysts in sterically hindered esterification reactions, a radio frequency (RF) plasma-modified SO42−/S2O82−/SnO2-Al2O₃ solid superacid catalyst was synthesized via sol-gel and impregnation, followed by RF plasma treatment and calcination. Comprehensive characterization revealed that the RF plasma modification endowed the catalyst with a uniform particle distribution (4.32 nm average size), larger specific surface area (104.44 m2·g−1), elevated total acid content (142.86 μmol·g−1), and increased oxygen vacancy concentration (16.4%), compared to the conventional sol-gel–impregnation–calcination-prepared catalyst. The RF plasma-modified SO42−-S2O82−/SnO2-Al2O3 was subsequently applied to perform the esterification reaction of Tyr, with a higher steric hindrance. Mechanistic studies indicated that the plasma-induced surface etching and electronic redistribution/intensified electron-withdrawing capability of SO42−/S2O82− groups synergistically strengthened Brønsted/Lewis acidity. For the esterification of tyrosine—a sterically demanding substrate—the modified catalyst achieved a 92.1% methyl tyrosine yield under the optimized conditions (180 °C, 0.8 MPa N2, 6 h), where the catalyst exhibited a better mechanical strength and better lifetime with five cycles. This work not only provides a scalable plasma-assisted strategy for tuning solid superacids but also establishes an eco-friendly alternative to traditional catalysts, and was applied to the esterification reactions of some high-steric-hindrance substrates.
{"title":"A Radio Frequency Plasma-Modified SO42−-S2O82−/SnO2-Al2O3 Solid Superacid Catalyst Applied for the Esterification of Tyrosine","authors":"Changhui Zhu, Xudong Zhang, Wenling Xu, Yanni Zheng, Baohe Tian, Xi Chen, Wenchao Zhu","doi":"10.3390/catal15030255","DOIUrl":"https://doi.org/10.3390/catal15030255","url":null,"abstract":"To overcome the limitations of conventional catalysts in sterically hindered esterification reactions, a radio frequency (RF) plasma-modified SO42−/S2O82−/SnO2-Al2O₃ solid superacid catalyst was synthesized via sol-gel and impregnation, followed by RF plasma treatment and calcination. Comprehensive characterization revealed that the RF plasma modification endowed the catalyst with a uniform particle distribution (4.32 nm average size), larger specific surface area (104.44 m2·g−1), elevated total acid content (142.86 μmol·g−1), and increased oxygen vacancy concentration (16.4%), compared to the conventional sol-gel–impregnation–calcination-prepared catalyst. The RF plasma-modified SO42−-S2O82−/SnO2-Al2O3 was subsequently applied to perform the esterification reaction of Tyr, with a higher steric hindrance. Mechanistic studies indicated that the plasma-induced surface etching and electronic redistribution/intensified electron-withdrawing capability of SO42−/S2O82− groups synergistically strengthened Brønsted/Lewis acidity. For the esterification of tyrosine—a sterically demanding substrate—the modified catalyst achieved a 92.1% methyl tyrosine yield under the optimized conditions (180 °C, 0.8 MPa N2, 6 h), where the catalyst exhibited a better mechanical strength and better lifetime with five cycles. This work not only provides a scalable plasma-assisted strategy for tuning solid superacids but also establishes an eco-friendly alternative to traditional catalysts, and was applied to the esterification reactions of some high-steric-hindrance substrates.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 3","pages":"255-255"},"PeriodicalIF":0.0,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/3/255/pdf?version=1741332163","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147330438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Long Chen, Jing Wu, Andrew Chang, Guoping Lu, Chun Cai
The abundant metal-catalyzed selective hydrodeoxygenation of lipids to alcohols has great industrial application potential. Herein, a carbon-coated Co catalyst has been fabricated by a simple detonation-reduction method. This material exhibits outstanding performance for the selective hydrodeoxygenation of lipids to alcohols (200 °C, 5 h, 2 MPa H2, over 5 runs), which mainly benefits from the carbon layer on the Co surface. This carbon layer optimizes substrate adsorption, which enhances the H2 adsorption process. The carbon coating also inhibits the oxidation of Co particles, resulting in the co-existence of Co0 and CoO, which is beneficial for H2 activation. In addition, kinetic studies indicate that hydrogen activation should be included in the rate-determining step of this reaction.
{"title":"Carbon-Coated Cobalt-Catalyzed Hydrodeoxygenation of Lipids to Alcohols","authors":"Long Chen, Jing Wu, Andrew Chang, Guoping Lu, Chun Cai","doi":"10.3390/catal15030254","DOIUrl":"https://doi.org/10.3390/catal15030254","url":null,"abstract":"The abundant metal-catalyzed selective hydrodeoxygenation of lipids to alcohols has great industrial application potential. Herein, a carbon-coated Co catalyst has been fabricated by a simple detonation-reduction method. This material exhibits outstanding performance for the selective hydrodeoxygenation of lipids to alcohols (200 °C, 5 h, 2 MPa H2, over 5 runs), which mainly benefits from the carbon layer on the Co surface. This carbon layer optimizes substrate adsorption, which enhances the H2 adsorption process. The carbon coating also inhibits the oxidation of Co particles, resulting in the co-existence of Co0 and CoO, which is beneficial for H2 activation. In addition, kinetic studies indicate that hydrogen activation should be included in the rate-determining step of this reaction.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 3","pages":"254-254"},"PeriodicalIF":0.0,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/3/254/pdf?version=1741315313","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333451","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shuchen Xing, Guiming Ba, Congyu Qin, Huilin Hu, Jinhua Ye, Defa Wang
The efficiency of CO2 photoreduction is often limited by the low reactivity of CO2 molecules and the rapid recombination of photogenerated charge carriers in most of the photocatalysts developed so far. In this study, we report a newly developed p-type Bi2Te3/SrTiO3 (pBT/STO) nanocomposite for efficient CO2 photoreduction. Upon light irradiation, the thermoelectric pBT with a strong light absorption capacity generates the photothermal effect favoring the activation of CO2 molecules. Meanwhile, a temperature gradient formed in pBT induces a thermoelectric field via the Seebeck effect, which promotes the charge carriers’ separation/transfer. In addition, the excellent electric conductivity and large work function render pBT an efficient cocatalyst for further improving the charge carriers’ separation/transfer. Owing to the synergistic photothermoelectric (PTE) effect on activation of CO2 molecules and promotion of charge separation/transfer, the efficiency of CO2 photoreduction over pBT/STO is significantly enhanced. We achieve the highest CO evolution rate of 28.0 μmol·gcat−1·h−1 over the optimal pBT(3)/STO, which is 12.8 times that of pure STO. This work suggests that a thermoelectric material and a semiconductor can be incorporated into a nanocomposite system for efficient CO2 reduction via the synergistic photothermoelectric effect on activating the CO2 molecules and promoting the charge carriers’ separation/transfer.
{"title":"Bi2Te3/SrTiO3 Nanocomposite for Enhanced CO2 Photoreduction via a Synergistic Photothermoelectric Effect","authors":"Shuchen Xing, Guiming Ba, Congyu Qin, Huilin Hu, Jinhua Ye, Defa Wang","doi":"10.3390/catal15030229","DOIUrl":"https://doi.org/10.3390/catal15030229","url":null,"abstract":"The efficiency of CO2 photoreduction is often limited by the low reactivity of CO2 molecules and the rapid recombination of photogenerated charge carriers in most of the photocatalysts developed so far. In this study, we report a newly developed p-type Bi2Te3/SrTiO3 (pBT/STO) nanocomposite for efficient CO2 photoreduction. Upon light irradiation, the thermoelectric pBT with a strong light absorption capacity generates the photothermal effect favoring the activation of CO2 molecules. Meanwhile, a temperature gradient formed in pBT induces a thermoelectric field via the Seebeck effect, which promotes the charge carriers’ separation/transfer. In addition, the excellent electric conductivity and large work function render pBT an efficient cocatalyst for further improving the charge carriers’ separation/transfer. Owing to the synergistic photothermoelectric (PTE) effect on activation of CO2 molecules and promotion of charge separation/transfer, the efficiency of CO2 photoreduction over pBT/STO is significantly enhanced. We achieve the highest CO evolution rate of 28.0 μmol·gcat−1·h−1 over the optimal pBT(3)/STO, which is 12.8 times that of pure STO. This work suggests that a thermoelectric material and a semiconductor can be incorporated into a nanocomposite system for efficient CO2 reduction via the synergistic photothermoelectric effect on activating the CO2 molecules and promoting the charge carriers’ separation/transfer.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 3","pages":"229-229"},"PeriodicalIF":0.0,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/3/229/pdf?version=1740730220","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332264","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiahui Shi, Qitong Ye, Qing Huang, Junhu Ma, Yipu Liu, Shiwei Lin
Designing efficient and cost-effective electrocatalysts is crucial for the large-scale development of sustainable hydrogen energy. Amorphous catalysts hold great promise for application due to their structural flexibility and high exposure of active sites. We report a novel method for the in situ growth of amorphous CoNiRuOx nanoparticle structures (CoNiRuOx/NF) on a nickel foam substrate. In 1 m KOH, CoNiRuOx/NF achieves a current density of 10 mA/cm2 with a hydrogen evolution reaction (HER) overpotential of only 43 mV and remains stable for over 100 h at a current density of 100 mA/cm2. An alkaline electrolyzer assembled with CoNiRuOx/NF as the cathode delivers a current density 2.97 times higher than that of an IrO2||Pt/C electrode pair at the potential of 2 V and exhibits excellent long-term durability exceeding 100 h. Experimental results reveal that the combined replacement and corrosion reactions facilitate the formation of the amorphous CoNiRuOx structure. This work provides valuable insights for developing efficient and scalable amorphous catalysts.
设计高效、经济的电催化剂是可持续氢能大规模开发的关键。非晶催化剂由于其结构的灵活性和活性位点的高暴露性而具有很大的应用前景。我们报道了一种在镍泡沫衬底上原位生长非晶CoNiRuOx纳米颗粒结构（CoNiRuOx/NF）的新方法。在1 m KOH条件下，CoNiRuOx/NF的电流密度为10 mA/cm2，析氢反应（HER）过电位仅为43 mV，并且在100 mA/cm2的电流密度下保持稳定超过100小时。以CoNiRuOx/NF为阴极的碱性电解槽在2 V电位下的电流密度是IrO2||Pt/C电极对的2.97倍，且具有超过100 h的长期耐用性。实验结果表明，替代和腐蚀反应的结合促进了CoNiRuOx非晶结构的形成。这项工作为开发高效和可扩展的非晶催化剂提供了有价值的见解。
{"title":"Engineering Amorphous CoNiRuOx Nanoparticles Grown on Nickel Foam for Boosted Electrocatalytic Hydrogen Evolution","authors":"Xiahui Shi, Qitong Ye, Qing Huang, Junhu Ma, Yipu Liu, Shiwei Lin","doi":"10.3390/catal15030211","DOIUrl":"https://doi.org/10.3390/catal15030211","url":null,"abstract":"Designing efficient and cost-effective electrocatalysts is crucial for the large-scale development of sustainable hydrogen energy. Amorphous catalysts hold great promise for application due to their structural flexibility and high exposure of active sites. We report a novel method for the in situ growth of amorphous CoNiRuOx nanoparticle structures (CoNiRuOx/NF) on a nickel foam substrate. In 1 m KOH, CoNiRuOx/NF achieves a current density of 10 mA/cm2 with a hydrogen evolution reaction (HER) overpotential of only 43 mV and remains stable for over 100 h at a current density of 100 mA/cm2. An alkaline electrolyzer assembled with CoNiRuOx/NF as the cathode delivers a current density 2.97 times higher than that of an IrO2||Pt/C electrode pair at the potential of 2 V and exhibits excellent long-term durability exceeding 100 h. Experimental results reveal that the combined replacement and corrosion reactions facilitate the formation of the amorphous CoNiRuOx structure. This work provides valuable insights for developing efficient and scalable amorphous catalysts.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 3","pages":"211-211"},"PeriodicalIF":0.0,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/3/211/pdf?version=1740215715","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
TiO2 aerogels have been employed for the degradation of formaldehyde (HCHO) via the photocatalytic generation of reactive oxygen species (ROS) (O2−, ·OH), and its pore size plays a crucial role in affecting the decomposition efficiency. However, there remains a lack of a comprehensive understanding regarding the internal mechanisms underlying the influence of pore size on HCHO decomposition. In this study, we prepared TiO2 aerogels by the sol–gel method, and added polyvinyl alcohol (PVA) to introduce flexible molecular chains for pore size regulation, and obtained anatase crystals after a heat treatment at 800 °C. The photocatalytic decomposition mechanism of HCHO was researched using TiO2 aerogels with varying pore sizes as catalysts. The results indicated that the pore size of TiO2 aerogels was one of the important factors for HCHO decomposition. We validated that the efficiency of HCHO decomposition was related to the oxygen pressure in the pores of the TiO2 aerogel, and the oxygen pressure was inversely proportional to the pore size, then the pore size of the TiO2 aerogel and the decomposition efficiency of HCHO were linked through the oxygen pressure. Finally, the optimal pore size of the TiO2 aerogel for the photocatalytic HCHO decomposition was 2 nm–10 nm. The present study aims to establish the relationship and influence of the pore size of TiO2 aerogels on the performance of photocatalytic decomposition and promoting further advancements in porous nanomaterials for catalysis.
{"title":"The Effect of the Pore Size of TiO2 Aerogel on the Photocatalytic Decomposition of Formaldehyde","authors":"Fenglei Sun, Xian Yue, Xianbo Yu, Yanan Di, Hu Chen, Shuao Xie, Wei Han, Xiaoxue Xi, Wenjing Zhang, Heng Zou, Huaxin Li, Junhui Xiang","doi":"10.3390/catal15020171","DOIUrl":"https://doi.org/10.3390/catal15020171","url":null,"abstract":"TiO2 aerogels have been employed for the degradation of formaldehyde (HCHO) via the photocatalytic generation of reactive oxygen species (ROS) (O2−, ·OH), and its pore size plays a crucial role in affecting the decomposition efficiency. However, there remains a lack of a comprehensive understanding regarding the internal mechanisms underlying the influence of pore size on HCHO decomposition. In this study, we prepared TiO2 aerogels by the sol–gel method, and added polyvinyl alcohol (PVA) to introduce flexible molecular chains for pore size regulation, and obtained anatase crystals after a heat treatment at 800 °C. The photocatalytic decomposition mechanism of HCHO was researched using TiO2 aerogels with varying pore sizes as catalysts. The results indicated that the pore size of TiO2 aerogels was one of the important factors for HCHO decomposition. We validated that the efficiency of HCHO decomposition was related to the oxygen pressure in the pores of the TiO2 aerogel, and the oxygen pressure was inversely proportional to the pore size, then the pore size of the TiO2 aerogel and the decomposition efficiency of HCHO were linked through the oxygen pressure. Finally, the optimal pore size of the TiO2 aerogel for the photocatalytic HCHO decomposition was 2 nm–10 nm. The present study aims to establish the relationship and influence of the pore size of TiO2 aerogels on the performance of photocatalytic decomposition and promoting further advancements in porous nanomaterials for catalysis.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 2","pages":"171-171"},"PeriodicalIF":0.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/2/171/pdf?version=1739354591","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333950","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of efficient electrocatalysts for the complete oxidation of ethylene glycol (EG) is crucial for enhancing the practicality of direct EG fuel cells (DEGFCs). However, significant challenges persist in developing highly active Pd-based catalytic electrodes. In this work, PdIrNi ternary telluride nanospheres (PdIrNiTe-MNSPs) with mesoporous morphology and an amorphous structure were successfully synthesized and applied in electrocatalytic EG oxidation reaction. Brunauer–Emmett–Teller analysis revealed typical mesoporous characteristics, with a surface area of 8.33 m2·g−1 and a total pore volume of 0.055 cm3·g−1, respectively. Transmission electron microscopy characterization showed that the outer layer of PdIrNiTe-MNSPs is entirely amorphous in structure. Electrochemical tests demonstrated that PdIrNiTe-MNSPs exhibit enhanced electrocatalytic specific activity (16.75 mA·cm−2) and mass activity (1372.22 mA·mg−1) for EG oxidation reaction (EGOR), achieving 3.17 and 2.09 times higher than commercial Pd/C, which can be attributed to its unique nanoarchitecture and optimized electron configuration. In situ spectroscopy revealed that with the incorporation of IrNi, PdIrNiTe-MNSPs facilitate C-C bond cleavage of EG, achieving a higher selectivity (≈93%) in oxidizing EG to C1 products, while PdTe-MNSPs demonstrated higher selectivity for glycolic acid in EGOR. Taken together, this work provides new insights into the application of Pd-based telluride nanomaterials in electrocatalysis for EGOR.
{"title":"Ternary PdIrNi Telluride Amorphous Mesoporous Nanocatalyst for Efficient Electro-Oxidation of Ethylene Glycol","authors":"Liang Fu, Manli Wang, Lulu Hao, Jinhua Lei, Tong Liu, Zelin Chen, Changjiu Li","doi":"10.3390/catal15020143","DOIUrl":"https://doi.org/10.3390/catal15020143","url":null,"abstract":"The development of efficient electrocatalysts for the complete oxidation of ethylene glycol (EG) is crucial for enhancing the practicality of direct EG fuel cells (DEGFCs). However, significant challenges persist in developing highly active Pd-based catalytic electrodes. In this work, PdIrNi ternary telluride nanospheres (PdIrNiTe-MNSPs) with mesoporous morphology and an amorphous structure were successfully synthesized and applied in electrocatalytic EG oxidation reaction. Brunauer–Emmett–Teller analysis revealed typical mesoporous characteristics, with a surface area of 8.33 m2·g−1 and a total pore volume of 0.055 cm3·g−1, respectively. Transmission electron microscopy characterization showed that the outer layer of PdIrNiTe-MNSPs is entirely amorphous in structure. Electrochemical tests demonstrated that PdIrNiTe-MNSPs exhibit enhanced electrocatalytic specific activity (16.75 mA·cm−2) and mass activity (1372.22 mA·mg−1) for EG oxidation reaction (EGOR), achieving 3.17 and 2.09 times higher than commercial Pd/C, which can be attributed to its unique nanoarchitecture and optimized electron configuration. In situ spectroscopy revealed that with the incorporation of IrNi, PdIrNiTe-MNSPs facilitate C-C bond cleavage of EG, achieving a higher selectivity (≈93%) in oxidizing EG to C1 products, while PdTe-MNSPs demonstrated higher selectivity for glycolic acid in EGOR. Taken together, this work provides new insights into the application of Pd-based telluride nanomaterials in electrocatalysis for EGOR.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 2","pages":"143-143"},"PeriodicalIF":0.0,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/2/143/pdf?version=1738650038","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333166","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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