Peracetic acid (PAA) is increasingly used in advanced oxidation processes (AOPs) for water purification, yet there remains a critical need for highly-efficient and low-cost activators. Here, we constructed abundant oxygen vacancies (OVs) into redox-active CoO by incorporating redox-inert Mg species (MgCoO), achieving ultrafast degradation of sulfamethoxazole (SMX) via PAA activation. The MgCoO/PAA system successfully degraded SMX within 3 min, with a removal rate 154.8 times higher than the CoO/PAA system, surpassing even previously reported single-atom catalysts. The primary active species identified was the acetylperoxyl radical (CHC(O)OO•), with Co-oxo acting as a secondary active species that produced O-labeled sulfone compounds. We proposed a novel mechanism involving redox-inert Mg species that simultaneously strengthened PAA adsorption and activation. The enriched surface hydroxyl groups after Mg incorporation elevated the affinity for PAA binding. Meanwhile, the reduced Co average valence state and enhanced electron transfer capability facilitated PAA activation. This study offers an in-depth knowledge of redox-inert alkaline earth metals in PAA-AOPs.
{"title":"Unusually improved peracetic acid activation for ultrafast organic compound removal through redox-inert Mg incorporation into active Co3O4","authors":"Xiaoyang Li, Jiahang Liu, Yingying Chu, Mengying Qian, Zhichao Yang, Weiming Zhang","doi":"10.1016/j.apcatb.2024.124601","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124601","url":null,"abstract":"Peracetic acid (PAA) is increasingly used in advanced oxidation processes (AOPs) for water purification, yet there remains a critical need for highly-efficient and low-cost activators. Here, we constructed abundant oxygen vacancies (OVs) into redox-active CoO by incorporating redox-inert Mg species (MgCoO), achieving ultrafast degradation of sulfamethoxazole (SMX) via PAA activation. The MgCoO/PAA system successfully degraded SMX within 3 min, with a removal rate 154.8 times higher than the CoO/PAA system, surpassing even previously reported single-atom catalysts. The primary active species identified was the acetylperoxyl radical (CHC(O)OO•), with Co-oxo acting as a secondary active species that produced O-labeled sulfone compounds. We proposed a novel mechanism involving redox-inert Mg species that simultaneously strengthened PAA adsorption and activation. The enriched surface hydroxyl groups after Mg incorporation elevated the affinity for PAA binding. Meanwhile, the reduced Co average valence state and enhanced electron transfer capability facilitated PAA activation. This study offers an in-depth knowledge of redox-inert alkaline earth metals in PAA-AOPs.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250051","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-12DOI: 10.1016/j.apcatb.2024.124588
Yucong Miao, Zhenhua Li, Lan Luo, Wangsong Chen, Lili Ma, Kui Fan, Yingjie Song, Yaofeng Hu, Rengui Li, Mingfei Shao
Allylic C–H bond oxidation of cycloolefins to allylic alcohols has attracted tremendous attention owing to its widespread application in pharmaceuticals production and natural synthesis. However, the production of allylic alcohols still suffers from the challenges of unsatisfactory selectivity and harsh conditions. Herein, we report the sustainable photoelectrocatalytic (PEC) allylic C–H oxidation to allylic alcohols, achieving the oxidation of cyclohexene to 2-cyclohexenol with a selectivity of 97.2 %. We reveal the reaction pathway wherein photogenerated holes and OH synergistically activate cyclohexene to carbocation intermediates, and these intermediates combine with OH to produce 2-cyclohexenol. Additionally, the mechanism by enriching OH in local area of photoanode surface to enhance PEC performance is uncovered. Furthermore, we designed a self-powered PEC reaction system, attaining a 2-cyclohexenol productivity of 11.95 μmol h (selectivity > 97 %) coupled with a H productivity of 1.44 mL h, demonstrating the application potential of this new strategy.
{"title":"Photoelectrocatalytic allylic C–H oxidation to allylic alcohols coupled with hydrogen evolution","authors":"Yucong Miao, Zhenhua Li, Lan Luo, Wangsong Chen, Lili Ma, Kui Fan, Yingjie Song, Yaofeng Hu, Rengui Li, Mingfei Shao","doi":"10.1016/j.apcatb.2024.124588","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124588","url":null,"abstract":"Allylic C–H bond oxidation of cycloolefins to allylic alcohols has attracted tremendous attention owing to its widespread application in pharmaceuticals production and natural synthesis. However, the production of allylic alcohols still suffers from the challenges of unsatisfactory selectivity and harsh conditions. Herein, we report the sustainable photoelectrocatalytic (PEC) allylic C–H oxidation to allylic alcohols, achieving the oxidation of cyclohexene to 2-cyclohexenol with a selectivity of 97.2 %. We reveal the reaction pathway wherein photogenerated holes and OH synergistically activate cyclohexene to carbocation intermediates, and these intermediates combine with OH to produce 2-cyclohexenol. Additionally, the mechanism by enriching OH in local area of photoanode surface to enhance PEC performance is uncovered. Furthermore, we designed a self-powered PEC reaction system, attaining a 2-cyclohexenol productivity of 11.95 μmol h (selectivity > 97 %) coupled with a H productivity of 1.44 mL h, demonstrating the application potential of this new strategy.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-12DOI: 10.1016/j.apcatb.2024.124586
Jindi Yang, Hanqing Yin, Aijun Du, Mike Tebyetekerwa, Chuanbiao Bie, Zhuyuan Wang, Zhimeng Sun, Zhongguo Zhang, Xiangkang Zeng, Xiwang Zhang
Photocatalytic oxygen reduction reaction (ORR) offers a promising pathway for sustainable hydrogen peroxide (HO) production but faces challenges in developing catalysts with good ORR selectivity. Herein, we report that tailoring O adsorption on non-metallic active sites can optimize ORR selectivity. This concept is demonstrated on three carbon nitrides with different atomic configurations: polymeric carbon nitride (PCN), lithium-poly triazine imide (Li-PTI), and sodium-poly heptazine imide (Na-PHI). Na-PHI emerges as a strong candidate for HO production due to the end-on adsorption mode and suitable adsorption strength with O. Synthesized Na-PHI, PCN, and Li-PTI are characterized, with Na-PHI showing superior light absorption, charge carrier separation, and remarkable selectivity (92 %) for two-electron ORR. Consequently, Na-PHI achieves a high HO generation rate of 3.48 mmol g h, surpassing Li-PTI and PCN by 9.2 and 33 times, respectively. This study underscores the importance of O adsorption on non-metallic active sites for selective photocatalytic HO generation.
光催化氧还原反应（ORR）为过氧化氢（HO）的可持续生产提供了一种前景广阔的途径，但在开发具有良好 ORR 选择性的催化剂方面却面临着挑战。在此，我们报告了在非金属活性位点上定制 O 吸附可以优化 ORR 选择性。这一概念在三种具有不同原子构型的氮化碳上得到了验证：聚合氮化碳（PCN）、聚三嗪亚胺锂（Li-PTI）和聚庚嗪亚胺钠（Na-PHI）。对合成的 Na-PHI、PCN 和 Li-PTI 进行了表征，Na-PHI 在双电子 ORR 方面表现出卓越的光吸收、电荷载流子分离和显著的选择性（92%）。因此，Na-PHI 的 HO 生成率高达 3.48 mmol g h，分别是 Li-PTI 和 PCN 的 9.2 倍和 33 倍。这项研究强调了非金属活性位点吸附 O 对于选择性光催化 HO 生成的重要性。
{"title":"Unveiling O2 adsorption on non-metallic active site for selective photocatalytic H2O2 production","authors":"Jindi Yang, Hanqing Yin, Aijun Du, Mike Tebyetekerwa, Chuanbiao Bie, Zhuyuan Wang, Zhimeng Sun, Zhongguo Zhang, Xiangkang Zeng, Xiwang Zhang","doi":"10.1016/j.apcatb.2024.124586","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124586","url":null,"abstract":"Photocatalytic oxygen reduction reaction (ORR) offers a promising pathway for sustainable hydrogen peroxide (HO) production but faces challenges in developing catalysts with good ORR selectivity. Herein, we report that tailoring O adsorption on non-metallic active sites can optimize ORR selectivity. This concept is demonstrated on three carbon nitrides with different atomic configurations: polymeric carbon nitride (PCN), lithium-poly triazine imide (Li-PTI), and sodium-poly heptazine imide (Na-PHI). Na-PHI emerges as a strong candidate for HO production due to the end-on adsorption mode and suitable adsorption strength with O. Synthesized Na-PHI, PCN, and Li-PTI are characterized, with Na-PHI showing superior light absorption, charge carrier separation, and remarkable selectivity (92 %) for two-electron ORR. Consequently, Na-PHI achieves a high HO generation rate of 3.48 mmol g h, surpassing Li-PTI and PCN by 9.2 and 33 times, respectively. This study underscores the importance of O adsorption on non-metallic active sites for selective photocatalytic HO generation.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249989","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-12DOI: 10.1016/j.apcatb.2024.124599
Junpeng Yue, Hanpei Yang, Lei Zhou, Chen Liu, Shi Wang, Xudong Kang
Benefit origins of potassium (K) and sodium (Na) co-doping on carbon nitride for integrating pharmaceutical degradation and hydrogen peroxide (HO) production was investigated. K and Na co-doped carbon nitride (CN-K/Na) with modified crystallinity and surface structure was synthesized by ionothermal polymerization of urea. The CN-K/Na exhibited an apparent quantum yield of 26.2 % in HO photosynthesis at 400 nm (isopropanol as proton donor), and it was better at extracting proton from pharmaceutical-laden wastewater to produce HO than pristine carbon nitride. These superior performances are attributed to the benefits directly or indirectly caused by the co-doping: i) Na optimizes in-plane charge transfer, ii) K builds channel for interplane charge transfer, iii) cyano group as Lewis acid site adsorbs and activates oxygen, iv) amino group as Lewis base site extracts and releases protons, v) increased visible-light absorption. This work offers significant insights into designing polymeric photocatalysts for environmental management and energy conservation.
研究了在氮化碳上共掺杂钾（K）和钠（Na）以整合药物降解和过氧化氢（HO）生产的益处。通过尿素的离子热聚合合成了钾和钠共掺杂的氮化碳（CN-K/Na），其结晶度和表面结构均有所改变。在 400 纳米波长的 HO 光合作用中，CN-K/Na 的表观量子产率为 26.2%（以异丙醇为质子供体），与原始氮化碳相比，它能更好地从含药废水中提取质子来产生 HO。这些优异的性能归功于共掺杂直接或间接带来的好处：i) Na 优化了面内电荷转移；ii) K 为面间电荷转移建立了通道；iii) 作为路易斯酸位点的氰基吸附并激活了氧；iv) 作为路易斯碱位点的氨基萃取并释放了质子；v) 增加了对可见光的吸收。这项工作为设计用于环境管理和节能的聚合物光催化剂提供了重要启示。
{"title":"At least five: Benefit origins of potassium and sodium co-doping on carbon nitride for integrating pharmaceuticals degradation and hydrogen peroxide production","authors":"Junpeng Yue, Hanpei Yang, Lei Zhou, Chen Liu, Shi Wang, Xudong Kang","doi":"10.1016/j.apcatb.2024.124599","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124599","url":null,"abstract":"Benefit origins of potassium (K) and sodium (Na) co-doping on carbon nitride for integrating pharmaceutical degradation and hydrogen peroxide (HO) production was investigated. K and Na co-doped carbon nitride (CN-K/Na) with modified crystallinity and surface structure was synthesized by ionothermal polymerization of urea. The CN-K/Na exhibited an apparent quantum yield of 26.2 % in HO photosynthesis at 400 nm (isopropanol as proton donor), and it was better at extracting proton from pharmaceutical-laden wastewater to produce HO than pristine carbon nitride. These superior performances are attributed to the benefits directly or indirectly caused by the co-doping: i) Na optimizes in-plane charge transfer, ii) K builds channel for interplane charge transfer, iii) cyano group as Lewis acid site adsorbs and activates oxygen, iv) amino group as Lewis base site extracts and releases protons, v) increased visible-light absorption. This work offers significant insights into designing polymeric photocatalysts for environmental management and energy conservation.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142268114","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-11DOI: 10.1016/j.apcatb.2024.124587
Yuanjun Hu, Guanhui Liu, Ting Song, Xiayi Hu, Bei Long, Guo-Jun Deng
CO to multicarbon fuels via photocatalytic conversion, especially propylene, is a viable pathway, but propylene remains unreported due to the two C-C coupling with the eighteen-electron reduction process. Herein, [1,1′-biphenyl]-3,3′,5,5′-tetracarbaldehyde, and [2,2-bipyridine]-5,5-diamine units were condensed and synthesized in combination with a post-modification strategy, named BTA-COF-M (M = H, Cu, Fe, Co, Ni or Zn). BTA-COF-Cu has distinct kagome lattices and abundant exposed-atom Cu sites, which can induce CO to undergo two C-C couplings into CH products under visible light illumination. According to experimental and theoretical analyses, the outstanding performance of BTA-COF-Cu can be attributed to the ideal synergistic contribution of the Kagome lattices and the atomic Cu active sites, which promote CO adsorption/activation, facilitate photoexcited charge carrier dynamics, and induce secondary coupling of key intermediates. This research provides an innovative perspective for the construction of Kagome lattice COF with monatomic metal sites for CO reduction to high value-added propylene.
通过光催化将一氧化碳（尤其是丙烯）转化为多碳燃料是一条可行的途径，但由于丙烯在十八电子还原过程中存在两个 C-C 偶联，因此仍未见报道。在这里，[1,1′-联苯]-3,3′,5,5′-四甲醛和[2,2-联吡啶]-5,5-二胺单元被缩合合成，并结合后修饰策略，命名为 BTA-COF-M（M = H、Cu、Fe、Co、Ni 或 Zn）。BTA-COF-Cu 具有独特的 Kagome 晶格和丰富的暴露原子 Cu 位点，可在可见光照射下诱导 CO 发生两次 C-C 偶联生成 CH 产物。根据实验和理论分析，BTA-COF-Cu 的优异性能可归因于 Kagome 晶格和原子 Cu 活性位点的理想协同贡献，它们促进了 CO 的吸附/活化，促进了光激发电荷载流子动力学，并诱导了关键中间产物的二次耦合。这项研究为构建具有单原子金属位点的 Kagome 晶格 COF 提供了一个创新的视角，用于将 CO 还原成高附加值的丙烯。
{"title":"Single-atom Cu sites on covalent organic frameworks with Kagome lattices for visible-light-driven CO2 reduction to propylene","authors":"Yuanjun Hu, Guanhui Liu, Ting Song, Xiayi Hu, Bei Long, Guo-Jun Deng","doi":"10.1016/j.apcatb.2024.124587","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124587","url":null,"abstract":"CO to multicarbon fuels via photocatalytic conversion, especially propylene, is a viable pathway, but propylene remains unreported due to the two C-C coupling with the eighteen-electron reduction process. Herein, [1,1′-biphenyl]-3,3′,5,5′-tetracarbaldehyde, and [2,2-bipyridine]-5,5-diamine units were condensed and synthesized in combination with a post-modification strategy, named BTA-COF-M (M = H, Cu, Fe, Co, Ni or Zn). BTA-COF-Cu has distinct kagome lattices and abundant exposed-atom Cu sites, which can induce CO to undergo two C-C couplings into CH products under visible light illumination. According to experimental and theoretical analyses, the outstanding performance of BTA-COF-Cu can be attributed to the ideal synergistic contribution of the Kagome lattices and the atomic Cu active sites, which promote CO adsorption/activation, facilitate photoexcited charge carrier dynamics, and induce secondary coupling of key intermediates. This research provides an innovative perspective for the construction of Kagome lattice COF with monatomic metal sites for CO reduction to high value-added propylene.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249992","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-11DOI: 10.1016/j.apcatb.2024.124597
Qinyue Wu, Xinfei Fan, Kaiyuan Liu, Xie Quan, Yanming Liu
Electrocatalytic nitrate reduction to ammonia is a promising method to mitigate nitrate contamination and produce valuable chemical. However, it still suffers from slow active hydrogen (*H) transfer kinetics and unfavorable thermodynamics. Here the *H transfer and reaction energy barrier of nitrate reduction reaction were regulated on B-doped Cu nanoneedles (Cu NNs-B) to enhance ammonia electrosynthesis via interfacial engineering. The high-curvature nanoneedles showed locally enhanced electric fields, which promoted *H supply from water dissociation. B-doping provided Cu/Cu active sites for the activation of nitrate and intermediates. Due to the simultaneously improved *H supply kinetics and reaction thermodynamics, Cu NNs-B was efficient for reducing nitrate to ammonia, achieving high Faradaic efficiencies (FEs) of 95.1–98.6 % and ammonia yields of 0.12–1.33 mmol·h·cm at 50–1500 mg·L NO-N. Nitrate was selectively converted to ammonia with the remaining nitrate and nitrite concentrations below drinking water standards. Experimental and DFT results revealed Cu NNs-B with properly higher nanotip curvature was more favorable for boosting ammonia electrosynthesis from both kinetics and thermodynamics.
{"title":"Efficient and selective electroreduction of nitrate to ammonia via interfacial engineering of B-doped Cu nanoneedles","authors":"Qinyue Wu, Xinfei Fan, Kaiyuan Liu, Xie Quan, Yanming Liu","doi":"10.1016/j.apcatb.2024.124597","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124597","url":null,"abstract":"Electrocatalytic nitrate reduction to ammonia is a promising method to mitigate nitrate contamination and produce valuable chemical. However, it still suffers from slow active hydrogen (*H) transfer kinetics and unfavorable thermodynamics. Here the *H transfer and reaction energy barrier of nitrate reduction reaction were regulated on B-doped Cu nanoneedles (Cu NNs-B) to enhance ammonia electrosynthesis via interfacial engineering. The high-curvature nanoneedles showed locally enhanced electric fields, which promoted *H supply from water dissociation. B-doping provided Cu/Cu active sites for the activation of nitrate and intermediates. Due to the simultaneously improved *H supply kinetics and reaction thermodynamics, Cu NNs-B was efficient for reducing nitrate to ammonia, achieving high Faradaic efficiencies (FEs) of 95.1–98.6 % and ammonia yields of 0.12–1.33 mmol·h·cm at 50–1500 mg·L NO-N. Nitrate was selectively converted to ammonia with the remaining nitrate and nitrite concentrations below drinking water standards. Experimental and DFT results revealed Cu NNs-B with properly higher nanotip curvature was more favorable for boosting ammonia electrosynthesis from both kinetics and thermodynamics.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-11DOI: 10.1016/j.apcatb.2024.124596
Jian Meng, Manfen Liang, Jinglin Mu, Zhichao Miao, Hong Huang, Ruirui Qi, Lechen Diao, Shuping Zhuo, Jin Zhou
As for developing efficient Indium (In)-based catalyst of CO reduction to HCOOH, the modulation of electronic structure stands as a pivotal factor. However, the precise control of -orbital electronic configuration of InO remains challenging. Herein, the carbon-coated InO (InO@C) with precisely controllable carbon thickness is developed. The InO modified by moderate carbon layer thickness exhibits an impressive FE exceeding 90 % and maintains a constant current density of 110 mA cm even after 100 h. Meanwhile, it achieves a FE of 97 % and a current of 550 mA in a membrane electrode assembly. The catalyst maintains satisfactory activity even under low CO concentration and acidic electrolytes. The density functional theory (DFT) calculations show that carbon layer successfully improves the -orbital electronic configuration of InO and perfects the adsorption energy of *OCHO intermediate. This work can provide a guidance for regulating electronic configuration and designing high-efficiency electrocatalyst.
要开发高效的铟（In）基催化剂，将 CO 还原成 HCOOH，电子结构的调节是一个关键因素。然而，如何精确控制 InO 的 - 轨道电子构型仍是一项挑战。在此，我们开发了可精确控制碳厚度的碳涂层 InO（InO@C）。经过适度碳层厚度修饰的氧化铟表现出了超过 90% 的令人印象深刻的 FE，并且在 100 小时后仍能保持 110 mA cm 的恒定电流密度。与此同时，它在膜电极组件中实现了 97 % 的 FE 和 550 mA 的电流。即使在低 CO 浓度和酸性电解质条件下，催化剂也能保持令人满意的活性。密度泛函理论（DFT）计算表明，碳层成功地改善了 InO 的 - 轨道电子构型，完善了 *OCHO 中间体的吸附能。这项工作可为调节电子构型和设计高效电催化剂提供指导。
{"title":"Regulating p-orbital electronic configuration of In2O3 by thickness-controlled carbon layer for efficient electrocatalytic CO2 reduction to HCOOH","authors":"Jian Meng, Manfen Liang, Jinglin Mu, Zhichao Miao, Hong Huang, Ruirui Qi, Lechen Diao, Shuping Zhuo, Jin Zhou","doi":"10.1016/j.apcatb.2024.124596","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124596","url":null,"abstract":"As for developing efficient Indium (In)-based catalyst of CO reduction to HCOOH, the modulation of electronic structure stands as a pivotal factor. However, the precise control of -orbital electronic configuration of InO remains challenging. Herein, the carbon-coated InO (InO@C) with precisely controllable carbon thickness is developed. The InO modified by moderate carbon layer thickness exhibits an impressive FE exceeding 90 % and maintains a constant current density of 110 mA cm even after 100 h. Meanwhile, it achieves a FE of 97 % and a current of 550 mA in a membrane electrode assembly. The catalyst maintains satisfactory activity even under low CO concentration and acidic electrolytes. The density functional theory (DFT) calculations show that carbon layer successfully improves the -orbital electronic configuration of InO and perfects the adsorption energy of *OCHO intermediate. This work can provide a guidance for regulating electronic configuration and designing high-efficiency electrocatalyst.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249991","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-10DOI: 10.1016/j.apcatb.2024.124591
Lizbeth Moreno Bravo, Frederic C. Meunier, Jan Kopyscinski
Dual-function materials (DFMs) combine sorbent and catalytic components to perform selective CO capture and subsequent hydrogenation. This study explores the performance of rare-earth oxides (REOs) as CO adsorption sites on Ru/AlO. REOs increase CO uptake by upwards of +60 % by enhancing the overall catalyst surface basicity and favoring metal–support interactions. Thermogravimetric analysis during CO adsorption-hydrogenation cycles exhibited significant catalytic activity and enhanced stability of Ru-REO/AlO at temperatures as low as 200 °C. This leads to methane production of 50–85 µmol g, surpassing recently reported values obtained for alkali and alkali-earth promoted Ru-based materials operated at 250 °C. The highest performing studied DFM, RuNdO/AlO, achieved 85 % CO capture efficiency and steadily produced methane in cyclic operation (+120 % CO uptake relative to Ru/AlO). DRIFTS revealed that the dominant mechanism for methane formation is the hydrogenation of ruthenium carbonyls, which are stabilized by REOs. Upon CO exposure, surface carbonates and bicarbonate species form more abundantly on DFMs than on Ru/AlO. This confirms that REOs enhance the adsorption and retention of carbonates, which generate additional promoter-related reaction pathways during low-temperature hydrogenation. These findings are crucial in the advancement of sustainable, wider operation range carbon capture and utilization technologies.
双功能材料 (DFM) 结合了吸附剂和催化元件，可进行选择性一氧化碳捕获和随后的氢化。本研究探讨了稀土氧化物 (REO) 作为 Ru/AlO 上 CO 吸附位点的性能。稀土氧化物提高了催化剂表面的整体碱性，有利于金属与支撑物之间的相互作用，从而将二氧化碳的吸收率提高了 60% 以上。在 CO 吸附-加氢循环过程中进行的热重分析表明，Ru-REO/AlO 在低至 200 °C 的温度下具有显著的催化活性和更高的稳定性。这使得甲烷产量达到 50-85 µmol g，超过了最近报道的在 250 °C 下运行的碱和碱土促进 Ru 基材料所获得的数值。所研究的性能最高的 DFM（RuNdO/AlO）达到了 85% 的一氧化碳捕集效率，并在循环操作中稳定地生产甲烷（相对于 Ru/AlO 的一氧化碳吸收率 +120%）。DRIFTS 显示，甲烷形成的主要机制是由 REOs 稳定的钌羰基的氢化作用。与 Ru/AlO 相比，暴露于 CO 时，DFMs 上形成的表面碳酸盐和碳酸氢盐物种更多。这证实了 REO 可增强碳酸盐的吸附和保留，从而在低温氢化过程中产生更多与促进剂相关的反应途径。这些发现对于推进可持续的、操作范围更广的碳捕获和利用技术至关重要。
{"title":"Rare earth oxide promoted Ru/Al2O3 dual function materials for CO2 capture and methanation: An operando DRIFTS and TGA study","authors":"Lizbeth Moreno Bravo, Frederic C. Meunier, Jan Kopyscinski","doi":"10.1016/j.apcatb.2024.124591","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124591","url":null,"abstract":"Dual-function materials (DFMs) combine sorbent and catalytic components to perform selective CO capture and subsequent hydrogenation. This study explores the performance of rare-earth oxides (REOs) as CO adsorption sites on Ru/AlO. REOs increase CO uptake by upwards of +60 % by enhancing the overall catalyst surface basicity and favoring metal–support interactions. Thermogravimetric analysis during CO adsorption-hydrogenation cycles exhibited significant catalytic activity and enhanced stability of Ru-REO/AlO at temperatures as low as 200 °C. This leads to methane production of 50–85 µmol g, surpassing recently reported values obtained for alkali and alkali-earth promoted Ru-based materials operated at 250 °C. The highest performing studied DFM, RuNdO/AlO, achieved 85 % CO capture efficiency and steadily produced methane in cyclic operation (+120 % CO uptake relative to Ru/AlO). DRIFTS revealed that the dominant mechanism for methane formation is the hydrogenation of ruthenium carbonyls, which are stabilized by REOs. Upon CO exposure, surface carbonates and bicarbonate species form more abundantly on DFMs than on Ru/AlO. This confirms that REOs enhance the adsorption and retention of carbonates, which generate additional promoter-related reaction pathways during low-temperature hydrogenation. These findings are crucial in the advancement of sustainable, wider operation range carbon capture and utilization technologies.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250054","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-10DOI: 10.1016/j.apcatb.2024.124594
Ling-Wei Wei, Shou-Heng Liu, Van-Can Nguyen, Meng-Wei Zheng, Hong Paul Wang
Antibiotics are recognized as emerging contaminants with non-biodegradation, complex structures, and abundant chemical energy, which are difficult to treat and recover energy through traditional wastewater treatment processes. A Z-scheme photocatalytic fuel cell (PFC) system, comprising CN and CuO/CuO dual-photoelectrodes, has been developed for simultaneous power generation and degradation of antibiotics, such as berberine hydrochloride (BH). Especially, the CN with its suitable energy potential for peroxymonosulfate (PMS) activation is synchronized with CuO/CuO, resulting in enhancing the performance of PFC system. Moreover, the interaction between PMS and Cu(I)/Cu(II) active sites on the photocathode can enhance the formation of highly reactive species (HRS) in the PFC-PMS system, thereby improving photocatalytic oxidation performance. Under visible-light illumination for 120 min, PFC-PMS system can rapidly and effectively oxidize BH (ca. 99.2 %, = 0.0039 min) with simultaneous power generation (0.018 mW cm). This approach presents a promising approach for both water cleanup and energy reuse applications.
{"title":"Visible-light driven O2-to-H2O2 synchronized activation of peroxymonosulfate in Z-scheme photocatalytic fuel cell for wastewater purification with power generation","authors":"Ling-Wei Wei, Shou-Heng Liu, Van-Can Nguyen, Meng-Wei Zheng, Hong Paul Wang","doi":"10.1016/j.apcatb.2024.124594","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124594","url":null,"abstract":"Antibiotics are recognized as emerging contaminants with non-biodegradation, complex structures, and abundant chemical energy, which are difficult to treat and recover energy through traditional wastewater treatment processes. A Z-scheme photocatalytic fuel cell (PFC) system, comprising CN and CuO/CuO dual-photoelectrodes, has been developed for simultaneous power generation and degradation of antibiotics, such as berberine hydrochloride (BH). Especially, the CN with its suitable energy potential for peroxymonosulfate (PMS) activation is synchronized with CuO/CuO, resulting in enhancing the performance of PFC system. Moreover, the interaction between PMS and Cu(I)/Cu(II) active sites on the photocathode can enhance the formation of highly reactive species (HRS) in the PFC-PMS system, thereby improving photocatalytic oxidation performance. Under visible-light illumination for 120 min, PFC-PMS system can rapidly and effectively oxidize BH (ca. 99.2 %, = 0.0039 min) with simultaneous power generation (0.018 mW cm). This approach presents a promising approach for both water cleanup and energy reuse applications.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249994","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-10DOI: 10.1016/j.apcatb.2024.124592
Lu Lin, Yongjian Zeng, Suyu Zhang, Di Hu, Zhiwei Jiang, Guoqing Guan, Kai Yan
The hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) to biofuel 2,5-dimethylfuran (DMF) serves as a vital reaction in biomass refineries. Herein, Pd-UiO-66 catalysts with controlled contents of ligand-vacancies were developed for the HMF-to-DMF conversion. Strikingly, a volcano-like relationship between defect level and HDO activity was obtained. The DMF yield was promoted ∼3 times, reaching 92.2 % at 160 °C and 15 bar H, which refers to a high-level turnover frequency value of 42.66 h among the reported candidates. The Pd-UiO-66 catalysts also afforded >80 % yield for the HDO of 5-methyl furfural, furfural, and vanillin. Besides, high HDO activity could be retained in five recycles. Manipulating the contents of ligand-vacancies was confirmed to create more Pd species and Bronsted acid sites, leading to remarkable performance. This work provides significant inspiration for tuning structural defects in MOFs to realize the efficient HDO of platform molecules in biomass valorization.
{"title":"Tuning ligand-vacancies in Pd-UiO-66 to boost biofuel production from 5-hydroxymethylfurfural hydrodeoxygenation","authors":"Lu Lin, Yongjian Zeng, Suyu Zhang, Di Hu, Zhiwei Jiang, Guoqing Guan, Kai Yan","doi":"10.1016/j.apcatb.2024.124592","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124592","url":null,"abstract":"The hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) to biofuel 2,5-dimethylfuran (DMF) serves as a vital reaction in biomass refineries. Herein, Pd-UiO-66 catalysts with controlled contents of ligand-vacancies were developed for the HMF-to-DMF conversion. Strikingly, a volcano-like relationship between defect level and HDO activity was obtained. The DMF yield was promoted ∼3 times, reaching 92.2 % at 160 °C and 15 bar H, which refers to a high-level turnover frequency value of 42.66 h among the reported candidates. The Pd-UiO-66 catalysts also afforded >80 % yield for the HDO of 5-methyl furfural, furfural, and vanillin. Besides, high HDO activity could be retained in five recycles. Manipulating the contents of ligand-vacancies was confirmed to create more Pd species and Bronsted acid sites, leading to remarkable performance. This work provides significant inspiration for tuning structural defects in MOFs to realize the efficient HDO of platform molecules in biomass valorization.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249993","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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