Pub Date : 2024-09-03DOI: 10.1016/j.apcatb.2024.124563
Bo Kang, Zhilin Chen, Jie Yang, Mingxin Lv, Hongli He, Guoxin Chen, Liyuan Huai, Chunlin Chen, Jian Zhang
Balancing the Cu/Cu ratio is a common strategy to improve catalytic activity of Cu-based catalysts but is still constrained by low atomic utilization and the inherent nature of charge distribution. Herein, we reported a strategy of replacing the Cu active sites in Cu-based catalysts by constructing bimetallic sites on ceria, which consist of spatially separated trace amounts of palladium metal and plate-shaped Cu clusters with one-atom layers. The catalytic activity of the prepared CuPd/CeO-FA catalyst (using formic acid) was 4 times that of conventional CuPd/CeO-H catalyst in selective hydrogenation of 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan, even outperforming some existing noble metal catalysts. Multiple characterizations and theoretical calculations demonstrated that the Pd atom is the heterolytic activation site for H molecules while plate-shaped Cu metal clusters act as effective hydrogenation places. This directional control involving both spatial relationship and electronic structure of the active site provides a new strategy for designing hydrogenated catalysts.
{"title":"Boosting hydrogenation properties of supported Cu-based catalysts by replacing Cu0 active sites","authors":"Bo Kang, Zhilin Chen, Jie Yang, Mingxin Lv, Hongli He, Guoxin Chen, Liyuan Huai, Chunlin Chen, Jian Zhang","doi":"10.1016/j.apcatb.2024.124563","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124563","url":null,"abstract":"Balancing the Cu/Cu ratio is a common strategy to improve catalytic activity of Cu-based catalysts but is still constrained by low atomic utilization and the inherent nature of charge distribution. Herein, we reported a strategy of replacing the Cu active sites in Cu-based catalysts by constructing bimetallic sites on ceria, which consist of spatially separated trace amounts of palladium metal and plate-shaped Cu clusters with one-atom layers. The catalytic activity of the prepared CuPd/CeO-FA catalyst (using formic acid) was 4 times that of conventional CuPd/CeO-H catalyst in selective hydrogenation of 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan, even outperforming some existing noble metal catalysts. Multiple characterizations and theoretical calculations demonstrated that the Pd atom is the heterolytic activation site for H molecules while plate-shaped Cu metal clusters act as effective hydrogenation places. This directional control involving both spatial relationship and electronic structure of the active site provides a new strategy for designing hydrogenated catalysts.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"36 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205128","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 : 2024-09-03DOI: 10.1016/j.apcatb.2024.124562
Xuechao Tan, Suk Bong Hong
Natural gas engines are the most viable alternative to diesel and gasoline ones. However, the current state-of-art catalyst, palladium (Pd) on alumina, for eliminating unburnt methane from engine exhaust suffers from high light-off temperature (> 400 °C) and poor water tolerance. Here we systematically investigated the effects of zeolite structure and Si/Al ratio, catalyst calcination temperature and extra-framework cation type on catalytic performance of zeolite-supported Pd catalysts for wet methane combustion to overcome these limitations. We found that a 3.0 wt% Pd catalyst supported on Na-post-exchanged 500 °C-calcined IWV zeolite with a Si/Al ratio of 45 has a light-off temperature as low as 290 °C for methane combustion in the presence of 10 % water vapor while maintaining ca. 85 % methane conversion at 330 °C for 100 h. This study provides a new direction for bringing supported Pd catalysts close to real-world applications.
天然气发动机是柴油和汽油发动机最可行的替代品。然而，目前用于消除发动机尾气中未燃烧甲烷的最先进催化剂--氧化铝上的钯（Pd）--存在着点火温度高（> 400 °C）和耐水性差的问题。在此，我们系统地研究了沸石结构和硅/铝比例、催化剂煅烧温度和框架外阳离子类型对湿法甲烷燃烧沸石支撑钯催化剂催化性能的影响，以克服这些局限性。我们发现，在 Si/Al 比率为 45 的 Na 后置换 500 °C 煅烧 IWV 沸石上支撑的 3.0 wt% Pd 催化剂，在 10% 水蒸汽存在下燃烧甲烷的熄灭温度低至 290 °C，同时在 330 °C 下 100 小时内保持约 85% 的甲烷转化率。这项研究为使支撑钯催化剂接近实际应用提供了新的方向。
{"title":"A highly active and stable palladium zeolite catalyst for wet methane combustion","authors":"Xuechao Tan, Suk Bong Hong","doi":"10.1016/j.apcatb.2024.124562","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124562","url":null,"abstract":"Natural gas engines are the most viable alternative to diesel and gasoline ones. However, the current state-of-art catalyst, palladium (Pd) on alumina, for eliminating unburnt methane from engine exhaust suffers from high light-off temperature (> 400 °C) and poor water tolerance. Here we systematically investigated the effects of zeolite structure and Si/Al ratio, catalyst calcination temperature and extra-framework cation type on catalytic performance of zeolite-supported Pd catalysts for wet methane combustion to overcome these limitations. We found that a 3.0 wt% Pd catalyst supported on Na-post-exchanged 500 °C-calcined IWV zeolite with a Si/Al ratio of 45 has a light-off temperature as low as 290 °C for methane combustion in the presence of 10 % water vapor while maintaining ca. 85 % methane conversion at 330 °C for 100 h. This study provides a new direction for bringing supported Pd catalysts close to real-world applications.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"404 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205084","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 : 2024-09-02DOI: 10.1016/j.apcatb.2024.124556
Yuekun Hu, Mingwang Lu, Guanhua Zhang, Xiaowei Zhao, Yan Liu, Xiaojing Yang, Xiaofei Yu, Xinghua Zhang, Zunming Lu, Lanlan Li
Developing efficient and durable Pt-based electrocatalysts for oxygen reduction reaction (ORR) is critical for the practical application of fuel cells but still remains challenge at present. Here we successfully synthesized a series of ternary L1-PtCoFe (x=0.33, 0.50 and 0.67) intermetallic nanoparticles (NPs) supported on reduced graphene oxide for ORR catalysis. L1-PtCoFe exhibits the highest mass activity (MA) of 0.93 A mg at 0.9 V (1.82 times the corresponding binary L1-PtCo intermetallics) and minimal activity loss (24.73 % loss in MA) after 30,000 potential cycles. By Density Functional Theory calculations, the excellent performance of ternary L1-PtCoFe can be ascribed to: (1) more efficient electronic structure regulation caused by dual-element driven electron transfer, which leads to more electron accumulation on Pt and weakens the over-binding of oxygen-containing species, (2) the unique two-center bridge pattern of O adsorption over Pt-Fe site leads to ORR proceeding the dissociative mechanism, avoiding the formation of OOH*.
{"title":"Ternary ordered L10-Pt-Co-Fe intermetallics for efficient ORR catalysis through dissociation pathway","authors":"Yuekun Hu, Mingwang Lu, Guanhua Zhang, Xiaowei Zhao, Yan Liu, Xiaojing Yang, Xiaofei Yu, Xinghua Zhang, Zunming Lu, Lanlan Li","doi":"10.1016/j.apcatb.2024.124556","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124556","url":null,"abstract":"Developing efficient and durable Pt-based electrocatalysts for oxygen reduction reaction (ORR) is critical for the practical application of fuel cells but still remains challenge at present. Here we successfully synthesized a series of ternary L1-PtCoFe (x=0.33, 0.50 and 0.67) intermetallic nanoparticles (NPs) supported on reduced graphene oxide for ORR catalysis. L1-PtCoFe exhibits the highest mass activity (MA) of 0.93 A mg at 0.9 V (1.82 times the corresponding binary L1-PtCo intermetallics) and minimal activity loss (24.73 % loss in MA) after 30,000 potential cycles. By Density Functional Theory calculations, the excellent performance of ternary L1-PtCoFe can be ascribed to: (1) more efficient electronic structure regulation caused by dual-element driven electron transfer, which leads to more electron accumulation on Pt and weakens the over-binding of oxygen-containing species, (2) the unique two-center bridge pattern of O adsorption over Pt-Fe site leads to ORR proceeding the dissociative mechanism, avoiding the formation of OOH*.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"48 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205111","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}
Direct synthesis of dimethyl carbonate (DMC) from CO is promising for CO utilization, however its efficiency remains far from industrial-scale implementation for lack of customized catalysts. Herein, a hydroxyl-functionalized ionic liquid (HFIL) was developed to enhance catalytic activity, and importantly, to facilitate IL recovery through spontaneous phase separation. A high DMC yield (6.5 g·kg·h) over HFIL was achieved under mild conditions compared to non- hydroxyl IL. Self-diffusion coefficients characterization revealed intensified diffusion of CHOH and HFIL, alongside reduced blockage of active sites after hydroxyl functionalization. Density functional theory calculations elucidated that cation polarization induced by hydroxyl group facilitated the synergistic activation of both substrates and monomethyl carbonate intermediate. The reaction mechanism was further verified through diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations. The self-separation behavior was demonstrated by molecular dynamics simulations. The deep insights into hydroxyl effects towards direct DMC synthesis provide a pioneering perspective for CO capture and utilization using functionalized ILs.
从一氧化碳直接合成碳酸二甲酯（DMC）在一氧化碳利用方面前景广阔，但由于缺乏定制催化剂，其效率仍远未达到工业规模。在此，我们开发了一种羟基官能化离子液体（HFIL），以提高催化活性，更重要的是，通过自发相分离促进离子液体的回收。与非羟基离子液体相比，HFIL 在温和条件下实现了较高的 DMC 产量（6.5 g-kg-h）。自扩散系数表征显示，羟基官能化后，CHOH 和 HFIL 的扩散加强，同时活性位点的阻塞减少。密度泛函理论计算阐明，羟基引起的阳离子极化促进了两种底物和碳酸单甲酯中间体的协同活化。通过漫反射红外傅立叶变换光谱和理论计算进一步验证了反应机理。分子动力学模拟证明了自分离行为。对羟基效应的深入了解为直接合成 DMC 提供了利用功能化 IL 捕获和利用 CO 的开创性视角。
{"title":"Hydroxyl-functionalization promoted activity and recovery of ionic liquids in direct dimethyl carbonate synthesis from CO2","authors":"Jiawei Ruan, Lifang Chen, Xinzi Wu, Shaokang Qian, Kunchi Xie, Xiaoyi Zhang, Hongye Cheng, Zhen Song, Zhiwen Qi","doi":"10.1016/j.apcatb.2024.124557","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124557","url":null,"abstract":"Direct synthesis of dimethyl carbonate (DMC) from CO is promising for CO utilization, however its efficiency remains far from industrial-scale implementation for lack of customized catalysts. Herein, a hydroxyl-functionalized ionic liquid (HFIL) was developed to enhance catalytic activity, and importantly, to facilitate IL recovery through spontaneous phase separation. A high DMC yield (6.5 g·kg·h) over HFIL was achieved under mild conditions compared to non- hydroxyl IL. Self-diffusion coefficients characterization revealed intensified diffusion of CHOH and HFIL, alongside reduced blockage of active sites after hydroxyl functionalization. Density functional theory calculations elucidated that cation polarization induced by hydroxyl group facilitated the synergistic activation of both substrates and monomethyl carbonate intermediate. The reaction mechanism was further verified through diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations. The self-separation behavior was demonstrated by molecular dynamics simulations. The deep insights into hydroxyl effects towards direct DMC synthesis provide a pioneering perspective for CO capture and utilization using functionalized ILs.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"4 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226216","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 : 2024-08-31DOI: 10.1016/j.apcatb.2024.124555
Jie Ren, Zeeshan Abbasi, Inam Ullah, Feng Zeng
Developing efficient Ni-based catalysts and understanding the mechanism of tar removal are crucial for upgrading biomass gasification technology. Literature has identified the superior performance of Ni-based catalysts in reforming tar model compounds like toluene under a steam atmosphere. In this work, we have synthesized LaCeNiO catalysts and examined their activity with benchmark ABO-type perovskites in dry reforming of toluene (DRT). Catalytic experiments revealed that LaCeNiO catalysts exhibited superior activity and stability regarding toluene conversion (85.4%) compared to LaCeNiO. The structural study, conducted through various techniques, highlighted the easier reducibility of Ni from the ABO perovskite lattice, leaving higher oxygen vacancies, and higher basicity for reactant adsorption in DRT. Besides, DRIFTS experiments confirmed the *CHO-participated pathway of syngas generation from DRT. The findings suggested potential pathways for designing catalysts to support biomass gasification while contributing to global carbon reduction.
{"title":"Dry reforming of toluene for syngas production over Ni-based perovskite-type oxides","authors":"Jie Ren, Zeeshan Abbasi, Inam Ullah, Feng Zeng","doi":"10.1016/j.apcatb.2024.124555","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124555","url":null,"abstract":"Developing efficient Ni-based catalysts and understanding the mechanism of tar removal are crucial for upgrading biomass gasification technology. Literature has identified the superior performance of Ni-based catalysts in reforming tar model compounds like toluene under a steam atmosphere. In this work, we have synthesized LaCeNiO catalysts and examined their activity with benchmark ABO-type perovskites in dry reforming of toluene (DRT). Catalytic experiments revealed that LaCeNiO catalysts exhibited superior activity and stability regarding toluene conversion (85.4%) compared to LaCeNiO. The structural study, conducted through various techniques, highlighted the easier reducibility of Ni from the ABO perovskite lattice, leaving higher oxygen vacancies, and higher basicity for reactant adsorption in DRT. Besides, DRIFTS experiments confirmed the *CHO-participated pathway of syngas generation from DRT. The findings suggested potential pathways for designing catalysts to support biomass gasification while contributing to global carbon reduction.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"6 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205112","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 : 2024-08-30DOI: 10.1016/j.apcatb.2024.124554
Jinxiong Tao, Hongxia Lin, Jiguang Deng, Yuxi Liu, Lin Jing, Zhiquan Hou, Lu Wei, Zhiwei Wang, Hongxing Dai
The long-standing contradiction between low-temperature activity and high-temperature stability is one of the difficulties in catalytic combustion of low-concentration methane. The traditional Pd−CeO catalyst system has been applied to the oxidation of methane with low concentrations. However, the problem of sintering at high temperatures still exists. In this work, we prepared the Pt-modified Pd−CeO nanowires (NW) sample (in which the actual Pt, Pd, and Ce contents were 0.12, 0.86, and 9.8 wt%, respectively) using the one-pot reverse-micelle emulsion method. It was found that Pt-Pd−CeONW@SiO showed the highest low-temperature catalytic activity at a space velocity of 20,000 mL/(g h) and the best water resistance and high-temperature stability in the combustion of methane. The and (the temperatures for achieving methane conversions of 50 and 90 %) were 298 and 342 ℃, respectively, methane reaction rate at 270 ℃ was 0.49 μmol/(g s), and turnover frequency (TOF) at 270 °C was 0.198 s over Pt-Pd−CeONW@SiO; whereas over Pd−CeONW@SiO (in which the actual Pd and Ce contents were 0.82 and 10.6 wt%, respectively), the and were 360 and 420 ℃, respectively, methane reaction rate at 270 ℃ was 0.074 μmol/(g s), and TOF at 270 °C was 0.032 s. The introduction of the highly dispersed Pt to Pd−CeONW@SiO could effectively increase the PdO sites of unsaturated coordination through the electron-donating interaction of the Pt with PdO, which played an important role in activating the C−H bonds in methane. In addition, the unique structure of encapsulation also rendered the Pt-Pd−CeONW@SiO sample to possess good water resistance and thermal stability in methane combustion. We are sure that the present work provides a possibility for developing the catalysts with stable catalytic and water-resistant performance at low and high temperatures in the combustion of methane.
{"title":"Enhanced low-temperature catalytic activity and stability in methane combustion of Pd−CeO2 nanowires@SiO2 by Pt dispersion","authors":"Jinxiong Tao, Hongxia Lin, Jiguang Deng, Yuxi Liu, Lin Jing, Zhiquan Hou, Lu Wei, Zhiwei Wang, Hongxing Dai","doi":"10.1016/j.apcatb.2024.124554","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124554","url":null,"abstract":"The long-standing contradiction between low-temperature activity and high-temperature stability is one of the difficulties in catalytic combustion of low-concentration methane. The traditional Pd−CeO catalyst system has been applied to the oxidation of methane with low concentrations. However, the problem of sintering at high temperatures still exists. In this work, we prepared the Pt-modified Pd−CeO nanowires (NW) sample (in which the actual Pt, Pd, and Ce contents were 0.12, 0.86, and 9.8 wt%, respectively) using the one-pot reverse-micelle emulsion method. It was found that Pt-Pd−CeONW@SiO showed the highest low-temperature catalytic activity at a space velocity of 20,000 mL/(g h) and the best water resistance and high-temperature stability in the combustion of methane. The and (the temperatures for achieving methane conversions of 50 and 90 %) were 298 and 342 ℃, respectively, methane reaction rate at 270 ℃ was 0.49 μmol/(g s), and turnover frequency (TOF) at 270 °C was 0.198 s over Pt-Pd−CeONW@SiO; whereas over Pd−CeONW@SiO (in which the actual Pd and Ce contents were 0.82 and 10.6 wt%, respectively), the and were 360 and 420 ℃, respectively, methane reaction rate at 270 ℃ was 0.074 μmol/(g s), and TOF at 270 °C was 0.032 s. The introduction of the highly dispersed Pt to Pd−CeONW@SiO could effectively increase the PdO sites of unsaturated coordination through the electron-donating interaction of the Pt with PdO, which played an important role in activating the C−H bonds in methane. In addition, the unique structure of encapsulation also rendered the Pt-Pd−CeONW@SiO sample to possess good water resistance and thermal stability in methane combustion. We are sure that the present work provides a possibility for developing the catalysts with stable catalytic and water-resistant performance at low and high temperatures in the combustion of methane.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"44 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226217","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}
The incorporation of rare earth (RE) elements into high-entropy alloys (HEAs) as electrocatalysts for hydrogen evolution reaction (HER) shows great potential in addressing the energy crisis. Here, we successfully synthesized cerium (Ce)-tailored PdCeMoCuRu HEA with chemical homogeneity and stability using a facile wet-chemical synthesis strategy. The obtained PdCeMoCuRu HEA provides abundant active metal sites, resulting in superior HER performance compared to state-of-the-art Pt/C. It only requires 12.8 mV to achieve a current density of 10 mA cm, which is nearly half that required for Pt/C (24.8 mV). Importantly, it exhibits excellent electrocatalytic durability for 100 hours even under a high current density of 1.0 A cm at the ampere level. Density functional theory (DFT) calculations confirm that the introduction of Ce can modify the electronic configuration and generate synergistic effects around Pd, Cu, and Ru active sites. This work establishes a novel approach for designing efficient RE-tailored HEA electrocatalysts.
在高熵合金（HEA）中加入稀土元素作为氢进化反应（HER）的电催化剂，在解决能源危机方面显示出巨大的潜力。在此，我们采用简便的湿化学合成策略，成功合成了具有化学均匀性和稳定性的铈（Ce）定制 PdCeMoCuRu HEA。所获得的 PdCeMoCuRu HEA 具有丰富的活性金属位点，因此与最先进的 Pt/C 相比，其 HER 性能更为优异。它只需要 12.8 mV 就能达到 10 mA cm 的电流密度，几乎是 Pt/C 所需值（24.8 mV）的一半。重要的是，即使在安培级 1.0 A cm 的高电流密度下，它也能表现出 100 小时的出色电催化耐久性。密度泛函理论（DFT）计算证实，引入 Ce 可以改变电子构型，并在钯、铜和钌活性位点周围产生协同效应。这项工作为设计高效的 RE 定制 HEA 电催化剂提供了一种新方法。
{"title":"Cerium-optimized platinum-free high-entropy alloy nanoclusters for enhanced ampere-level sustainable hydrogen generation","authors":"Yujia Zhang, Kunkun Nie, Binjie Li, Lixin Yi, Chen Hu, Ziyi Wang, Xiaorong Hao, Wenlin Zhang, Zhengqing Liu, Wei Huang","doi":"10.1016/j.apcatb.2024.124529","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124529","url":null,"abstract":"The incorporation of rare earth (RE) elements into high-entropy alloys (HEAs) as electrocatalysts for hydrogen evolution reaction (HER) shows great potential in addressing the energy crisis. Here, we successfully synthesized cerium (Ce)-tailored PdCeMoCuRu HEA with chemical homogeneity and stability using a facile wet-chemical synthesis strategy. The obtained PdCeMoCuRu HEA provides abundant active metal sites, resulting in superior HER performance compared to state-of-the-art Pt/C. It only requires 12.8 mV to achieve a current density of 10 mA cm, which is nearly half that required for Pt/C (24.8 mV). Importantly, it exhibits excellent electrocatalytic durability for 100 hours even under a high current density of 1.0 A cm at the ampere level. Density functional theory (DFT) calculations confirm that the introduction of Ce can modify the electronic configuration and generate synergistic effects around Pd, Cu, and Ru active sites. This work establishes a novel approach for designing efficient RE-tailored HEA electrocatalysts.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"9 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205120","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 : 2024-08-30DOI: 10.1016/j.apcatb.2024.124553
Yuan Qin, Zihao Ou, Chaozhong Guo, Yao Liu, Rong Jin, Chuanlan Xu, Haifeng Chen, Yujun Si, Honglin Li
Regulating the electronic structure by phosphor-doping is a preferred strategy to boost the performance of carbon-based catalysts for oxygen reduction reaction (ORR). Here, a porous Fe, P, N-codoped carbon catalyst (PCF-FeTz-900) is designed by a phytic acid-assisted thermal etching strategy, in which P atoms are first doped into the carbon matrix to form a stable PC bond, and then FeN sites are produced from Fe-2,4,6-Tris(2-pyridyl)-s-triazine complex (Fe-TPTz). Theoretical calculations suggest that the electrons are transferred from the doped P atom to the neighboring FeN sites, which facilitates the ORR at the Fe sites by reducing the energy barrier and the adsorption energy of intermediates. Additionally, the P-doped FeN (FeNP) structure manifests a lower free energy difference than that of FeN and the -band center of Fe is also lowered, which further ensures its higher ORR catalytic ability. As a result, the PCF-FeTz-900 catalyst exhibits superior ORR activity and stability in alkaline electrolyte, and the assembled primary zinc-air battery shows greater performances compared to the commercial Pt/C catalyst. This work can provide an effective pathway for modulating the performance of doped-carbon materials in energy conversion devices.
通过磷掺杂调节电子结构是提高氧还原反应（ORR）碳基催化剂性能的首选策略。本文采用植酸辅助热蚀刻策略设计了一种多孔的Fe、P、N掺杂碳催化剂（PCF-FeTz-900），首先在碳基体中掺入P原子以形成稳定的PC键，然后从Fe-2,4,6-三(2-吡啶基)-s-三嗪络合物（Fe-TPTz）中产生FeN位点。理论计算表明，电子从掺杂的 P 原子转移到邻近的 FeN 位点，通过降低中间产物的能障和吸附能，促进了 Fe 位点的 ORR。此外，掺杂 P 原子的 FeN（FeNP）结构表现出比 FeN 更低的自由能差，Fe 的-带中心也降低了，这进一步确保了其更高的 ORR 催化能力。因此，PCF-FeTz-900 催化剂在碱性电解液中表现出更高的 ORR 活性和稳定性，与商用 Pt/C 催化剂相比，组装后的一次锌-空气电池性能更佳。这项研究为调节掺碳材料在能源转换设备中的性能提供了有效途径。
{"title":"Phosphor-doping modulates the d-band center of Fe atoms in Fe-N4 catalytic sites to boost the activity of oxygen reduction","authors":"Yuan Qin, Zihao Ou, Chaozhong Guo, Yao Liu, Rong Jin, Chuanlan Xu, Haifeng Chen, Yujun Si, Honglin Li","doi":"10.1016/j.apcatb.2024.124553","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124553","url":null,"abstract":"Regulating the electronic structure by phosphor-doping is a preferred strategy to boost the performance of carbon-based catalysts for oxygen reduction reaction (ORR). Here, a porous Fe, P, N-codoped carbon catalyst (PCF-FeTz-900) is designed by a phytic acid-assisted thermal etching strategy, in which P atoms are first doped into the carbon matrix to form a stable PC bond, and then FeN sites are produced from Fe-2,4,6-Tris(2-pyridyl)-s-triazine complex (Fe-TPTz). Theoretical calculations suggest that the electrons are transferred from the doped P atom to the neighboring FeN sites, which facilitates the ORR at the Fe sites by reducing the energy barrier and the adsorption energy of intermediates. Additionally, the P-doped FeN (FeNP) structure manifests a lower free energy difference than that of FeN and the -band center of Fe is also lowered, which further ensures its higher ORR catalytic ability. As a result, the PCF-FeTz-900 catalyst exhibits superior ORR activity and stability in alkaline electrolyte, and the assembled primary zinc-air battery shows greater performances compared to the commercial Pt/C catalyst. This work can provide an effective pathway for modulating the performance of doped-carbon materials in energy conversion devices.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"61 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205114","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}
The solvothermal synthesis of optimized micron-sized spherical CeMnO-350 yields remarkable results in ultra-low temperature NH-SCR of NO, with over 91 % NO conversion achieved between 59 and 255 ℃. Notably, under 5 vol% HO and 50 ppm SO, the CeMnO maintains NO conversion >99 % at 127 ℃ for extended periods, surpassing current ultra-low temperature deNO standards. This superior performance is attributed to the material's unique characteristics: the regular and porous surface morphology enhances exposure to active sites, particularly MnO(112) facets crucial for ultra-low temperature deNO, while the rough and loose surface and high MnO(222) exposure mitigate water vapor and SO poisoning. Furthermore, the thermal storage effect of the MnO/MnO system within CeMnO facilitates rapid thermal dissipation and ammonium sulfite decomposition. This process is further augmented by the pores, which aid in the confinement of deNO reaction heat and facilitate the flushing of flowing flue gas, thereby impeding the formation of ammonium bisulfate.
{"title":"Ultra-low temperature selective catalytic reduction of NOx into N2 by micron spherical CeMnOx in high-humidity atmospheres containing SO2","authors":"Xixi Chen, Peng Gao, Ling Huang, Yongji Hu, Jianhai Wang, Zonghang Liu, Yuesong Shen","doi":"10.1016/j.apcatb.2024.124552","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124552","url":null,"abstract":"The solvothermal synthesis of optimized micron-sized spherical CeMnO-350 yields remarkable results in ultra-low temperature NH-SCR of NO, with over 91 % NO conversion achieved between 59 and 255 ℃. Notably, under 5 vol% HO and 50 ppm SO, the CeMnO maintains NO conversion >99 % at 127 ℃ for extended periods, surpassing current ultra-low temperature deNO standards. This superior performance is attributed to the material's unique characteristics: the regular and porous surface morphology enhances exposure to active sites, particularly MnO(112) facets crucial for ultra-low temperature deNO, while the rough and loose surface and high MnO(222) exposure mitigate water vapor and SO poisoning. Furthermore, the thermal storage effect of the MnO/MnO system within CeMnO facilitates rapid thermal dissipation and ammonium sulfite decomposition. This process is further augmented by the pores, which aid in the confinement of deNO reaction heat and facilitate the flushing of flowing flue gas, thereby impeding the formation of ammonium bisulfate.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"44 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205118","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 : 2024-08-28DOI: 10.1016/j.apcatb.2024.124550
Luosong Zheng, Heping Luo, Yuxin Zhong, Wanqian Li, Han Xu, Fuquan Xiong, Jiahao Pi, Yan Qing, Yiqiang Wu
Interface engineering has emerged as a promising strategy for efficiently enhancing catalytic performance. Herein, we present a built-in electric field (BEF) strategy to assemble CoS/NiS heterojunctions confined in S-doped carbon matrix (SC) and anchored S-doped carbide wood framework (SCW). Leveraging BEF, Co-S-Ni charge transfer channels and the superior mass transfer properties inherent in wood’s unique structure, (CoS/NiS)@SC/SCW exhibits a low overpotential of 220 mV at 50 mA cm, and remarkable stability. The experimental characterizations and theoretical simulation indicate that the constructed BEF can induce the directional transfer of electrons from CoS to NiS, which is beneficial for the adsorption of OH owing to the electrostatic interaction, thereby promotes the formation of the highly active amorphous metal hydroxide oxides at lower OER potentials. This work provides a new perspective for exploring the design of energy storage and conversion catalysts based on renewable wood substrates.
界面工程已成为有效提高催化性能的一种有前途的策略。在此，我们提出了一种内置电场（BEF）策略，用于在掺杂 S 的碳基质（SC）和锚定掺杂 S 的碳化木框架（SCW）中组装 CoS/NiS 异质结。利用 BEF、Co-S-Ni 电荷转移通道和木材独特结构中固有的优异传质特性，(CoS/NiS)@SC/SCW 在 50 mA cm 时具有 220 mV 的低过电位和出色的稳定性。实验表征和理论模拟表明，所构建的 BEF 能诱导电子从 CoS 定向转移到 NiS，由于静电作用，这有利于 OH 的吸附，从而在较低的 OER 电位下促进高活性非晶态金属氢氧化物氧化物的形成。这项工作为探索基于可再生木材基质的能量存储和转换催化剂的设计提供了一个新的视角。
{"title":"Wood-derived continuously oriented channels coupled with tunable built-in electric fields for efficient oxygen evolution","authors":"Luosong Zheng, Heping Luo, Yuxin Zhong, Wanqian Li, Han Xu, Fuquan Xiong, Jiahao Pi, Yan Qing, Yiqiang Wu","doi":"10.1016/j.apcatb.2024.124550","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124550","url":null,"abstract":"Interface engineering has emerged as a promising strategy for efficiently enhancing catalytic performance. Herein, we present a built-in electric field (BEF) strategy to assemble CoS/NiS heterojunctions confined in S-doped carbon matrix (SC) and anchored S-doped carbide wood framework (SCW). Leveraging BEF, Co-S-Ni charge transfer channels and the superior mass transfer properties inherent in wood’s unique structure, (CoS/NiS)@SC/SCW exhibits a low overpotential of 220 mV at 50 mA cm, and remarkable stability. The experimental characterizations and theoretical simulation indicate that the constructed BEF can induce the directional transfer of electrons from CoS to NiS, which is beneficial for the adsorption of OH owing to the electrostatic interaction, thereby promotes the formation of the highly active amorphous metal hydroxide oxides at lower OER potentials. This work provides a new perspective for exploring the design of energy storage and conversion catalysts based on renewable wood substrates.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"5 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226218","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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