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":null,"pages":null},"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":null,"pages":null},"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":null,"pages":null},"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":null,"pages":null},"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":null,"pages":null},"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":null,"pages":null},"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":null,"pages":null},"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}
Pub Date : 2024-08-28DOI: 10.1016/j.apcatb.2024.124549
Menghui Liu, Rui Zou, Chang-jun Liu
Increasing interests in the supported Ru catalysts for CO methanation can be recently found in the literature. In this work, we demonstrated that the enhanced surface hydrophilicity of ZrO via air plasma treatment has significant effects on the properties of Ru/ZrO catalyst for CO methanation. At the same CO conversions, the reaction temperature over the catalysts on ZrO with enhanced hydrophilicity is 20–70 °C lower than those on untreated ZrO. The catalyst characterization confirms that the enhanced hydrophilicity leads to more hydroxyl groups and oxygen vacancies on the support, which further promotes CO adsorption and activation, facilitating the conversion of CO to HCO* and HCOO* in formate pathway. The enhanced hydrophilicity also causes a high Ru dispersion with stronger electronic interaction between Ru and ZrO, which forms more interfacial active sites and improves the adsorption and dissociation of H, promoting the linear-CO-Ru adsorption in CO* pathway.
最近，人们对用于一氧化碳甲烷化的支撑型 Ru 催化剂的兴趣日益浓厚。在这项工作中，我们证明了通过空气等离子体处理增强 ZrO 表面亲水性对 Ru/ZrO 催化剂甲烷化 CO 的性能有显著影响。在相同的 CO 转化率下，亲水性增强的 ZrO 催化剂的反应温度比未经处理的 ZrO 催化剂低 20-70 ℃。催化剂表征证实，亲水性的增强会在载体上产生更多的羟基和氧空位，从而进一步促进 CO 的吸附和活化，促进 CO 通过甲酸途径转化为 HCO* 和 HCOO*。亲水性的增强还能使 Ru 高度分散，Ru 和 ZrO 之间的电子相互作用更强，从而形成更多的界面活性位点，改善 H 的吸附和解离，促进 CO* 途径中的线性-CO-Ru 吸附。
{"title":"Improvement in the activity of Ru/ZrO2 for CO2 methanation by the enhanced hydrophilicity of zirconia","authors":"Menghui Liu, Rui Zou, Chang-jun Liu","doi":"10.1016/j.apcatb.2024.124549","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124549","url":null,"abstract":"Increasing interests in the supported Ru catalysts for CO methanation can be recently found in the literature. In this work, we demonstrated that the enhanced surface hydrophilicity of ZrO via air plasma treatment has significant effects on the properties of Ru/ZrO catalyst for CO methanation. At the same CO conversions, the reaction temperature over the catalysts on ZrO with enhanced hydrophilicity is 20–70 °C lower than those on untreated ZrO. The catalyst characterization confirms that the enhanced hydrophilicity leads to more hydroxyl groups and oxygen vacancies on the support, which further promotes CO adsorption and activation, facilitating the conversion of CO to HCO* and HCOO* in formate pathway. The enhanced hydrophilicity also causes a high Ru dispersion with stronger electronic interaction between Ru and ZrO, which forms more interfacial active sites and improves the adsorption and dissociation of H, promoting the linear-CO-Ru adsorption in CO* pathway.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226219","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.2024.124551
Wei Deng, Xuqiang Hao, Jiaqi Yang, Zhiliang Jin
Photocatalytic hydrogen production technology utilizes solar energy to decompose water into hydrogen, helping to alleviate the pressure of energy depletion. Engineering of non-precious metal nanomaterials as cocatalysts can play a significant role in low-cost, sustainable, and large-scale photocatalytic hydrogen production. Herein, MnCdS-Vs/NiCoS (MCSN) Schottky junction nanomaterials with strong electron coupling effect were prepared by a two-step hydrothermal method and successfully applied to a square meter hydrogen evolution device. The optimized MCSN material demonstrated high hydrogen evolution activity of 34.28 mmol g h, which is 9.34 and 685.60 times higher than that of pure MnCdS-Vs and NiCoS, respectively. More importantly, in a square meter (1 m) flat-plate reactor, MCSN produced H evolution approximately 201 mmol in 5 h, showcasing its potential for large-scale applications. XPS and DFT calculations demonstrated that MnCdS-V interacts with NiCoS to produce a strong electron coupling effect and form a Schottky junction. It promotes the facilitated the directional migration of photogenerated electrons from MnCdS-Vs to NiCoS, but also effectively suppressed electron backflow through the Schottky barrier. Furthermore, the abundance of sulfur vacancies enhanced visible light absorption capability, further improving photocatalytic hydrogen evolution performance. This work delves into the role of defect engineering and Schottky junction design in enhancing photocatalytic performance, providing new insights into transitioning photocatalytic hydrogen production technologies from small-scale laboratory experiments to large-scale practical applications.
{"title":"Strong electron coupling effect of non-precious metal Schottky junctions enhanced square meter level photocatalytic hydrogen evolution","authors":"Wei Deng, Xuqiang Hao, Jiaqi Yang, Zhiliang Jin","doi":"10.1016/j.apcatb.2024.124551","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124551","url":null,"abstract":"Photocatalytic hydrogen production technology utilizes solar energy to decompose water into hydrogen, helping to alleviate the pressure of energy depletion. Engineering of non-precious metal nanomaterials as cocatalysts can play a significant role in low-cost, sustainable, and large-scale photocatalytic hydrogen production. Herein, MnCdS-Vs/NiCoS (MCSN) Schottky junction nanomaterials with strong electron coupling effect were prepared by a two-step hydrothermal method and successfully applied to a square meter hydrogen evolution device. The optimized MCSN material demonstrated high hydrogen evolution activity of 34.28 mmol g h, which is 9.34 and 685.60 times higher than that of pure MnCdS-Vs and NiCoS, respectively. More importantly, in a square meter (1 m) flat-plate reactor, MCSN produced H evolution approximately 201 mmol in 5 h, showcasing its potential for large-scale applications. XPS and DFT calculations demonstrated that MnCdS-V interacts with NiCoS to produce a strong electron coupling effect and form a Schottky junction. It promotes the facilitated the directional migration of photogenerated electrons from MnCdS-Vs to NiCoS, but also effectively suppressed electron backflow through the Schottky barrier. Furthermore, the abundance of sulfur vacancies enhanced visible light absorption capability, further improving photocatalytic hydrogen evolution performance. This work delves into the role of defect engineering and Schottky junction design in enhancing photocatalytic performance, providing new insights into transitioning photocatalytic hydrogen production technologies from small-scale laboratory experiments to large-scale practical applications.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205135","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 integration of nitrogen vacancies (Nv) exhibits significant role in promoting the efficiency of single-atom catalysts (SACs). Herein, a novel dual SAC, FeNi-Nv/CN, was developed via immobilizing Fe-Ni dual atoms onto graphitic carbon nitride with Nv sites. The FeNi-Nv/CN could effectively activate peroxymonosulfate (PMS) and generate plentiful reactive oxygen owing to the excellent Fenton-like catalytic property of FeNi, which could facilitate the degradation of Orange II. Moreover, the Nv in FeNi-Nv/CN could augment electron density around Fe-Ni atomic pairs obviously, which was beneficial to strengthen the electron transfer process (ETP) and further improve the degradation efficiency of Orange II. The density functional theory (DFT) calculations and experimental results of FeNi-Nv/CN testified the robust synergistic capacity between dual single-atomic reaction sites and Nv. This work provided a valuable strategy for the construction of dual SAC and could be a promising candidate in the effective degradation of environmental contaminant.
{"title":"Heterogeneous Fe-Ni dual-atom catalysts coupled N-vacancy engineering for enhanced activation of peroxymonosulfate","authors":"Jiewen Qin, Qian Wang, Bei Han, Chen Jin, Cuihong Luo, Yunqiang Sun, Zhichao Dai, Shoucui Wang, Hongmei Liu, Xiuwen Zheng, Zunfu Hu","doi":"10.1016/j.apcatb.2024.124538","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124538","url":null,"abstract":"The integration of nitrogen vacancies (Nv) exhibits significant role in promoting the efficiency of single-atom catalysts (SACs). Herein, a novel dual SAC, FeNi-Nv/CN, was developed via immobilizing Fe-Ni dual atoms onto graphitic carbon nitride with Nv sites. The FeNi-Nv/CN could effectively activate peroxymonosulfate (PMS) and generate plentiful reactive oxygen owing to the excellent Fenton-like catalytic property of FeNi, which could facilitate the degradation of Orange II. Moreover, the Nv in FeNi-Nv/CN could augment electron density around Fe-Ni atomic pairs obviously, which was beneficial to strengthen the electron transfer process (ETP) and further improve the degradation efficiency of Orange II. The density functional theory (DFT) calculations and experimental results of FeNi-Nv/CN testified the robust synergistic capacity between dual single-atomic reaction sites and Nv. This work provided a valuable strategy for the construction of dual SAC and could be a promising candidate in the effective degradation of environmental contaminant.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205117","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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