The efficiency of CO photoreduction is limited by slow charge kinetics and the mass transfer of hydrophobic CO and HO over the photocatalyst. Herein, we present a copper–alkynyl bond coordination polymer (CA-CP) with atomically-dispersed copper–alkynyl units (ADCAUs). By incorporating hydrophobic CA-CP with hydrophilic iodine vacancy-rich bismuth oxyhalides (I-BX), we construct amphiphilic heterojunction photocatalysts (CA-CP/I-BX) for visible-light-driven CO photoreduction. CA-CP/I-BX achieves excellent stability, 100 % CO selectivity and a CO-evolution rate of 157.6 μmol g h coupled with O releasing. Experimental and theoretical calculations elucidate that the ADCAUs favor adsorption and activation of CO, and have high CO selectivity. Moreover, the amphiphilic janus structure not only ensures the spatial synergy effect of CO reduction and HO oxidation, but also promotes charge separation and proton feeding, boosting CO photoreduction activity. This work develops Cu–alkynyl coordination polymer photocatalysts with ADCAUs and provides insights into hydrophobic–hydrophilic biphasic photocatalysts for synergistic CO reduction and HO oxidation.
光催化剂上缓慢的电荷动力学和疏水性 CO 和 HO 的传质限制了 CO 光还原的效率。在此，我们提出了一种具有原子分散铜-炔基单元（ADCAUs）的铜-炔基键配位聚合物（CA-CP）。通过将疏水性的 CA-CP 与亲水性的富碘空位氧卤化铋（I-BX）结合在一起，我们构建了两亲异质结光催化剂（CA-CP/I-BX），用于可见光驱动的 CO 光还原。CA-CP/I-BX 具有出色的稳定性、100% 的一氧化碳选择性以及 157.6 μmol g h 的一氧化碳转化率，同时还能释放 O。实验和理论计算表明，ADCAUs 有利于 CO 的吸附和活化，并具有较高的 CO 选择性。此外，两亲破环结构不仅确保了 CO 还原和 HO 氧化的空间协同效应，还促进了电荷分离和质子馈入，提高了 CO 光还原活性。这项研究开发了具有 ADCAUs 的铜-炔基配位聚合物光催化剂，为协同 CO 还原和 HO 氧化的疏水-亲水双相光催化剂提供了新的见解。
{"title":"Amphiphilic heterojunctions with atomically dispersed copper–alkynyl active units for highly efficient CO2 photoreduction","authors":"Fangjie Xu, Baoxin Ge, Pengyang Jiang, Xinlin Cai, Fangshu Xing, Caijin Huang","doi":"10.1016/j.apcatb.2024.124518","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124518","url":null,"abstract":"The efficiency of CO photoreduction is limited by slow charge kinetics and the mass transfer of hydrophobic CO and HO over the photocatalyst. Herein, we present a copper–alkynyl bond coordination polymer (CA-CP) with atomically-dispersed copper–alkynyl units (ADCAUs). By incorporating hydrophobic CA-CP with hydrophilic iodine vacancy-rich bismuth oxyhalides (I-BX), we construct amphiphilic heterojunction photocatalysts (CA-CP/I-BX) for visible-light-driven CO photoreduction. CA-CP/I-BX achieves excellent stability, 100 % CO selectivity and a CO-evolution rate of 157.6 μmol g h coupled with O releasing. Experimental and theoretical calculations elucidate that the ADCAUs favor adsorption and activation of CO, and have high CO selectivity. Moreover, the amphiphilic janus structure not only ensures the spatial synergy effect of CO reduction and HO oxidation, but also promotes charge separation and proton feeding, boosting CO photoreduction activity. This work develops Cu–alkynyl coordination polymer photocatalysts with ADCAUs and provides insights into hydrophobic–hydrophilic biphasic photocatalysts for synergistic CO reduction and HO oxidation.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"33 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226225","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 : 2024-08-22DOI: 10.1016/j.apcatb.2024.124519
Raka G. Dastidar, Javier E. Chavarrio, Zhen Jiang, Daniel J. McClelland, Manos Mavrikakis, George W. Huber
δ-Valerolactone (DVL) is a five-carbon (C5) cyclic ester that can undergo ring-opening polymerization to yield high-performance, biocompatible polyesters. But current market prices of C5 chemicals like DVL are very high due to poor availability of C5 feedstock in petroleum. Herein, we demonstrate a novel route to DVL synthesis via dehydrogenation of biomass-derived 2-hydroxytetrahydropyran (HTHP) over Cu/SiO without the use of toxic reagents. Since HTHP exists in thermal equilibrium with 3,4-dihydropyran (DHP) via dehydration, and with 2,2’-oxybis(tetrahydropyran) and 5-(tetrahydropyran-2-yloxy)pentanal via acetalization, we have also determined the thermochemistry (ΔH and ΔG) of each competing reaction using density functional theory (DFT) calculations at the M06–2X/cc-pVTZ level. Lastly, by developing a kinetic model of all 8 reactions involved, we have achieved 84 % selectivity to DVL at 150°C in a packed bed reactor for over 72 hours of time on stream.
{"title":"Catalytic production of δ-valerolactone (DVL) from biobased 2-hydroxytetrahydropyran (HTHP) – Combined experimental and modeling study","authors":"Raka G. Dastidar, Javier E. Chavarrio, Zhen Jiang, Daniel J. McClelland, Manos Mavrikakis, George W. Huber","doi":"10.1016/j.apcatb.2024.124519","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124519","url":null,"abstract":"δ-Valerolactone (DVL) is a five-carbon (C5) cyclic ester that can undergo ring-opening polymerization to yield high-performance, biocompatible polyesters. But current market prices of C5 chemicals like DVL are very high due to poor availability of C5 feedstock in petroleum. Herein, we demonstrate a novel route to DVL synthesis via dehydrogenation of biomass-derived 2-hydroxytetrahydropyran (HTHP) over Cu/SiO without the use of toxic reagents. Since HTHP exists in thermal equilibrium with 3,4-dihydropyran (DHP) via dehydration, and with 2,2’-oxybis(tetrahydropyran) and 5-(tetrahydropyran-2-yloxy)pentanal via acetalization, we have also determined the thermochemistry (ΔH and ΔG) of each competing reaction using density functional theory (DFT) calculations at the M06–2X/cc-pVTZ level. Lastly, by developing a kinetic model of all 8 reactions involved, we have achieved 84 % selectivity to DVL at 150°C in a packed bed reactor for over 72 hours of time on stream.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"71 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205171","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}
Designing and constructing novel discrete architecture for quantum dots modified ultrathin hollow nanotube BiSnO/BiOI S-scheme heterojunctions for the first time in this work is an ideal strategy to improve the photocatalytic activity. As expected, the BiSnO/BiOI heterojunction exhibited outstanding performance of degradation bisphenol A (BPA), the rate constant of BiSnO/BiOI heterojunction was 1.7 and 41.8 times higher than that of BiOI and BiSnO, respectively. The promoted activity could be attributed to the spatial separation of photogenerated carriers as well as redox reaction sites due to the discrete structure, and the enhanced charge separation due to the S-scheme mechanism via Bi-O channels as derived from DFT calculations. Furthermore, BiSnO/BiOI heterojunction exhibited unprecedented ultra-efficient in BPA degradation compared to other published Bi-based catalysts, and excellent performance under actual sunlight contributes to its prospective practical application. This strategy affords a novel approach for fabricating discrete S-scheme heterojunctions photocatalysts with high-efficiency, strong-stable, and sustainable.
本研究首次设计并构建了新型离散结构的量子点修饰超细空心纳米管 BiSnO/BiOI S 型异质结，是提高光催化活性的理想策略。不出所料，BiSnO/BiOI异质结在降解双酚A（BPA）方面表现突出，BiSnO/BiOI异质结的速率常数分别是BiOI和BiSnO的1.7倍和41.8倍。活性的提高可归因于离散结构导致的光生载流子和氧化还原反应位点的空间分离，以及 DFT 计算得出的通过 Bi-O 通道的 S 型机制导致的电荷分离增强。此外，与其他已发表的铋基催化剂相比，BiSnO/BiOI 异质结在降解双酚 A 方面表现出前所未有的超高效率，而且在实际日照下的优异性能也为其实际应用前景做出了贡献。这种策略为制造高效、强稳定、可持续的离散 S 型异质结光催化剂提供了一种新方法。
{"title":"Novel discrete architecture for quantum dots modified ultrathin hollow nanotube Bi2Sn2O7/Bi4O5I2 S-scheme heterojunction for ultra-efficient photocatalytic degradation of bisphenol A","authors":"Huizhong Wu, Jiana Jing, ShaSha Li, Shuaishuai Li, Jingyang Liu, Ruiheng Liang, Yican Zhang, Zehua Xia, Minghua Zhou","doi":"10.1016/j.apcatb.2024.124517","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124517","url":null,"abstract":"Designing and constructing novel discrete architecture for quantum dots modified ultrathin hollow nanotube BiSnO/BiOI S-scheme heterojunctions for the first time in this work is an ideal strategy to improve the photocatalytic activity. As expected, the BiSnO/BiOI heterojunction exhibited outstanding performance of degradation bisphenol A (BPA), the rate constant of BiSnO/BiOI heterojunction was 1.7 and 41.8 times higher than that of BiOI and BiSnO, respectively. The promoted activity could be attributed to the spatial separation of photogenerated carriers as well as redox reaction sites due to the discrete structure, and the enhanced charge separation due to the S-scheme mechanism via Bi-O channels as derived from DFT calculations. Furthermore, BiSnO/BiOI heterojunction exhibited unprecedented ultra-efficient in BPA degradation compared to other published Bi-based catalysts, and excellent performance under actual sunlight contributes to its prospective practical application. This strategy affords a novel approach for fabricating discrete S-scheme heterojunctions photocatalysts with high-efficiency, strong-stable, and sustainable.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"64 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205136","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 : 2024-08-22DOI: 10.1016/j.apcatb.2024.124516
Qingzheng Tian, Li Wang, Weiwei Sun, Alan Meng, Lina Yang, Zhenjiang Li
The industrial interest of ZnCdS as the photocatalytic media for hydrogen evolution reaction (HER) is severely hindered by its sluggish interfacial charge transfer, limited active sites, and serious photocorrosions. Herein, to catalyze more efficient and robust HER, a series of Se-doped ZnCdS with sulfur vacancies (denoted as Se/V-ZnCdS) are ingeniously designed and facilely synthesized. Experimental and theoretical studies reveal that by inducing dipole polarization through defect engineering synergistic elemental doping, spontaneous polarization field is generated in the bulk phase of ZnCdS, which together with elevated Fermi level renders the Se/V-ZnCdS with desirable spatial charge separation and transfer. Thus, the optimal 0.6 %Se/V-ZnCdS exhibits the outstanding performance of 85.3 mmol·g·h and excellent stability up to 24 h. This work highlights the high efficiency of dipole polarization realized by vacancy synergistic atomic doping in optimizing HER kinetics, and provides a new pathway to develop robust photocatalysts based on metal sulfoselenide for water-splitting reactions.
{"title":"Dipole polarization-driven spatial charge separation in defective zinc cadmium sulfoselenide for boosting photocatalytic hydrogen evolution","authors":"Qingzheng Tian, Li Wang, Weiwei Sun, Alan Meng, Lina Yang, Zhenjiang Li","doi":"10.1016/j.apcatb.2024.124516","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124516","url":null,"abstract":"The industrial interest of ZnCdS as the photocatalytic media for hydrogen evolution reaction (HER) is severely hindered by its sluggish interfacial charge transfer, limited active sites, and serious photocorrosions. Herein, to catalyze more efficient and robust HER, a series of Se-doped ZnCdS with sulfur vacancies (denoted as Se/V-ZnCdS) are ingeniously designed and facilely synthesized. Experimental and theoretical studies reveal that by inducing dipole polarization through defect engineering synergistic elemental doping, spontaneous polarization field is generated in the bulk phase of ZnCdS, which together with elevated Fermi level renders the Se/V-ZnCdS with desirable spatial charge separation and transfer. Thus, the optimal 0.6 %Se/V-ZnCdS exhibits the outstanding performance of 85.3 mmol·g·h and excellent stability up to 24 h. This work highlights the high efficiency of dipole polarization realized by vacancy synergistic atomic doping in optimizing HER kinetics, and provides a new pathway to develop robust photocatalysts based on metal sulfoselenide for water-splitting reactions.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205172","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 high hydrogen release temperature and thermodynamic stability of the coordination hydride LiAlH render it unsuitable for direct application. This work intends to improve the hydrogen release properties via compositing LiAlH and AlH with similar initial hydrogen release temperatures and introduce efficient additive Ni/CeO composite. The thermal stability of the composite system LiAlH-AlH is enormously reduced compared to that of LiAlH. In addition, the preferential release of hydrogen from LiAlH in the composite system provides additional heat for the subsequent release of hydrogen from AlH, accelerating the hydrogen release process. As a result, LiAlH-AlH-Ni/CeO composite performs enhanced hydrogen release performance with a hydrogen release capacity of 8.27 wt% hydrogen within 300 ℃ and a dehydrogenation onset temperature as low as 72.9 ℃. The enthalpy change of the first step hydrogen release reaction decreases from −11.99 kJ mol (LiAlH) to −2.02 kJ mol (LiAlH-AlH). Theoretical calculations indicate that both atomic dehybridisation and electron redistribution expedite the breaking of the Al-H bond and the consequent release of hydrogen.
{"title":"Constructing Ni/CeO2 synergistic catalysts into LiAlH4 and AlH3 composite for enhanced hydrogen released properties","authors":"Chunmin Zhang, Chunli Wang, Qingyun Shi, Xiaoli Wang, Shaolei Zhao, Long Liang, Qingshuang Wang, Limin Wang, Yong Cheng","doi":"10.1016/j.apcatb.2024.124521","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124521","url":null,"abstract":"The high hydrogen release temperature and thermodynamic stability of the coordination hydride LiAlH render it unsuitable for direct application. This work intends to improve the hydrogen release properties via compositing LiAlH and AlH with similar initial hydrogen release temperatures and introduce efficient additive Ni/CeO composite. The thermal stability of the composite system LiAlH-AlH is enormously reduced compared to that of LiAlH. In addition, the preferential release of hydrogen from LiAlH in the composite system provides additional heat for the subsequent release of hydrogen from AlH, accelerating the hydrogen release process. As a result, LiAlH-AlH-Ni/CeO composite performs enhanced hydrogen release performance with a hydrogen release capacity of 8.27 wt% hydrogen within 300 ℃ and a dehydrogenation onset temperature as low as 72.9 ℃. The enthalpy change of the first step hydrogen release reaction decreases from −11.99 kJ mol (LiAlH) to −2.02 kJ mol (LiAlH-AlH). Theoretical calculations indicate that both atomic dehybridisation and electron redistribution expedite the breaking of the Al-H bond and the consequent release of hydrogen.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"35 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205137","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}
Low degradation efficiency and significant transition metal leaching are two challenges in persulfate activation systems based on metal-organic frameworks (MOFs) for organic pollutant degradation. Here, the challenges were solved by designing and synthesizing a micron-sized core-shell material, γ-AlO-C-MIL-100(Fe) (γACM), by coating the γ-AlO core with carbon (γ-AlO-C) and futher modifying with MIL-100(Fe). Testing γACM with sulfamethazine (SMZ) demonstrated its outstanding peroxydisulfate (PDS) activation, achieving 92.5 % SMZ removal within 20 min at a low oxidant/pollutant ratio. Fe leaching from γACM was effectively inhibited, with only 3.59 % Fe lost after three recycles. The system showed adaptability across a wide pH range, and usability in sewage effluent, indicating promise for practical application. The hydrophobicity of γ-AlO-C, the coordinatively unsaturated sites in MIL-100(Fe), and the strong bounding of MIL-100(Fe) on γ-AlO-C ensured the effective SMZ gather, PDS activation, and Fe stability respectively, which led to the excellent performances of γACM.
{"title":"Efficient peroxydisulfate activation with γ-Al2O3-C-MIL-100(Fe) framework for sulfamethazine degradation: Enhanced oxidant utilization and reduced metal leaching","authors":"Jianxin Zhu, Haiyang Liu, Haijun Chen, Xiuyi Hua, Deming Dong, Dapeng Liang, Zhiyong Guo, Na Zheng","doi":"10.1016/j.apcatb.2024.124520","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124520","url":null,"abstract":"Low degradation efficiency and significant transition metal leaching are two challenges in persulfate activation systems based on metal-organic frameworks (MOFs) for organic pollutant degradation. Here, the challenges were solved by designing and synthesizing a micron-sized core-shell material, γ-AlO-C-MIL-100(Fe) (γACM), by coating the γ-AlO core with carbon (γ-AlO-C) and futher modifying with MIL-100(Fe). Testing γACM with sulfamethazine (SMZ) demonstrated its outstanding peroxydisulfate (PDS) activation, achieving 92.5 % SMZ removal within 20 min at a low oxidant/pollutant ratio. Fe leaching from γACM was effectively inhibited, with only 3.59 % Fe lost after three recycles. The system showed adaptability across a wide pH range, and usability in sewage effluent, indicating promise for practical application. The hydrophobicity of γ-AlO-C, the coordinatively unsaturated sites in MIL-100(Fe), and the strong bounding of MIL-100(Fe) on γ-AlO-C ensured the effective SMZ gather, PDS activation, and Fe stability respectively, which led to the excellent performances of γACM.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"64 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205173","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 synthesis of valuable aromatics via CO transformation, especially -xylene (PX), is of paramount significance but still remains greatly challenging due to the low efficiency and poor selectivity. The present work utilized a composite catalyst based on ZnZrO with a modified H-ZSM-5 exhibiting nano-prism stacking to realize the selective synthesis of PX. Methoxy species generated from CO-derived formate produced as an intermediate over the ZnZrO were readily incorporated into the xylene products for effective alkylation, contributed to an enhanced aromatics-based cycle that provided a selectivity for xylenes among all C hydrocarbons of 91.1 %. The lengthened straight channels in the H-ZSM-5 along the -axis, derived from the crystal stacking pattern, increased differences in the diffusion properties of the xylene isomers, and thereby steering the movement of molecules toward a product shape-selective pathway, leading to 90.1 % selectivity for PX among all xylenes, and provided exceptional CO utilization efficiency of ∼60 %.
{"title":"Regulating anisotropic diffusion in zeolite for reinforced para-xylene synthesis via CO2 hydrogenation in the presence of toluene","authors":"Xin Shang, Jingfeng Han, Qiao Han, Guangjin Hou, Anmin Zheng, Xiaofeng Yang, Zhiqiang Liu, Guodong Liu, Xiong Su, Yanqiang Huang, Tao Zhang","doi":"10.1016/j.apcatb.2024.124523","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124523","url":null,"abstract":"The synthesis of valuable aromatics via CO transformation, especially -xylene (PX), is of paramount significance but still remains greatly challenging due to the low efficiency and poor selectivity. The present work utilized a composite catalyst based on ZnZrO with a modified H-ZSM-5 exhibiting nano-prism stacking to realize the selective synthesis of PX. Methoxy species generated from CO-derived formate produced as an intermediate over the ZnZrO were readily incorporated into the xylene products for effective alkylation, contributed to an enhanced aromatics-based cycle that provided a selectivity for xylenes among all C hydrocarbons of 91.1 %. The lengthened straight channels in the H-ZSM-5 along the -axis, derived from the crystal stacking pattern, increased differences in the diffusion properties of the xylene isomers, and thereby steering the movement of molecules toward a product shape-selective pathway, leading to 90.1 % selectivity for PX among all xylenes, and provided exceptional CO utilization efficiency of ∼60 %.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"52 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205138","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 : 2024-08-18DOI: 10.1016/j.apcatb.2024.124512
Youmei Kong, Wei Yang, Jingjing Bao, Licheng Sun, Yang Qiu, Yu Chen, Qiang Zhao, Min Du, Zhengyu Mo
Engineering a robust non-platinum electrode toward hydrogen evolution reaction (HER) is important for water electrolysis. Here we develop a nanotip-structured electrode through a solution phase etching procedure. Based on the experimental and finite element simulation, the results show that the nanotip-structured design of electrodes cannot only lower the adhesion force of bubbles, but also induce a local-concentrated electric field that can promote the formation of Marangoni effect, and K concentrated and local acid-like microenvironment, consequently facilitating the detachment of bubbles and the HER kinetics. The electrochemical measurements and density function theory (DFT) calculation indicate that the constructed electrode exhibits a low H* binding energy and an outstanding HER performance that outperforms the commercial Pt/C in pH-universal medium. Overall, this work provides a feasible strategy for electrode design with a pH-universal feasibility by precisely constructing electrode interfaces.
设计一种坚固耐用的非铂电极以实现氢进化反应（HER）对于电解水非常重要。在这里，我们通过溶液相蚀刻程序开发了一种纳米尖端结构电极。基于实验和有限元模拟的结果表明，纳米尖端结构的电极设计不仅能降低气泡的粘附力，还能诱导局部集中的电场，促进马兰戈尼效应的形成，以及 K 浓度和局部酸样微环境的形成，从而促进气泡的脱落和 HER 动力学的产生。电化学测量和密度函数理论（DFT）计算表明，所构建的电极具有较低的 H* 结合能和出色的 HER 性能，在 pH 值通用介质中优于商用 Pt/C。总之，这项研究通过精确构建电极界面，为具有 pH 通用性的电极设计提供了一种可行的策略。
{"title":"Tip-intensified engineering of interfacial microenvironment toward pH-universal hydrogen evolution reaction","authors":"Youmei Kong, Wei Yang, Jingjing Bao, Licheng Sun, Yang Qiu, Yu Chen, Qiang Zhao, Min Du, Zhengyu Mo","doi":"10.1016/j.apcatb.2024.124512","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124512","url":null,"abstract":"Engineering a robust non-platinum electrode toward hydrogen evolution reaction (HER) is important for water electrolysis. Here we develop a nanotip-structured electrode through a solution phase etching procedure. Based on the experimental and finite element simulation, the results show that the nanotip-structured design of electrodes cannot only lower the adhesion force of bubbles, but also induce a local-concentrated electric field that can promote the formation of Marangoni effect, and K concentrated and local acid-like microenvironment, consequently facilitating the detachment of bubbles and the HER kinetics. The electrochemical measurements and density function theory (DFT) calculation indicate that the constructed electrode exhibits a low H* binding energy and an outstanding HER performance that outperforms the commercial Pt/C in pH-universal medium. Overall, this work provides a feasible strategy for electrode design with a pH-universal feasibility by precisely constructing electrode interfaces.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"59 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205139","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 nitrogen fertilizer industry, particularly urea production, notably contributes to greenhouse gas emissions and energy consumption. Urea synthesis via solar energy encounters several challenges. Specifically, solar urea synthesis methods often exhibit low efficiency and yield, primarily stemming from inefficient energy conversion processes and intricate reaction pathways. Moreover, the kinetics of the urea synthesis reaction may be sluggish, thereby impacting the overall production rate. Therefore, in this study, we introduce a novel electron-reserve-enhanced CsCuBr/TiO-Ar (CCBT-Ar) structure for the photocatalytic synthesis of urea from CO and nitrate waste. Theoretical calculations and spectroscopic analysis underscore the critical role of oxygen vacancies (O) within the amorphous TiO shell, enhancing reactant adsorption and catalyzing the rate-determining step (*OCONH→*HOCONH). However, the presence of O also results in significant carrier recombination, acting as trapping centers and reducing urea production activity. Importantly, we demonstrate that -grown carbon nanosheets, in conjunction with TiO, function as efficient electron reservoirs, markedly mitigating trapping-induced recombination and facilitating electron redistribution. These reserved electrons can then actively participate in the urea synthesis process. As a result, the electron-reserve-enhanced structure exhibits robust solar urea yield and selectivity, even in challenging wastewater conditions. This work provides a rational and innovative approach to catalyst development in complex solar synthesis, offering promising avenues for the sustainable production of value-added chemicals while concurrently reducing carbon emissions.
氮肥工业，尤其是尿素生产，是温室气体排放和能源消耗的主要来源。利用太阳能合成尿素遇到了一些挑战。具体来说，太阳能尿素合成方法通常效率和产量较低，这主要源于能量转换过程效率低下和反应途径错综复杂。此外，尿素合成反应的动力学过程可能比较缓慢，从而影响整体生产率。因此，在本研究中，我们引入了一种新型的电子储备增强型 CsCuBr/TiO-Ar （CCBT-Ar）结构，用于从 CO 和硝酸盐废料中光催化合成尿素。理论计算和光谱分析强调了氧空位（O）在无定形氧化钛外壳中的关键作用，它能增强反应物的吸附力并催化速率决定步骤（*OCONH→*HOCONH）。然而，O 的存在也会导致大量载流子重组，成为捕集中心，降低尿素生产活性。重要的是，我们证明了-生长的碳纳米片与 TiO 结合可作为高效的电子贮存器，显著减轻捕获引起的重组，促进电子的再分配。这些储备电子可以积极参与尿素合成过程。因此，即使在具有挑战性的废水条件下，电子储备增强型结构也能表现出强大的太阳能尿素产率和选择性。这项工作为复杂太阳能合成中催化剂的开发提供了一种合理而创新的方法，为可持续生产高附加值化学品并同时减少碳排放提供了前景广阔的途径。
{"title":"Enhanced solar urea synthesis from CO2 and nitrate waste via oxygen vacancy mediated-TiOx support lead-free perovskite","authors":"Haoyue Sun, Zhisheng Lin, Rui Tang, Yuhang Liang, Sibei Zou, Xingmo Zhang, Kaijuan Chen, Rongkun Zheng, Jun Huang","doi":"10.1016/j.apcatb.2024.124511","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124511","url":null,"abstract":"The nitrogen fertilizer industry, particularly urea production, notably contributes to greenhouse gas emissions and energy consumption. Urea synthesis via solar energy encounters several challenges. Specifically, solar urea synthesis methods often exhibit low efficiency and yield, primarily stemming from inefficient energy conversion processes and intricate reaction pathways. Moreover, the kinetics of the urea synthesis reaction may be sluggish, thereby impacting the overall production rate. Therefore, in this study, we introduce a novel electron-reserve-enhanced CsCuBr/TiO-Ar (CCBT-Ar) structure for the photocatalytic synthesis of urea from CO and nitrate waste. Theoretical calculations and spectroscopic analysis underscore the critical role of oxygen vacancies (O) within the amorphous TiO shell, enhancing reactant adsorption and catalyzing the rate-determining step (*OCONH→*HOCONH). However, the presence of O also results in significant carrier recombination, acting as trapping centers and reducing urea production activity. Importantly, we demonstrate that -grown carbon nanosheets, in conjunction with TiO, function as efficient electron reservoirs, markedly mitigating trapping-induced recombination and facilitating electron redistribution. These reserved electrons can then actively participate in the urea synthesis process. As a result, the electron-reserve-enhanced structure exhibits robust solar urea yield and selectivity, even in challenging wastewater conditions. This work provides a rational and innovative approach to catalyst development in complex solar synthesis, offering promising avenues for the sustainable production of value-added chemicals while concurrently reducing carbon emissions.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205167","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 : 2024-08-17DOI: 10.1016/j.apcatb.2024.124515
Keivan Rahimi, Aditya Rawal, Yi Fen Zhu, Judy N. Hart, Emma C. Lovell, Jason Scott
Defect engineering in metal oxides is an effective approach for improving advanced oxidation processes. Herein, we report that regulating the defect types present on SnO enables deconvolution of their distinct effects on organic oxidation. Nitrogen annealing created E′ center and non-bridging oxygen hole center (NBOHC) defects, while optimum hydrogenation introduced oxygen vacancies, significantly enhancing catalytic oxidation performance. Based on spectroscopic analysis, extended hydrogenation times passivated NBOHCs and formed new types of defects, such as electrons trapped in oxygen vacancies, which are less catalytically active in comparison with NBOHCs. DFT indicated that oxygen vacancies lower the energy barrier for oxygen activation as well as activation of the C-H bonds in formic acid, corroborating the experimental results of enhanced catalytic activity in samples with optimized defect concentrations. The current work advances understanding of the roles different defects play in enhancing organic oxidation in the ongoing search for efficient materials for oxidation reactions.
{"title":"Defect engineering in SnO2 catalysts for the organic oxidation reaction","authors":"Keivan Rahimi, Aditya Rawal, Yi Fen Zhu, Judy N. Hart, Emma C. Lovell, Jason Scott","doi":"10.1016/j.apcatb.2024.124515","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124515","url":null,"abstract":"Defect engineering in metal oxides is an effective approach for improving advanced oxidation processes. Herein, we report that regulating the defect types present on SnO enables deconvolution of their distinct effects on organic oxidation. Nitrogen annealing created E′ center and non-bridging oxygen hole center (NBOHC) defects, while optimum hydrogenation introduced oxygen vacancies, significantly enhancing catalytic oxidation performance. Based on spectroscopic analysis, extended hydrogenation times passivated NBOHCs and formed new types of defects, such as electrons trapped in oxygen vacancies, which are less catalytically active in comparison with NBOHCs. DFT indicated that oxygen vacancies lower the energy barrier for oxygen activation as well as activation of the C-H bonds in formic acid, corroborating the experimental results of enhanced catalytic activity in samples with optimized defect concentrations. The current work advances understanding of the roles different defects play in enhancing organic oxidation in the ongoing search for efficient materials for oxidation reactions.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"29 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226226","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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