Abstract The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry. In this study, we present a straightforward solvothermal strategy for fabricating a defect-engineered ZrO 2 /UiO-66-NH 2 hybrid material with abundant oxygen vacancies, enabling the visible-light-driven oxidation of benzyl alcohol to benzaldehyde. By optimizing the solvothermal treatment duration, the composite (UiO-66-NH 2 -2 h) achieves a 74.1% conversion of benzyl alcohol with > 99% selectivity toward benzaldehyde under mild conditions, substantially outperforming pristine UiO-66-NH 2 . Structural and mechanistic studies reveal that the solvothermal process induces the in situ formation of ultrasmall, uniformly dispersed ZrO 2 nanoparticles (~ 2.3 nm) within the MOF matrix, while simultaneously generating abundant oxygen vacancies, as confirmed by XPS, EPR, and HRTEM analyses. The defect-mediated electronic structure of the ZrO 2 /UiO-66-NH 2 hybrid enhances visible-light absorption, facilitates charge carrier separation, and promotes efficient activation of O 2 into superoxide radicals (·O 2 − ), the primary reactive species. Transient photocurrent measurements and electrochemical impedance spectroscopy further verify the improved charge separation efficiency. The synergistic interplay between oxygen vacancies and the intimate ZrO 2 /UiO-66-NH 2 interface provides a unique defect-mediated charge transfer pathway, distinguishing this system from conventional heterojunctions. This study demonstrates a facile, one-step approach to integrate defect engineering with interfacial hybridization in MOF-based photocatalysts, offering a scalable route for solar-driven organic synthesis. Graphical Abstract
{"title":"MOF-Derived Oxygen-Vacancy-Rich ZrO2/UiO-66-NH2 for Efficient Visible-Light-Driven Oxidation of Benzyl Alcohol","authors":"Yan‐Yan Song, Zhichao Sun, Jiamin Sun, Ying‐Ya Liu, Anjie Wang, Chong Peng","doi":"10.1007/s12209-025-00447-z","DOIUrl":"https://doi.org/10.1007/s12209-025-00447-z","url":null,"abstract":"Abstract The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry. In this study, we present a straightforward solvothermal strategy for fabricating a defect-engineered ZrO 2 /UiO-66-NH 2 hybrid material with abundant oxygen vacancies, enabling the visible-light-driven oxidation of benzyl alcohol to benzaldehyde. By optimizing the solvothermal treatment duration, the composite (UiO-66-NH 2 -2 h) achieves a 74.1% conversion of benzyl alcohol with > 99% selectivity toward benzaldehyde under mild conditions, substantially outperforming pristine UiO-66-NH 2 . Structural and mechanistic studies reveal that the solvothermal process induces the in situ formation of ultrasmall, uniformly dispersed ZrO 2 nanoparticles (~ 2.3 nm) within the MOF matrix, while simultaneously generating abundant oxygen vacancies, as confirmed by XPS, EPR, and HRTEM analyses. The defect-mediated electronic structure of the ZrO 2 /UiO-66-NH 2 hybrid enhances visible-light absorption, facilitates charge carrier separation, and promotes efficient activation of O 2 into superoxide radicals (·O 2 − ), the primary reactive species. Transient photocurrent measurements and electrochemical impedance spectroscopy further verify the improved charge separation efficiency. The synergistic interplay between oxygen vacancies and the intimate ZrO 2 /UiO-66-NH 2 interface provides a unique defect-mediated charge transfer pathway, distinguishing this system from conventional heterojunctions. This study demonstrates a facile, one-step approach to integrate defect engineering with interfacial hybridization in MOF-based photocatalysts, offering a scalable route for solar-driven organic synthesis. Graphical Abstract","PeriodicalId":23296,"journal":{"name":"Transactions of Tianjin University","volume":"31 4","pages":"421-435"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s12209-025-00447-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334021","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract NiFe(oxy)hydroxide (NiFeOOH) has been widely studied as a catalyst for oxygen evolution reaction (OER), but its activity is still not satisfactory. Although metal doping has been employed as a promising strategy for addressing this issue, the instability and leaching of the high-valence dopant metals remain considerable challenges. Herein, an array of Cr-doped NiFeOOH nanosheets was in situ synthesized on nickel foam via a one-step hydrothermal method. The doping of NiFeOOH with Cr was found to induce partial electron transfer from Ni and Fe to Cr atoms, thereby modulating the electronic structure of the catalyst and enhancing its intrinsic activity. Electrochemical and in situ Raman spectroscopy analyses showed that Fe active sites with lower charge density enhance the adsorption of *OH and reduce the formation energy barrier of the *OOH intermediate during OER, thereby accelerating the OER. Moreover, Fe was found to promote the transfer of additional electrons to Cr, leading to electron accumulation at Cr sites. This electron accumulation effectively prevents Cr from excessive oxidation and leaching under anode potentials, thereby maintaining the structural stability of the catalyst. The optimized Cr-doped NiFeOOH self-supported electrode exhibited a current density of 50 mA/cm 2 with an overpotential of only 239 mV and remained stable for 100 h at 600 mA/cm 2 in 1 mol/L KOH.
{"title":"Electron Modulation in Cr-Doped NiFeOOH Enhances Oxygen Evolution Reaction Activity and Stabilizes Cr Dopant","authors":"Xiaorui Huang, Wei Zhang, Liyang Xiao, Chunyan Han, Ying Liu, Jingtong Zhang, Haiwen Tan, Pengfei Yin, Rui Zhang, Cunku Dong, Hui Liu, Xi‐Wen Du, Jing Yang","doi":"10.1007/s12209-025-00434-4","DOIUrl":"https://doi.org/10.1007/s12209-025-00434-4","url":null,"abstract":"Abstract NiFe(oxy)hydroxide (NiFeOOH) has been widely studied as a catalyst for oxygen evolution reaction (OER), but its activity is still not satisfactory. Although metal doping has been employed as a promising strategy for addressing this issue, the instability and leaching of the high-valence dopant metals remain considerable challenges. Herein, an array of Cr-doped NiFeOOH nanosheets was in situ synthesized on nickel foam via a one-step hydrothermal method. The doping of NiFeOOH with Cr was found to induce partial electron transfer from Ni and Fe to Cr atoms, thereby modulating the electronic structure of the catalyst and enhancing its intrinsic activity. Electrochemical and in situ Raman spectroscopy analyses showed that Fe active sites with lower charge density enhance the adsorption of *OH and reduce the formation energy barrier of the *OOH intermediate during OER, thereby accelerating the OER. Moreover, Fe was found to promote the transfer of additional electrons to Cr, leading to electron accumulation at Cr sites. This electron accumulation effectively prevents Cr from excessive oxidation and leaching under anode potentials, thereby maintaining the structural stability of the catalyst. The optimized Cr-doped NiFeOOH self-supported electrode exhibited a current density of 50 mA/cm 2 with an overpotential of only 239 mV and remained stable for 100 h at 600 mA/cm 2 in 1 mol/L KOH.","PeriodicalId":23296,"journal":{"name":"Transactions of Tianjin University","volume":"31 3","pages":"292-305"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s12209-025-00434-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-06-01DOI: 10.1007/s12209-025-00437-1
Shuntai Chi, Chenhui Wang, Jie Liao, Peng Sun, Yuhan Fei, You Han, Jinli Zhang, Jiangjiexing Wu, Wei Li
Abstract Aiming at inhibiting the irreversible P2–O2 phase transition of conventional P2-type cathode materials at high voltage and enhancing the cycling stability of sodium-ion batteries, in this article, based on a strategy of adjusting the Na + ion occupancy within the crystal structure, Na 0.67 Ni 0.33 Mn 0.67– x Fe x O 2 (NM– x Fe, x = 0.10, 0.15, 0.20) cathode materials were synthesized by high shear mixer (HSM)-assisted co-precipitation method and evaluated the electrochemical performance at high voltage (4.35 V). The optimal sample NM–0.15Fe exhibits an initial discharge capacity of 130.8 mAh/g (0.1 C), with exceptional retention of 95.9% after 100 cycles (1 C). XRD analysis reveals that Fe intercalation promotes the more amount of Nae-similar occupation; the Nae/Naf ratio equals 1.93 for NM–0.15Fe versus 1.62 for NM, which enhances Na + diffusion kinetics, as confirmed by GITT tests. Through characterizations of in situ XRD, XPS, HRTEM, CV, etc., it is illustrated that the Fe 3+ intercalation can effectively disrupt the Na + /vacancy ordering and inhibit the harmful P2–O2 phase transition, and then improve the cycling stability of the cathode. DFT calculations disclose that intercalated Fe can reduce the electron densities of adjacent transition metallic elements, generating more repulsive forces impacted on sodium and consequently appearance of more Nae sites, leading to a lower Na + diffusion energy barrier. Such strategy of modulating Na occupation sites in crystal structure is conducive to the development of low-cost and high-performance layered cathode materials for sodium-ion batteries.
摘要：为了抑制传统p2型正极材料在高压下P2-O2不可逆相变，提高钠离子电池的循环稳定性，本文基于调整晶体结构内Na +离子占据率的策略，将Na 0.67 Ni 0.33 Mn 0.67 - x Fe x o2 (NM - x Fe, x = 0.10, 0.15，采用高剪切混合器（HSM）辅助共沉淀法合成了0.20)正极材料，并对其在4.35 V高压下的电化学性能进行了评价。最佳样品NM-0.15Fe的初始放电容量为130.8 mAh/g (0.1 C)，在100次循环（1 C）后的保留率为95.9%。XRD分析表明，Fe的插入促进了nae -相似物的大量占据；纳米- 0.15 fe的Nae/Naf比为1.93，NM的Nae/Naf比为1.62，通过GITT试验证实，纳米- 0.15 fe的Nae/Naf比增强了Na +扩散动力学。通过原位XRD、XPS、HRTEM、CV等表征表明，fe3 +的插入可以有效地破坏Na + /空位有序，抑制有害的P2-O2相变，从而提高阴极的循环稳定性。DFT计算表明，插入Fe可以降低相邻过渡金属元素的电子密度，对钠产生更大的排斥力，从而出现更多的Nae位，导致Na +扩散能垒降低。这种调节晶体结构中Na占位位的策略有利于开发低成本、高性能的钠离子电池层状正极材料。
{"title":"P2–Na0.67Ni0.33Mn0.67–xFexO2 with Superior Na+ Diffusion and Cycle Stability at High Voltage for Sodium-Ion Batteries","authors":"Shuntai Chi, Chenhui Wang, Jie Liao, Peng Sun, Yuhan Fei, You Han, Jinli Zhang, Jiangjiexing Wu, Wei Li","doi":"10.1007/s12209-025-00437-1","DOIUrl":"https://doi.org/10.1007/s12209-025-00437-1","url":null,"abstract":"Abstract Aiming at inhibiting the irreversible P2–O2 phase transition of conventional P2-type cathode materials at high voltage and enhancing the cycling stability of sodium-ion batteries, in this article, based on a strategy of adjusting the Na + ion occupancy within the crystal structure, Na 0.67 Ni 0.33 Mn 0.67– x Fe x O 2 (NM– x Fe, x = 0.10, 0.15, 0.20) cathode materials were synthesized by high shear mixer (HSM)-assisted co-precipitation method and evaluated the electrochemical performance at high voltage (4.35 V). The optimal sample NM–0.15Fe exhibits an initial discharge capacity of 130.8 mAh/g (0.1 C), with exceptional retention of 95.9% after 100 cycles (1 C). XRD analysis reveals that Fe intercalation promotes the more amount of Nae-similar occupation; the Nae/Naf ratio equals 1.93 for NM–0.15Fe versus 1.62 for NM, which enhances Na + diffusion kinetics, as confirmed by GITT tests. Through characterizations of in situ XRD, XPS, HRTEM, CV, etc., it is illustrated that the Fe 3+ intercalation can effectively disrupt the Na + /vacancy ordering and inhibit the harmful P2–O2 phase transition, and then improve the cycling stability of the cathode. DFT calculations disclose that intercalated Fe can reduce the electron densities of adjacent transition metallic elements, generating more repulsive forces impacted on sodium and consequently appearance of more Nae sites, leading to a lower Na + diffusion energy barrier. Such strategy of modulating Na occupation sites in crystal structure is conducive to the development of low-cost and high-performance layered cathode materials for sodium-ion batteries.","PeriodicalId":23296,"journal":{"name":"Transactions of Tianjin University","volume":"31 3","pages":"278-291"},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332973","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1007/s12209-025-00430-8
Ke Jia, Yanan Zhang, Rui Zuo, Hongbing Lu, Kemeng Ji, Mingming Chen
Abstract The sluggish bidirectional conversion rate between Li 2 S n (2 ≤ n ≤ 4) and Li 2 S, coupled with the uncontrolled deposition of Li 2 S, significantly impedes the realization of high-performance lithium–sulfur batteries (LSBs). In this study, a metal–organic framework was employed as a precursor for the synthesis of a CoO x –CeO 2− y /C (0 < x < 3/2, 0 < y < 1/2) heterojunction via pyrolysis, which was subsequently introduced onto the cathode side of the polypropylene (PP) separator in LSBs. The modification of CoO x –CeO 2− y /C enhances the kinetics of converting of Li 2 S n to Li 2 S during the discharge process. The Tafel slope for the Li 2 S deposition reaction is reduced to 52.1 mV/dec, representing a 56.6% decrease compared to LSBs with bare PP separator. Conversely, during the charging process, the modification lowers the energy barrier for the Li 2 S decomposition reaction, with the activation energy reduced to 6.12 kJ/mol, indicating a 70.3% decrease relative to LSBs with PP separator only. Consequently, more Li 2 S is promoted to undergo decomposition. The CoO x –CeO 2− y /C heterojunction facilitates uniform deposition of Li 2 S, featuring fine particles and a uniform distribution, after brief potentiostatic charging for decomposition, thereby effectively mitigating the deactivation of sulfur species. Thanks to the enhanced bidirectional conversion of lithium polysulfides (LiPS) facilitated by the CoO x –CeO 2− y /C modification layer, the (−)Li|CoO x –CeO 2− y /C@PP|S(+) coin cell maintains a Coulombic efficiency of 90.4% after 500 cycles at a current density of 1 C, exhibiting a low capacity-decay rate of only 0.081% per cycle, thereby demonstrating excellent long-cycle stability.
摘要Li 2s n（2≤n≤4）与Li 2s之间的双向转化率缓慢，加上Li 2s沉积不受控制，严重阻碍了高性能锂硫电池（LSBs）的实现。在本研究中，采用金属-有机框架作为前体，通过热解合成CoO x -CeO 2 - y /C （0 < x < 3/ 2,0 < y < 1/2）异质结，随后将其引入lbs中聚丙烯（PP）分离器的阴极侧。CoO x -CeO 2−y /C的改性提高了放电过程中Li 2s n向Li 2s转化的动力学。Li 2s沉积反应的Tafel斜率降至52.1 mV/dec，与使用裸PP分离器的LSBs相比降低了56.6%。相反，在充电过程中，改性降低了Li 2s分解反应的能垒，活化能降至6.12 kJ/mol，与仅使用PP分离器的LSBs相比，降低了70.3%。因此，更多的Li 2s被促进进行分解。CoO x -CeO 2−y /C异质结有利于Li 2s在短暂的恒电位充电分解后均匀沉积，具有颗粒细、分布均匀的特点，从而有效地减轻了硫种的失活。由于CoO x -CeO 2−y /C改性层促进了多硫化锂（LiPS）的双向转化，（−）Li|CoO x -CeO 2−y /C@PP|S（+）硬币电池在1 C电流密度下循环500次后仍保持90.4%的库伦效率，每循环的容量衰减率仅为0.081%，从而表现出优异的长周期稳定性。
{"title":"MOF-Derived CoOx–CeO2−y/C Heterojunction Synergistically Promotes the Deposition and Decomposition of Li2S in Lithium–Sulfur Batteries","authors":"Ke Jia, Yanan Zhang, Rui Zuo, Hongbing Lu, Kemeng Ji, Mingming Chen","doi":"10.1007/s12209-025-00430-8","DOIUrl":"https://doi.org/10.1007/s12209-025-00430-8","url":null,"abstract":"Abstract The sluggish bidirectional conversion rate between Li 2 S n (2 ≤ n ≤ 4) and Li 2 S, coupled with the uncontrolled deposition of Li 2 S, significantly impedes the realization of high-performance lithium–sulfur batteries (LSBs). In this study, a metal–organic framework was employed as a precursor for the synthesis of a CoO x –CeO 2− y /C (0 < x < 3/2, 0 < y < 1/2) heterojunction via pyrolysis, which was subsequently introduced onto the cathode side of the polypropylene (PP) separator in LSBs. The modification of CoO x –CeO 2− y /C enhances the kinetics of converting of Li 2 S n to Li 2 S during the discharge process. The Tafel slope for the Li 2 S deposition reaction is reduced to 52.1 mV/dec, representing a 56.6% decrease compared to LSBs with bare PP separator. Conversely, during the charging process, the modification lowers the energy barrier for the Li 2 S decomposition reaction, with the activation energy reduced to 6.12 kJ/mol, indicating a 70.3% decrease relative to LSBs with PP separator only. Consequently, more Li 2 S is promoted to undergo decomposition. The CoO x –CeO 2− y /C heterojunction facilitates uniform deposition of Li 2 S, featuring fine particles and a uniform distribution, after brief potentiostatic charging for decomposition, thereby effectively mitigating the deactivation of sulfur species. Thanks to the enhanced bidirectional conversion of lithium polysulfides (LiPS) facilitated by the CoO x –CeO 2− y /C modification layer, the (−)Li|CoO x –CeO 2− y /C@PP|S(+) coin cell maintains a Coulombic efficiency of 90.4% after 500 cycles at a current density of 1 C, exhibiting a low capacity-decay rate of only 0.081% per cycle, thereby demonstrating excellent long-cycle stability.","PeriodicalId":23296,"journal":{"name":"Transactions of Tianjin University","volume":"31 2","pages":"189-203"},"PeriodicalIF":0.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s12209-025-00430-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-22DOI: 10.1007/s12209-023-00375-w
Zhiqin Wu, Yang Li, Xiang Ma
{"title":"Recent Advances in Pure-Organic Host–Guest Room-Temperature Phosphorescence Systems Toward Bioimaging","authors":"Zhiqin Wu, Yang Li, Xiang Ma","doi":"10.1007/s12209-023-00375-w","DOIUrl":"https://doi.org/10.1007/s12209-023-00375-w","url":null,"abstract":"","PeriodicalId":23296,"journal":{"name":"Transactions of Tianjin University","volume":"43 16","pages":""},"PeriodicalIF":7.1,"publicationDate":"2023-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138946413","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-12-17DOI: 10.1007/s12209-023-00376-9
Long Jiang, Hanrui Du, Le Li, X. Guan, Yihao Zhang, Liwei Li, Xiaoxu Liu, Lei Li, Yingcheng Tian, Li Zhang, Shuai Wang, Jie Chen, Shaohua Shen
{"title":"Sequential Growth of Cs3Bi2I9/BiVO4 Direct Z-Scheme Heterojunction for Visible-Light-Driven Photocatalytic CO2 Reduction","authors":"Long Jiang, Hanrui Du, Le Li, X. Guan, Yihao Zhang, Liwei Li, Xiaoxu Liu, Lei Li, Yingcheng Tian, Li Zhang, Shuai Wang, Jie Chen, Shaohua Shen","doi":"10.1007/s12209-023-00376-9","DOIUrl":"https://doi.org/10.1007/s12209-023-00376-9","url":null,"abstract":"","PeriodicalId":23296,"journal":{"name":"Transactions of Tianjin University","volume":"7 4","pages":""},"PeriodicalIF":7.1,"publicationDate":"2023-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138966526","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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