Hanhong Zhang, Wenjing Hou, Yuanlong Deng, Jun Song, Fan Zhang
NiOx nanoparticles are the preferred hole transport material in perovskite solar cells due to their high hole mobility, ease of fabrication, excellent stability, and suitable Fermi level for hole extraction. However, NiOx nanoparticles can undergo interfacial reactions with the perovskite active layer, potentially causing significant interface issues that limit the photovoltaic conversion efficiency and stability of perovskite solar cells. In this study, we discovered a liquid coupling agent, aluminum di(isopropoxide)acetoacetic ester chelate, which reacts with NiOx to form a hydrophilic monolayer modification through an alcoholysis process. This modification enhances both the photovoltaic conversion efficiency and stability of perovskite solar cells. The maximum efficiency of the modified perovskite solar cell reached 23.82%. Furthermore, the coupling agent is compatible with large-area coating processes. A large-area (14 cm²) perovskite solar cell module achieved an efficiency of 21.80%, retaining 97.7% of its initial performance after 600 hours under AM1.5G illumination.
{"title":"Enhancing Inverted Perovskite Solar Cells via Hydrophilic Surface Modification of NiOx Using Aluminate Coupling Agents","authors":"Hanhong Zhang, Wenjing Hou, Yuanlong Deng, Jun Song, Fan Zhang","doi":"10.1039/d5ta01516b","DOIUrl":"https://doi.org/10.1039/d5ta01516b","url":null,"abstract":"NiOx nanoparticles are the preferred hole transport material in perovskite solar cells due to their high hole mobility, ease of fabrication, excellent stability, and suitable Fermi level for hole extraction. However, NiOx nanoparticles can undergo interfacial reactions with the perovskite active layer, potentially causing significant interface issues that limit the photovoltaic conversion efficiency and stability of perovskite solar cells. In this study, we discovered a liquid coupling agent, aluminum di(isopropoxide)acetoacetic ester chelate, which reacts with NiOx to form a hydrophilic monolayer modification through an alcoholysis process. This modification enhances both the photovoltaic conversion efficiency and stability of perovskite solar cells. The maximum efficiency of the modified perovskite solar cell reached 23.82%. Furthermore, the coupling agent is compatible with large-area coating processes. A large-area (14 cm²) perovskite solar cell module achieved an efficiency of 21.80%, retaining 97.7% of its initial performance after 600 hours under AM1.5G illumination.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"7 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832350","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xueli Zhang, Shihao Ding, Qianqian Shen, Shilong Feng, Jinlong Li, Zhe Sun, Chengkun Lei, Jinbo Xue, Min Liu
The development of inexpensive and stable hydrogen evolution reaction (HER)/oxygen evolution reaction (OER) bifunctional electrocatalysts is extremely important to advance the commercial application of alkaline water electrolysis (AWE). However, the majority of bifunctional catalysts exhibit optimal activity in only one reaction, leading to suboptimal overall water splitting efficiency. The development of a satisfactory bifunctional catalyst capable of simultaneously accelerating both HER and OER kinetics remains an ongoing challenge. Here, we report efficient bifunctional electrocatalytic water splitting by constructing long-range ordered oxygen vacancies in hematite nanobelt arrays. Notably, HNBs-30 with long-range ordered oxygen vacancies exhibits lower OER (317 mV @ 10 mA cm−2, 369 mV @ 100 mA cm−2) and HER (178 mV @ 10 mA cm−2, 321 mV @ 100 mA cm−2) overpotentials, and exhibits a low overpotential of 2.22 V and long-term stability of 40 hours at 100 mA cm−2 in overall water splitting. This study shows that long-range ordered oxygen vacancies not only optimize the adsorption/desorption kinetics of intermediates, but also establish a highly efficient conduit for charge transport, which can simultaneously accelerate the kinetics of HER and OER. This is a key factor in HNBs-30 achieving bifunctional and high catalytic activity.
{"title":"Hematite nanobelts with ordered oxygen vacancies for bifunctional electrocatalytic water splitting","authors":"Xueli Zhang, Shihao Ding, Qianqian Shen, Shilong Feng, Jinlong Li, Zhe Sun, Chengkun Lei, Jinbo Xue, Min Liu","doi":"10.1039/d5ta01217a","DOIUrl":"https://doi.org/10.1039/d5ta01217a","url":null,"abstract":"The development of inexpensive and stable hydrogen evolution reaction (HER)/oxygen evolution reaction (OER) bifunctional electrocatalysts is extremely important to advance the commercial application of alkaline water electrolysis (AWE). However, the majority of bifunctional catalysts exhibit optimal activity in only one reaction, leading to suboptimal overall water splitting efficiency. The development of a satisfactory bifunctional catalyst capable of simultaneously accelerating both HER and OER kinetics remains an ongoing challenge. Here, we report efficient bifunctional electrocatalytic water splitting by constructing long-range ordered oxygen vacancies in hematite nanobelt arrays. Notably, HNBs-30 with long-range ordered oxygen vacancies exhibits lower OER (317 mV @ 10 mA cm<small><sup>−2</sup></small>, 369 mV @ 100 mA cm<small><sup>−2</sup></small>) and HER (178 mV @ 10 mA cm<small><sup>−2</sup></small>, 321 mV @ 100 mA cm<small><sup>−2</sup></small>) overpotentials, and exhibits a low overpotential of 2.22 V and long-term stability of 40 hours at 100 mA cm<small><sup>−2</sup></small> in overall water splitting. This study shows that long-range ordered oxygen vacancies not only optimize the adsorption/desorption kinetics of intermediates, but also establish a highly efficient conduit for charge transport, which can simultaneously accelerate the kinetics of HER and OER. This is a key factor in HNBs-30 achieving bifunctional and high catalytic activity.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"8 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Investigating a single multifunctional electrode in an integrated device, such as self-powered overall water splitting (OWS), is extremely valuable since it may substantially decrease the system complexity and expense. Hence, a full rice-spike-like 400N-CDs/FeNi-TDC nanoarray combining N-hybridized carbon dots (N-CDs) and FeNi-TDC with 2,5-thiophenedicarboxylic acid (H2TDC) as ligands is constructed on the surface of a nickel foam by a one-pot solvothermal method for OWS and supercapacitor applications. Based on interface-heterojunction engineering, the morphology and electronic environment at the active sites of the nanomaterial successfully controlled by N-CDs and the heterojunction synergistically promoted efficient catalysis. The optimized 400N-CDs/FeNi-TDC electrode exhibits a 209 mV overpotential and a Tafel slope of 18.91 mV dec−1 at 10 mA cm−2 during the oxygen evolution reaction (OER) activity, as well as a low overpotential of 99 mV to reach 10 mA cm−2 with a Tafel slope of 77.01 mV dec−1 in the hydrogen evolution reaction (HER). As the positive electrode of the supercapacitor, the high specific capacitance of 400N-CDs/FeNi-TDC is 2388 F g−1 at 1 A g−1. The assembled self-powered OWS device uses the 400N-CDs/FeNi-TDC‖AC/NF with pre-charged 3 V as the power supply to achieve simultaneous green hydrogen and oxygen production for ∼4 min. This research provides a new platform to build state-of-the-art and sustainable energy conversion and storage devices.
{"title":"In situ formation of heterojunction of thiophene-based metal–organic frameworks with carbon dots for efficient overall water splitting and supercapacitor applications","authors":"Qianqian Wang, Xiaoyan Ma, Ran Bi, Xiangpan Hu, Senyang Song, Pengcheng Ma, Fang Chen","doi":"10.1039/d4ta08523j","DOIUrl":"https://doi.org/10.1039/d4ta08523j","url":null,"abstract":"Investigating a single multifunctional electrode in an integrated device, such as self-powered overall water splitting (OWS), is extremely valuable since it may substantially decrease the system complexity and expense. Hence, a full rice-spike-like 400N-CDs/FeNi-TDC nanoarray combining N-hybridized carbon dots (N-CDs) and FeNi-TDC with 2,5-thiophenedicarboxylic acid (H<small><sub>2</sub></small>TDC) as ligands is constructed on the surface of a nickel foam by a one-pot solvothermal method for OWS and supercapacitor applications. Based on interface-heterojunction engineering, the morphology and electronic environment at the active sites of the nanomaterial successfully controlled by N-CDs and the heterojunction synergistically promoted efficient catalysis. The optimized 400N-CDs/FeNi-TDC electrode exhibits a 209 mV overpotential and a Tafel slope of 18.91 mV dec<small><sup>−1</sup></small> at 10 mA cm<small><sup>−2</sup></small> during the oxygen evolution reaction (OER) activity, as well as a low overpotential of 99 mV to reach 10 mA cm<small><sup>−2</sup></small> with a Tafel slope of 77.01 mV dec<small><sup>−1</sup></small> in the hydrogen evolution reaction (HER). As the positive electrode of the supercapacitor, the high specific capacitance of 400N-CDs/FeNi-TDC is 2388 F g<small><sup>−1</sup></small> at 1 A g<small><sup>−1</sup></small>. The assembled self-powered OWS device uses the 400N-CDs/FeNi-TDC‖AC/NF with pre-charged 3 V as the power supply to achieve simultaneous green hydrogen and oxygen production for ∼4 min. This research provides a new platform to build state-of-the-art and sustainable energy conversion and storage devices.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"39 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Min Woo Kim, Jong Min Lee, Chi-Young Jung, Jung-Eun Cha, Kwang Shik Myung, Nam Jin Lee, Nam Dong Kim, Jae Young Jung
Enhancing the durability of platinum catalysts in proton exchange membrane fuel cells (PEMFCs) remains a key challenge for long-haul truck applications. In this study, we employed a commercialized high-surface-area carbon support and performed thermal annealing under oxidizing/reducing conditions to precisely control the oxygen functional groups on its surface. Subsequently, platinum nanoparticles (Pt NPs) were uniformly dispersed on the carbon support via a polyol method. We systematically investigated the Pt NPs/carbon interface effect using advanced spectroscopic techniques combined with electrochemical surface analyses, while isolating the effects of Pt location and pore structure. Consequently, we significantly improved the durability of the platinum catalyst, with mass activity retention increasing from 40.9% to 78.6% of initial performance (0.393–0.403 A mgPt−1), and the electrochemical surface area (ECSA) rising from 57.9% to 84.2% of initial ECSA values (95–97 m2 gPt−1). These improvements were achieved while maintaining highly precise initial parameters. Through extensive material characterization, we demonstrated that the improved durability of the platinum catalyst is attributed to the increased binding energy between the oxygen functional groups and Pt nanoparticles (NPs), as well as the suppression of Pt ionization. This study highlights the crucial role of carbon supports in fuel cells and provides guidelines for optimal design, paving the way for platinum catalysts intended for long-range fuel cell applications in areas such as ecofriendly hydrogen vehicles and distributed power generation.
{"title":"Thermally driven oxygen functionalization for durable Pt electrocatalysts in the oxygen reduction reaction","authors":"Min Woo Kim, Jong Min Lee, Chi-Young Jung, Jung-Eun Cha, Kwang Shik Myung, Nam Jin Lee, Nam Dong Kim, Jae Young Jung","doi":"10.1039/d5ta01939g","DOIUrl":"https://doi.org/10.1039/d5ta01939g","url":null,"abstract":"Enhancing the durability of platinum catalysts in proton exchange membrane fuel cells (PEMFCs) remains a key challenge for long-haul truck applications. In this study, we employed a commercialized high-surface-area carbon support and performed thermal annealing under oxidizing/reducing conditions to precisely control the oxygen functional groups on its surface. Subsequently, platinum nanoparticles (Pt NPs) were uniformly dispersed on the carbon support <em>via</em> a polyol method. We systematically investigated the Pt NPs/carbon interface effect using advanced spectroscopic techniques combined with electrochemical surface analyses, while isolating the effects of Pt location and pore structure. Consequently, we significantly improved the durability of the platinum catalyst, with mass activity retention increasing from 40.9% to 78.6% of initial performance (0.393–0.403 A mg<small><sub>Pt</sub></small><small><sup>−1</sup></small>), and the electrochemical surface area (ECSA) rising from 57.9% to 84.2% of initial ECSA values (95–97 m<small><sup>2</sup></small> g<small><sub>Pt</sub></small><small><sup>−1</sup></small>). These improvements were achieved while maintaining highly precise initial parameters. Through extensive material characterization, we demonstrated that the improved durability of the platinum catalyst is attributed to the increased binding energy between the oxygen functional groups and Pt nanoparticles (NPs), as well as the suppression of Pt ionization. This study highlights the crucial role of carbon supports in fuel cells and provides guidelines for optimal design, paving the way for platinum catalysts intended for long-range fuel cell applications in areas such as ecofriendly hydrogen vehicles and distributed power generation.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"74 5 Pt 1 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832341","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Due to the complexity of insoluble Li2S2-Li2S conversion, few descriptors exist to correlate the catalytic performance and the underlying electronic structures of a given catalyst, which inhibits the development of lithium−sulfur catalysts. In this article, we employ the cluster expansion method to select 17 optimal structures for TaXTi(1-X)S2 (0≤X≤1) and apply density functional theory calculations to probe the electronic structures and the conversion of Li2S2 to Li2S relationships across different doping concentrations. We found the simultaneous pathway is most possible in propose five possible reaction pathways. Notably, we identify Ta0.38Ti0.62S2 as a promising candidate for electrocatalytic applications in the conversion from Li2S2 to Li2S. Furthermore, our study analyzes the charge transfer of Li2S2(QLi2S2), the electronegative difference(ΔX), the adsorption energy of Li2S(EaLi2S), and work function(WF) significantly influence the conversion process from Li2S2 to Li2S by machine learning based on various descriptors. This research contributes to a deeper theoretical understanding of the complex mechanisms underlying the Li2S2-Li2S conversion and provides valuable insights into the rational design of sulfur redox catalysts.
{"title":"Density Functional Theory Studies on Tuning TaXTi(1-X)S2 For Insoluble Li2S2-Li2S Conversion in Lithium-Sulfur Batteries","authors":"Jinyan Chen, Shuai Zhao, Yuhan Wang, Ruiyu Hao, Chao Gao, Jianhua Hou","doi":"10.1039/d5ta01770j","DOIUrl":"https://doi.org/10.1039/d5ta01770j","url":null,"abstract":"Due to the complexity of insoluble Li2S2-Li2S conversion, few descriptors exist to correlate the catalytic performance and the underlying electronic structures of a given catalyst, which inhibits the development of lithium−sulfur catalysts. In this article, we employ the cluster expansion method to select 17 optimal structures for TaXTi(1-X)S2 (0≤X≤1) and apply density functional theory calculations to probe the electronic structures and the conversion of Li2S2 to Li2S relationships across different doping concentrations. We found the simultaneous pathway is most possible in propose five possible reaction pathways. Notably, we identify Ta0.38Ti0.62S2 as a promising candidate for electrocatalytic applications in the conversion from Li2S2 to Li2S. Furthermore, our study analyzes the charge transfer of Li2S2(QLi2S2), the electronegative difference(ΔX), the adsorption energy of Li2S(EaLi2S), and work function(WF) significantly influence the conversion process from Li2S2 to Li2S by machine learning based on various descriptors. This research contributes to a deeper theoretical understanding of the complex mechanisms underlying the Li2S2-Li2S conversion and provides valuable insights into the rational design of sulfur redox catalysts.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"15 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832352","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yanet Belén Mansilla, Catalina Jiménez, Juan Basbus, Horacio E. Troiani, Daniel M Többens, Adriana C. Serquis, Mauricio D. Arce
Thin film approach for Solid Oxide Cell (SOC) electrolytes offers a pathway to reduce the high fabrication and operation temperature of these devices. In this work, we present a detailed ex-situ and in-situ study of 8 mol % yttria-stabilized zirconia (8YSZ) nanostructured dense thin films with a thickness of 100 nm. These films were synthesised through the sol-gel method and deposited by dip-coating on a fused glass. The microstructural and crystalline evolution in the range 300-800 °C was studied by synchrotron Grazing Incidence X-Ray Diffraction (GIXRD). Crystallisation of the 8YSZ films was observed to start at 343 °C with 4-5 nm crystallites consisting only of the cubic phase. With increasing temperature, this phase is maintained and the crystallite size reaches 38 nm at 800 °C. Additionally, the evolution of the lattice parameter was studied, which allowed to determine the variation of the thermal expansion coefficient (TEC) of the films during both heating and cooling. The TEC as a function of temperature has three linear regions during heating and two during cooling, with values between 9.6 × 10-7K-1 and 3.7 × 10-5 K-1. These findings provide valuable insights into the structural response of the material under thermal cycling, relevant on the performance and stability of SOC devices. Coupled with the crystallographic characterisation, the electrical properties of the thin films were studied through conductivity measurements, obtaining conductivities about 1.5 to 5 times higher than the conductivity of 8YSZ bulk samples, with values of 0.06 Scm-1 at 700 °C. Thus, the conjunction of a reduced electrolyte thickness with the enhanced conductivity of nanostructured 8YSZ makes these films attractive for intermediate temperature SOC applications.
{"title":"Thermal Evolution of Sol-Gel Synthesized 8YSZ Thin Films: Insights from coupled In-Situ Synchrotron Diffraction and Electrical Conductivity Measurements","authors":"Yanet Belén Mansilla, Catalina Jiménez, Juan Basbus, Horacio E. Troiani, Daniel M Többens, Adriana C. Serquis, Mauricio D. Arce","doi":"10.1039/d5ta01967b","DOIUrl":"https://doi.org/10.1039/d5ta01967b","url":null,"abstract":"Thin film approach for Solid Oxide Cell (SOC) electrolytes offers a pathway to reduce the high fabrication and operation temperature of these devices. In this work, we present a detailed ex-situ and in-situ study of 8 mol % yttria-stabilized zirconia (8YSZ) nanostructured dense thin films with a thickness of 100 nm. These films were synthesised through the sol-gel method and deposited by dip-coating on a fused glass. The microstructural and crystalline evolution in the range 300-800 °C was studied by synchrotron Grazing Incidence X-Ray Diffraction (GIXRD). Crystallisation of the 8YSZ films was observed to start at 343 °C with 4-5 nm crystallites consisting only of the cubic phase. With increasing temperature, this phase is maintained and the crystallite size reaches 38 nm at 800 °C. Additionally, the evolution of the lattice parameter was studied, which allowed to determine the variation of the thermal expansion coefficient (TEC) of the films during both heating and cooling. The TEC as a function of temperature has three linear regions during heating and two during cooling, with values between 9.6 × 10<small><sup>-7</sup></small>K<small><sup>-1</sup></small> and 3.7 × 10<small><sup>-5</sup></small> K<small><sup>-1</sup></small>. These findings provide valuable insights into the structural response of the material under thermal cycling, relevant on the performance and stability of SOC devices. Coupled with the crystallographic characterisation, the electrical properties of the thin films were studied through conductivity measurements, obtaining conductivities about 1.5 to 5 times higher than the conductivity of 8YSZ bulk samples, with values of 0.06 Scm<small><sup>-1</sup></small> at 700 °C. Thus, the conjunction of a reduced electrolyte thickness with the enhanced conductivity of nanostructured 8YSZ makes these films attractive for intermediate temperature SOC applications.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"24 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832353","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shohreh Faridi, Samad Razzaq, Diwakar Singh, Ling Meng, Francesc Viñes, Francesc Illas, Kai S. Exner
Single-atom catalysts (SACs) have garnered widespread attention in the catalysis community due to their ability to catalyze transformations relevant to energy conversion and storage with high activity and selectivity and maximum atomic efficiency. Although considerable efforts are being made to develop synthetic routes for SACs based on non-noble metal atoms, the state-of-the-art SACs are largely based on rare Pt-group metals. MXenes, a new class of two-dimensional materials, offer the exciting possibility of synthesizing single-atom centers with structural similarity to archetypical SACs and without the need for scarce metal atoms such as Pt or Ir. Instead of a dedicated synthetic protocol, only a sufficiently large anodic electrode potential is required to enable the activation of the MXene basal plane by surface oxidation, and the as-formed single-atom centers are sufficiently stable under anodic bias. The electrochemically formed single-atom centers of MXenes based on surface reconstruction differ significantly from previous studies based on SAC sites obtained by doping with foreign metal atoms. In the present work, we demonstrate that the in situ formed single-atom centers of MXenes can be effectively used to catalyze energy conversion processes relevant to the chemical industry. By combining electronic structure theory calculations and descriptor-based analysis, we determine activity and selectivity trends in competing oxygen and chlorine evolution reactions and derive activity and selectivity trends for a noble metal-free electrochemical synthesis of gaseous chlorine. Our results indicate that electrochemically formed single-atom centers of two-dimensional materials can play a crucial role for the development of next-generation catalysts for sustainable energy.
{"title":"Trends in competing oxygen and chlorine evolution reactions over electrochemically formed single-atom centers of MXenes","authors":"Shohreh Faridi, Samad Razzaq, Diwakar Singh, Ling Meng, Francesc Viñes, Francesc Illas, Kai S. Exner","doi":"10.1039/d5ta02220g","DOIUrl":"https://doi.org/10.1039/d5ta02220g","url":null,"abstract":"Single-atom catalysts (SACs) have garnered widespread attention in the catalysis community due to their ability to catalyze transformations relevant to energy conversion and storage with high activity and selectivity and maximum atomic efficiency. Although considerable efforts are being made to develop synthetic routes for SACs based on non-noble metal atoms, the state-of-the-art SACs are largely based on rare Pt-group metals. MXenes, a new class of two-dimensional materials, offer the exciting possibility of synthesizing single-atom centers with structural similarity to archetypical SACs and without the need for scarce metal atoms such as Pt or Ir. Instead of a dedicated synthetic protocol, only a sufficiently large anodic electrode potential is required to enable the activation of the MXene basal plane by surface oxidation, and the as-formed single-atom centers are sufficiently stable under anodic bias. The electrochemically formed single-atom centers of MXenes based on surface reconstruction differ significantly from previous studies based on SAC sites obtained by doping with foreign metal atoms. In the present work, we demonstrate that the <em>in situ</em> formed single-atom centers of MXenes can be effectively used to catalyze energy conversion processes relevant to the chemical industry. By combining electronic structure theory calculations and descriptor-based analysis, we determine activity and selectivity trends in competing oxygen and chlorine evolution reactions and derive activity and selectivity trends for a noble metal-free electrochemical synthesis of gaseous chlorine. Our results indicate that electrochemically formed single-atom centers of two-dimensional materials can play a crucial role for the development of next-generation catalysts for sustainable energy.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"170 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832351","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Engineering power factor (PF) of molecular junctions is one of the most attractive research in the field of thermoelectronics for the applications in thermal management and high-performance thermoelectric energy conversion at the nanoscale. Here, we modified the chemical structure of self-assembled monolayers (SAMs) formed by the widely investigated alkanethiolate (HS-Cn) through heteroatom substitutions, including the terminal iodine (I) atom substitution and replacing backbone methylene units (-CH2-) with oxygen (O) atoms, to obtain iodo-substituted oligo(ethylene glycol) thiolates (HS-(C2O)m-C2-I). The electrical conductivity (σ) and Seebeck coefficient (S) of the SAMs with HS-(C2O)m-C2-I can be enhanced simultaneously compared to the length-matched SAMs of HS-Cn, resulting in the PF of HS-(C2O)4-C2-I being over five orders of magnitude higher than that of HS-C14, which was attributed to the resonant states contributed from the substituted HS-(C2O)m-C2-I near the Fermi energy. Our findings highlight the significance of chemically engineering the organic molecules to dramatically boost PF of molecular junctions for the further applications of high-efficient nanoscale thermoelectric devices.
{"title":"Heteroatom Engineering Enhancing Thermoelectric Power Factor of Molecular Junctions","authors":"Wuxian Peng, Ningyue Chen, Yu Xie, Liang Ma, Jing-Tao Lü, Yuan Li","doi":"10.1039/d5ta01503k","DOIUrl":"https://doi.org/10.1039/d5ta01503k","url":null,"abstract":"Engineering power factor (PF) of molecular junctions is one of the most attractive research in the field of thermoelectronics for the applications in thermal management and high-performance thermoelectric energy conversion at the nanoscale. Here, we modified the chemical structure of self-assembled monolayers (SAMs) formed by the widely investigated alkanethiolate (HS-Cn) through heteroatom substitutions, including the terminal iodine (I) atom substitution and replacing backbone methylene units (-CH2-) with oxygen (O) atoms, to obtain iodo-substituted oligo(ethylene glycol) thiolates (HS-(C2O)m-C2-I). The electrical conductivity (σ) and Seebeck coefficient (S) of the SAMs with HS-(C2O)m-C2-I can be enhanced simultaneously compared to the length-matched SAMs of HS-Cn, resulting in the PF of HS-(C2O)4-C2-I being over five orders of magnitude higher than that of HS-C14, which was attributed to the resonant states contributed from the substituted HS-(C2O)m-C2-I near the Fermi energy. Our findings highlight the significance of chemically engineering the organic molecules to dramatically boost PF of molecular junctions for the further applications of high-efficient nanoscale thermoelectric devices.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"25 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822588","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The problems of inadequate waste plastic (WP) treatment methods, serious electromagnetic hazards, and the difficulty of metal-based electromagnetic shielding interference (EMI) materials to meet demand have become increasingly prominent. This work uses WP and melamine as raw materials, combined with CaCO3 in WP as a self-sacrificial template agent, to synthesize nitrogen-doped waste plastic porous carbon (WPPC) by sintering. N doping endows WPPC-3 with high hydrophobicity, high electrical conductivity, and high EMI efficiency (20.5 dB in Ku-band). First-principles calculations also demonstrate that WPPC-3 has a more excellent conductive structure than WPPC-0. The low-density polyethylene (LDPE)/template agent (TEM)-40 and LDPE/graphite tailing (GT)-70 have high toughness and high EMI efficiency, respectively. The EMI SET of the multi-scale pore structure functional composite material modified by WPPC (MSP-WPPC) increases by 670.93% in Ku-band, compared with LDPE/GT-40. The synergistic effect of the matrix pore and WPPC mesoporous structure greatly improves the multiple reflection and absorption loss of MSP-WPPC. Polyethylene glycol (PEG) effectively fills the pore space within the structure of MSP-WPPC, thereby conferring upon MSP-WPPC/PEG the remarkable capacity for thermal management. The benefits of multi-solid waste utilization, low cost, and wide frequency EMI make MSP-WPPC/PEG well-suited for military, construction, and communication industries. It will be a creative solution to the above problems.
{"title":"Multiscale-void-containing low-density polyethylene/waste plastic porous carbon composites with electromagnetic shielding interference and thermal management capabilities","authors":"Youpeng Zhang, Na Zhang, Xiaojun Zhang, Shouhang Cui, Chengqian Zhang, Xuemei Wang, Yingge Zhang, HongFen Li, Yihe Zhang","doi":"10.1039/d5ta01561h","DOIUrl":"https://doi.org/10.1039/d5ta01561h","url":null,"abstract":"The problems of inadequate waste plastic (WP) treatment methods, serious electromagnetic hazards, and the difficulty of metal-based electromagnetic shielding interference (EMI) materials to meet demand have become increasingly prominent. This work uses WP and melamine as raw materials, combined with CaCO3 in WP as a self-sacrificial template agent, to synthesize nitrogen-doped waste plastic porous carbon (WPPC) by sintering. N doping endows WPPC-3 with high hydrophobicity, high electrical conductivity, and high EMI efficiency (20.5 dB in Ku-band). First-principles calculations also demonstrate that WPPC-3 has a more excellent conductive structure than WPPC-0. The low-density polyethylene (LDPE)/template agent (TEM)-40 and LDPE/graphite tailing (GT)-70 have high toughness and high EMI efficiency, respectively. The EMI SET of the multi-scale pore structure functional composite material modified by WPPC (MSP-WPPC) increases by 670.93% in Ku-band, compared with LDPE/GT-40. The synergistic effect of the matrix pore and WPPC mesoporous structure greatly improves the multiple reflection and absorption loss of MSP-WPPC. Polyethylene glycol (PEG) effectively fills the pore space within the structure of MSP-WPPC, thereby conferring upon MSP-WPPC/PEG the remarkable capacity for thermal management. The benefits of multi-solid waste utilization, low cost, and wide frequency EMI make MSP-WPPC/PEG well-suited for military, construction, and communication industries. It will be a creative solution to the above problems.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"103 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143822587","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Changyu Weng, Hongmei Yuan, Yuxin Ji, Weidong Liu, Longlong Ma, Jianguo Liu
Covalent organic networks (CONs) with reversible redox behaviour hold great promise as electrode materials for lithium-ion batteries (LIBs). However, the traditional synthesis of CONs relies heavily on organic monomers derived from fossil fuels, posing a significant challenge to the sustainable development of CONs materials. In this study, we present a novel proof-of-concept CON material, named BIO, synthesized from biomass-derived monomers using a mild and straightforward process. This approach aligns with the principles of green and sustainable development while offering potential for large-scale preparation. The BIO-4C was in-situ grown on carbon nanotubes (CNT) to enhance electronic conductivity. As a result, BIO-4C exhibited satisfactory long-cycle performance and high-rate capability. During the long cycle process, the maximum specific capacity of BIO-4C reached 804 mAh g⁻¹ (at 2,000 mA g⁻¹), significantly surpassing most previous reports and commercial graphite anodes. Detailed analysis, including X-ray photoelectron spectroscopy (XPS), density functional theory (DFT) calculations, theoretical capacity, and capacity contribution studies, revealed a storage mechanism based on an 11-electron redox process. This mechanism involves the reversible interaction of lithium ions with benzene rings, furan rings, and imine linkages in the BIO monomer. This work represents a step forward in the development of biomass-based sustainable organic electrodes, offering high performance and practicality for future organic rechargeable batteries.
{"title":"Facile synthesis of biomass-based sustainable covalent organic network (CON) anode for high-performance LIBs","authors":"Changyu Weng, Hongmei Yuan, Yuxin Ji, Weidong Liu, Longlong Ma, Jianguo Liu","doi":"10.1039/d5ta00620a","DOIUrl":"https://doi.org/10.1039/d5ta00620a","url":null,"abstract":"Covalent organic networks (CONs) with reversible redox behaviour hold great promise as electrode materials for lithium-ion batteries (LIBs). However, the traditional synthesis of CONs relies heavily on organic monomers derived from fossil fuels, posing a significant challenge to the sustainable development of CONs materials. In this study, we present a novel proof-of-concept CON material, named BIO, synthesized from biomass-derived monomers using a mild and straightforward process. This approach aligns with the principles of green and sustainable development while offering potential for large-scale preparation. The BIO-4C was in-situ grown on carbon nanotubes (CNT) to enhance electronic conductivity. As a result, BIO-4C exhibited satisfactory long-cycle performance and high-rate capability. During the long cycle process, the maximum specific capacity of BIO-4C reached 804 mAh g⁻¹ (at 2,000 mA g⁻¹), significantly surpassing most previous reports and commercial graphite anodes. Detailed analysis, including X-ray photoelectron spectroscopy (XPS), density functional theory (DFT) calculations, theoretical capacity, and capacity contribution studies, revealed a storage mechanism based on an 11-electron redox process. This mechanism involves the reversible interaction of lithium ions with benzene rings, furan rings, and imine linkages in the BIO monomer. This work represents a step forward in the development of biomass-based sustainable organic electrodes, offering high performance and practicality for future organic rechargeable batteries.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"25 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819122","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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