Huan Zheng, Tao Yin, Jialong Yu, Wei Xu, Weizhen Zhang, Qihui Yu, Yingnan Guo, Li Guan, Xiaolei Huang, Fenghe Wang
Designing efficient, economical bifunctional electrocatalysts for overall water splitting is important and challenging. This paper demonstrates a cobalt-based electrocatalyst modified with stable ceria (CeO2) and adjustable copper metal/oxide (Cu/CuO) to regulate electrochemical reconfigurations during the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Theoretical calculations reveal that CeO2 substantially impacts the electronic configuration and D-band center of catalysts. Surprisingly, CeO2 moves the D-band center of cobalt oxyhydroxide closer to the Fermi level but shifts the D-band center of cobalt hydroxide away from the Fermi level. Therefore, CeO2 optimizes the adsorption energy of the intermediates and boosts the OER activity, while reducing the ability of absorbed hydrogen atoms to bond with the catalyst and enhancing the electron-donor performance of the catalyst in the HER. Furthermore, the presence of Cu/CuO dramatically improves the catalytic activity. Hence, the utilization of CeO2 and CuO/Cu in cobalt-based nanosheet arrays enhances catalytic efficiency in overall water splitting. The overpotentials are only 94 mV and 246 mV (@10 mA cm−2) for the HER and OER, respectively, superior to those of pure cobalt-based catalysts. This study presents an innovative approach to developing efficient overall water splitting catalysts and offers insights into future developments in this field.
为整体水分离设计高效、经济的双功能电催化剂既重要又具有挑战性。本文展示了一种用稳定铈（CeO2）和可调金属铜/氧化物（Cu/CuO）修饰的钴基电催化剂，以调节氢进化反应（HER）和氧进化反应（OER）过程中的电化学重构。理论计算显示，CeO2 对催化剂的电子构型和 D 波段中心有重大影响。令人惊讶的是，CeO2 使氢氧化钴的 D 波段中心更接近费米级，但却使氢氧化钴的 D 波段中心远离费米级。因此，CeO2 优化了中间产物的吸附能，提高了 OER 活性，同时降低了吸收的氢原子与催化剂结合的能力，增强了催化剂在 HER 中的电子负载性能。此外，Cu/CuO 的存在还能显著提高催化活性。因此，在钴基纳米片阵列中利用 CeO2 和 CuO/Cu 可以提高整体水分离的催化效率。HER 和 OER 的过电位分别仅为 94 mV 和 246 mV（@10 mA cm-2），优于纯钴基催化剂。这项研究提出了一种开发高效整体水分离催化剂的创新方法，并为该领域的未来发展提供了启示。
{"title":"Regulating the electronic structure of catalysts via stable ceria and adjustable copper metal/oxide towards efficient overall water splitting","authors":"Huan Zheng, Tao Yin, Jialong Yu, Wei Xu, Weizhen Zhang, Qihui Yu, Yingnan Guo, Li Guan, Xiaolei Huang, Fenghe Wang","doi":"10.1039/d4ta06305h","DOIUrl":"https://doi.org/10.1039/d4ta06305h","url":null,"abstract":"Designing efficient, economical bifunctional electrocatalysts for overall water splitting is important and challenging. This paper demonstrates a cobalt-based electrocatalyst modified with stable ceria (CeO<small><sub>2</sub></small>) and adjustable copper metal/oxide (Cu/CuO) to regulate electrochemical reconfigurations during the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Theoretical calculations reveal that CeO<small><sub>2</sub></small> substantially impacts the electronic configuration and D-band center of catalysts. Surprisingly, CeO<small><sub>2</sub></small> moves the D-band center of cobalt oxyhydroxide closer to the Fermi level but shifts the D-band center of cobalt hydroxide away from the Fermi level. Therefore, CeO<small><sub>2</sub></small> optimizes the adsorption energy of the intermediates and boosts the OER activity, while reducing the ability of absorbed hydrogen atoms to bond with the catalyst and enhancing the electron-donor performance of the catalyst in the HER. Furthermore, the presence of Cu/CuO dramatically improves the catalytic activity. Hence, the utilization of CeO<small><sub>2</sub></small> and CuO/Cu in cobalt-based nanosheet arrays enhances catalytic efficiency in overall water splitting. The overpotentials are only 94 mV and 246 mV (@10 mA cm<small><sup>−2</sup></small>) for the HER and OER, respectively, superior to those of pure cobalt-based catalysts. This study presents an innovative approach to developing efficient overall water splitting catalysts and offers insights into future developments in this field.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"36 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601791","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}
Ziqiang Wang, Yanan Wang, Shan Xu, Kai Deng, Hongjie Yu, You Xu, Hongjing Wang, Liang Wang
Electrochemical co-reduction of carbon dioxide and nitrate is a green technology to replace traditional energy-intensive method for urea synthesis, and the development of high-performance catalysts is still a great challenge. Here, we propose the incorporation of nonmetal hydrogen and oxophilic zinc into palladium metallene for the preparation of hydrogen-intercalation PdZn (H-PdZn) bimetallene, serving as an active electrocatalyst for co-reduction of carbon dioxide and nitrate to synthesize urea via C-N coupling reaction. The H-PdZn bimetallene shows high urea yield of 314.17 μg h-1 mg-1 and Faraday efficiency of 24.39%, better than PdZn bimetallene (144.25 μg h-1 mg-1 and 16.03%). The strong electronic effect among the Pd, Zn and H atoms can induce the downshift of Pd d-band center of H-PdZn bimetallene, which can promote the formation of the key intermediates of *NH2 and *CO, and lower the energy barrier for their C-N coupling to synthesize urea. This work offers hydrogenation strategy for the construction of advanced PdH-based metallenes towards electrochemical C-N coupling to synthesize urea.
{"title":"Hydrogen-intercalation PdZn bimetallene for urea electro-synthesis from nitrate and carbon dioxide","authors":"Ziqiang Wang, Yanan Wang, Shan Xu, Kai Deng, Hongjie Yu, You Xu, Hongjing Wang, Liang Wang","doi":"10.1039/d4ta04802d","DOIUrl":"https://doi.org/10.1039/d4ta04802d","url":null,"abstract":"Electrochemical co-reduction of carbon dioxide and nitrate is a green technology to replace traditional energy-intensive method for urea synthesis, and the development of high-performance catalysts is still a great challenge. Here, we propose the incorporation of nonmetal hydrogen and oxophilic zinc into palladium metallene for the preparation of hydrogen-intercalation PdZn (H-PdZn) bimetallene, serving as an active electrocatalyst for co-reduction of carbon dioxide and nitrate to synthesize urea via C-N coupling reaction. The H-PdZn bimetallene shows high urea yield of 314.17 μg h-1 mg-1 and Faraday efficiency of 24.39%, better than PdZn bimetallene (144.25 μg h-1 mg-1 and 16.03%). The strong electronic effect among the Pd, Zn and H atoms can induce the downshift of Pd d-band center of H-PdZn bimetallene, which can promote the formation of the key intermediates of *NH2 and *CO, and lower the energy barrier for their C-N coupling to synthesize urea. This work offers hydrogenation strategy for the construction of advanced PdH-based metallenes towards electrochemical C-N coupling to synthesize urea.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"15 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601796","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}
Irlan Santos Lima, Josué M. Gonçalves, Lúcio Angnes
Catalysts capable of overcoming the bottleneck of water splitting, known as the oxygen evolution reaction (OER), are indispensable to the expansion of renewable energy systems. Thus, we report the synthesis of ternary glycerolate containing Ni, Fe, and Co metals by an easy one-pot solvothermal method. Interestingly, the iron precursor content plays a key role in the formation of microspheres, as confirmed by scanning electronic microscopy (SEM) images. In fact, when Fe-acetate precursor content exceeds 33.3% in molar proportions, particles without a defined morphology are generated. By comparing three distinct compositions of Ni1-2xFexCox-Gly (x = 0.2;0.3;0.33, respectively), the best performance is achieved with Ni0.4Fe0.3Co0.3-Gly, showing an excellent overpotential of 277 mV and a Tafel Slope of 36.24 mV dec1. The presence of in-situ formed metal oxyhydroxide species on the electrode surface is the key to the high-performance catalyst presented in this work. Where the interaction between Ni²⁺/³⁺, Fe²⁺/³⁺, and Co²⁺/³⁺ provides significant electroactivity under OER conditions over 16 h at 10 mA cm⁻², with a positive potential shift of 19 mV in alkaline medium (1M KOH). These findings highlight the potential of NiFeCo-Gly catalyst as an efficient material for OER in renewable energy applications.
能够克服水分裂瓶颈（即氧进化反应）的催化剂对于可再生能源系统的发展不可或缺。因此，我们报告了通过简单的一锅溶热法合成含有镍、铁和钴金属的三元甘油酸酯。有趣的是，扫描电子显微镜（SEM）图像证实，铁前驱体的含量对微球的形成起着关键作用。事实上，当乙酸铁前驱体的摩尔比例超过 33.3% 时，就会生成没有明确形态的颗粒。通过比较 Ni1-2xFexCox-Gly（x 分别为 0.2；0.3；0.33）的三种不同成分，Ni0.4Fe0.3Co0.3-Gly 的性能最佳，显示出 277 mV 的出色过电位和 36.24 mV 的塔菲尔斜率1。电极表面存在原位形成的金属氢氧化物物种是这项工作中提出的高性能催化剂的关键。其中，Ni²⁺/³⁺、Fe²⁺/³⁺和 Co²⁺/³⁺ 之间的相互作用在 10 mA cm-² 的 OER 条件下提供了 16 小时的显著电活性，在碱性介质（1M KOH）中产生了 19 mV 的正电位移动。这些发现凸显了镍铁钴釉催化剂作为一种高效材料用于可再生能源应用中的 OER 的潜力。
{"title":"Ternary NiFeCo-Glycerolate Catalysts: Rational Design for Improved Oxygen Evolution Reaction Efficiency","authors":"Irlan Santos Lima, Josué M. Gonçalves, Lúcio Angnes","doi":"10.1039/d4ta06455k","DOIUrl":"https://doi.org/10.1039/d4ta06455k","url":null,"abstract":"Catalysts capable of overcoming the bottleneck of water splitting, known as the oxygen evolution reaction (OER), are indispensable to the expansion of renewable energy systems. Thus, we report the synthesis of ternary glycerolate containing Ni, Fe, and Co metals by an easy one-pot solvothermal method. Interestingly, the iron precursor content plays a key role in the formation of microspheres, as confirmed by scanning electronic microscopy (SEM) images. In fact, when Fe-acetate precursor content exceeds 33.3% in molar proportions, particles without a defined morphology are generated. By comparing three distinct compositions of Ni1-2xFexCox-Gly (x = 0.2;0.3;0.33, respectively), the best performance is achieved with Ni0.4Fe0.3Co0.3-Gly, showing an excellent overpotential of 277 mV and a Tafel Slope of 36.24 mV dec1. The presence of in-situ formed metal oxyhydroxide species on the electrode surface is the key to the high-performance catalyst presented in this work. Where the interaction between Ni²⁺/³⁺, Fe²⁺/³⁺, and Co²⁺/³⁺ provides significant electroactivity under OER conditions over 16 h at 10 mA cm⁻², with a positive potential shift of 19 mV in alkaline medium (1M KOH). These findings highlight the potential of NiFeCo-Gly catalyst as an efficient material for OER in renewable energy applications.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"63 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601811","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}
Seungju Oh, Sang Woo Bae, Tae Hyung Kim, Gumin Kang, Heesuk Jung, Young-Hoon Kim, Minwoo Park
Luminescent solar concentrators (LSCs) play a major role as light suppliers at the boundaries between indoor and outdoor spaces in buildings. The performances of solar panels coupled with LSCs are directly influenced by the photoluminescence (PL) characteristics of fluorophores, among which inorganic perovskite nanocrystals (PeNCs) have shown great potential. A large Stokes shift in these NCs spanning the ultraviolet (UV), visible, and near-infrared regions can be achieved through metal doping, leading to significant improvements in the PL quantum yields and reduced PL reabsorption. However, practical approaches for coupling perovskite LSCs (PeLSCs) with perovskite solar cells (PSCs) are lacking. The design of all-perovskite LSC/photovoltaic (PV) windows is essential to prepare perovskite-based building-integrated PV systems. Thus, Mn-doped CsPbCl3 NCs were employed as PL-reabsorption-free fluorophores for LSCs. Their significant Stokes shift allowed for efficient PL propagation to the LSC edges. The Mn:CsPbCl3/polystyrene composite films used in the LSCs demonstrated excellent optical transparencies and low haze values. When coupled with 16 series-connected high-efficiency PSCs, the PeLSC/PV windows exhibited impressive optical (5.38%) and power conversion (0.43%) efficiencies at a large geometric factor of 25 under 1 sun illumination. Using PeLSC/PV windows as self-powered UV light detectors, an excellent responsivity, specific detectivity, and noise equivalent power were obtained due to strong PL emission from the LSCs, even under weak UV light. An excellent power conversion efficiency was retained (86.3%) after 1000 h of operation due to protection of the solar absorbers from UV light by the long-wavelength PL emission of the LSCs.
{"title":"Highly transparent all-perovskite luminescent solar concentrator/photovoltaic windows","authors":"Seungju Oh, Sang Woo Bae, Tae Hyung Kim, Gumin Kang, Heesuk Jung, Young-Hoon Kim, Minwoo Park","doi":"10.1039/d4ta06249c","DOIUrl":"https://doi.org/10.1039/d4ta06249c","url":null,"abstract":"Luminescent solar concentrators (LSCs) play a major role as light suppliers at the boundaries between indoor and outdoor spaces in buildings. The performances of solar panels coupled with LSCs are directly influenced by the photoluminescence (PL) characteristics of fluorophores, among which inorganic perovskite nanocrystals (PeNCs) have shown great potential. A large Stokes shift in these NCs spanning the ultraviolet (UV), visible, and near-infrared regions can be achieved through metal doping, leading to significant improvements in the PL quantum yields and reduced PL reabsorption. However, practical approaches for coupling perovskite LSCs (PeLSCs) with perovskite solar cells (PSCs) are lacking. The design of all-perovskite LSC/photovoltaic (PV) windows is essential to prepare perovskite-based building-integrated PV systems. Thus, Mn-doped CsPbCl<small><sub>3</sub></small> NCs were employed as PL-reabsorption-free fluorophores for LSCs. Their significant Stokes shift allowed for efficient PL propagation to the LSC edges. The Mn:CsPbCl<small><sub>3</sub></small>/polystyrene composite films used in the LSCs demonstrated excellent optical transparencies and low haze values. When coupled with 16 series-connected high-efficiency PSCs, the PeLSC/PV windows exhibited impressive optical (5.38%) and power conversion (0.43%) efficiencies at a large geometric factor of 25 under 1 sun illumination. Using PeLSC/PV windows as self-powered UV light detectors, an excellent responsivity, specific detectivity, and noise equivalent power were obtained due to strong PL emission from the LSCs, even under weak UV light. An excellent power conversion efficiency was retained (86.3%) after 1000 h of operation due to protection of the solar absorbers from UV light by the long-wavelength PL emission of the LSCs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"69 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601792","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}
Encapsulating metal in zeolite is an effective tactic to up-regulate the catalytic selectivity of metal/zeolite catalysts in hydrogenation reaction by virtue of the spatial confinement of the zeolite microchannels. Herein, we present the synthesis of Pt encapsulated in zeolite with TON topology (Pt@ZSM-22) by adopting the ligand-protected and lowered-temperature hydrothermal crystallization. The XRD, SEM, TEM, TG-DSC-MS, and 13C CP/MAS NMR are used to track the hydrothermal process. The experimental results indicate the decomposition and reduction of metal precursor ([Pt(en)2]2+), which usually occurs at the harsh hydrothermal conditions, is effectively restrained at the lowered hydrothermal temperature (140 °C) and with the protection of the ligand (ethylenediamine). The intact [Pt(en)2]2+ is electrostatically adsorbed on the amorphous silicate nanoparticles (the zeolite precursor) and is encapsulated inside the ZSM-22 crystals as these nanoparticles are crystallized. The highly-dispersed and uniform Pt particles embedded inside the ZSM-22 zeolite are successfully obtained by adopting the direct H2 reduction to remove the template and reduce the [Pt(en)2]2+. The hydrogenation of furfural to furfuryl alcohol was conducted to evaluate the selective hydrogenation performance of the encapsulated Pt@ZSM-22. The reaction results reveal the furfuryl alcohol selectivity reaches as high as 97.6% at a conversion of 99.5% over the encapsulated Pt@ZSM-22, which is superior to the supported Pt/ZSM-22. The excellent furfuryl alcohol selectivity reflects the shape selectivity conferred by the spatial confinement of the one-dimensional microchannels of ZSM-22. The CO-FT-IR, XPS, XAFS and FT-IR of adsorbed furfural are used to disclose the structure-activity relationship of Pt@ZSM-22. Our work not only successfully realizes the direct hydrothermal synthesis of metal encapsulation in zeolite with 1D straight channels but also demonstrates the great application potentials of such catalysts in selective catalysis.
{"title":"Ligand-protected and lowered-temperature hydrothermal synthesis of platinum encapsulated in TON zeolite for shape-selective hydrogenation of furfural to furfuryl alcohol","authors":"Xuelin Wang, Congxin Wang, Wentao Bi, Wei Qu, Zhijian Tian","doi":"10.1039/d4ta07243j","DOIUrl":"https://doi.org/10.1039/d4ta07243j","url":null,"abstract":"Encapsulating metal in zeolite is an effective tactic to up-regulate the catalytic selectivity of metal/zeolite catalysts in hydrogenation reaction by virtue of the spatial confinement of the zeolite microchannels. Herein, we present the synthesis of Pt encapsulated in zeolite with TON topology (Pt@ZSM-22) by adopting the ligand-protected and lowered-temperature hydrothermal crystallization. The XRD, SEM, TEM, TG-DSC-MS, and <small><sup>13</sup></small>C CP/MAS NMR are used to track the hydrothermal process. The experimental results indicate the decomposition and reduction of metal precursor ([Pt(en)<small><sub>2</sub></small>]<small><sup>2+</sup></small>), which usually occurs at the harsh hydrothermal conditions, is effectively restrained at the lowered hydrothermal temperature (140 °C) and with the protection of the ligand (ethylenediamine). The intact [Pt(en)<small><sub>2</sub></small>]<small><sup>2+</sup></small> is electrostatically adsorbed on the amorphous silicate nanoparticles (the zeolite precursor) and is encapsulated inside the ZSM-22 crystals as these nanoparticles are crystallized. The highly-dispersed and uniform Pt particles embedded inside the ZSM-22 zeolite are successfully obtained by adopting the direct H<small><sub>2</sub></small> reduction to remove the template and reduce the [Pt(en)<small><sub>2</sub></small>]<small><sup>2+</sup></small>. The hydrogenation of furfural to furfuryl alcohol was conducted to evaluate the selective hydrogenation performance of the encapsulated Pt@ZSM-22. The reaction results reveal the furfuryl alcohol selectivity reaches as high as 97.6% at a conversion of 99.5% over the encapsulated Pt@ZSM-22, which is superior to the supported Pt/ZSM-22. The excellent furfuryl alcohol selectivity reflects the shape selectivity conferred by the spatial confinement of the one-dimensional microchannels of ZSM-22. The CO-FT-IR, XPS, XAFS and FT-IR of adsorbed furfural are used to disclose the structure-activity relationship of Pt@ZSM-22. Our work not only successfully realizes the direct hydrothermal synthesis of metal encapsulation in zeolite with 1D straight channels but also demonstrates the great application potentials of such catalysts in selective catalysis.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"158 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601794","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}
Hyerin Jeon, Jin-Woo Lee, Kihyun Bae, Tan Ngoc-Lan Phan, Chulhee Lim, Jaeyoung Choi, Cheng Wang, Seungjin Lee, Bumjoon Kim
Conventional processing solvents for organic electronics pose significant health/environmental risks, prompting the search for greener/safer alternatives. Herein, we develop organic solar cells (OSCs), processed from a single terpene solvent, eucalyptol (Eu), with almost no environmental hazards and toxicity. Notably, a record-high power conversion efficiency (PCE) of 15.1% is achieved without any additive, which is particularly significant given the low PCEs (0.1–3.0%) of previous OSCs using a single terpene. First, we design a small-molecule acceptor (MYBO) with optimized side-chains, offering sufficient solubility while maintaining excellent optoelectronic properties. Second, we develop a processing technique which controls the film-formation kinetics to independently tune the aggregation of polymer donor and MYBO. This enables the formation of well-developed MYBO crystallites embedded within interconnected polymer fibrillar structures. And, all the solution processing can be performed in air without using a glove box, thanks to the eco-friendly Eu process. The devices also exhibit excellent air-stability, retaining more than 92% of the initial PCE after 2300 hr in air. This work provides important guidelines for material designs and processing methods to achieve eco-friendly processed, high-performance OSCs.
{"title":"High-Performance, Ambient-Processable Organic Solar Cells Achieved by Single Terpene-Based Entirely Eco-Friendly Process","authors":"Hyerin Jeon, Jin-Woo Lee, Kihyun Bae, Tan Ngoc-Lan Phan, Chulhee Lim, Jaeyoung Choi, Cheng Wang, Seungjin Lee, Bumjoon Kim","doi":"10.1039/d4ta07223e","DOIUrl":"https://doi.org/10.1039/d4ta07223e","url":null,"abstract":"Conventional processing solvents for organic electronics pose significant health/environmental risks, prompting the search for greener/safer alternatives. Herein, we develop organic solar cells (OSCs), processed from a single terpene solvent, eucalyptol (Eu), with almost no environmental hazards and toxicity. Notably, a record-high power conversion efficiency (PCE) of 15.1% is achieved without any additive, which is particularly significant given the low PCEs (0.1–3.0%) of previous OSCs using a single terpene. First, we design a small-molecule acceptor (MYBO) with optimized side-chains, offering sufficient solubility while maintaining excellent optoelectronic properties. Second, we develop a processing technique which controls the film-formation kinetics to independently tune the aggregation of polymer donor and MYBO. This enables the formation of well-developed MYBO crystallites embedded within interconnected polymer fibrillar structures. And, all the solution processing can be performed in air without using a glove box, thanks to the eco-friendly Eu process. The devices also exhibit excellent air-stability, retaining more than 92% of the initial PCE after 2300 hr in air. This work provides important guidelines for material designs and processing methods to achieve eco-friendly processed, high-performance OSCs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"80 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601795","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}
Developing efficient and low-energy hydrogen isotope separation technology is one of the key requirements for fuel cycle and deuterium tritium wastewater treatment in the current development of nuclear fusion. Due to the almost identical physical and chemical properties of hydrogen isotopes, the rapid production of H2 is an important challenge for selective photocatalytic hydrogen isotope separation. We report an effective strategy for hydrogen isotope separation based on N–O–C3N4 photocatalysis. By simultaneously doping nitrogen and oxygen, the microstructure and band structure of the g-C3N4 catalyst were significantly optimized, resulting in improved catalytic activity. The inherent differences in flow states between H2O and D2O, as well as the differences in binding energy between H–O and D–O, provide opportunities for the separation of hydrogen isotopes. The hydrogen production rate of the N–O–C3N4 catalyst under visible light conditions is 7.439 mmol g−1 h−1 and the H/D separation factor is about 6.44. The photocatalytic strategy has mild and environmentally friendly reaction conditions, and this research work provides a reference for the development of efficient and advanced isotope separation systems.
{"title":"Efficient hydrogen isotope separation utilizing photocatalytic capability","authors":"Linzhen Wu, Sifan Zeng, Weiwei Wang, Shengtai Zhang, Hongbo Li, Xiaosong Zhou","doi":"10.1039/d4ta07355j","DOIUrl":"https://doi.org/10.1039/d4ta07355j","url":null,"abstract":"Developing efficient and low-energy hydrogen isotope separation technology is one of the key requirements for fuel cycle and deuterium tritium wastewater treatment in the current development of nuclear fusion. Due to the almost identical physical and chemical properties of hydrogen isotopes, the rapid production of H<small><sub>2</sub></small> is an important challenge for selective photocatalytic hydrogen isotope separation. We report an effective strategy for hydrogen isotope separation based on N–O–C<small><sub>3</sub></small>N<small><sub>4</sub></small> photocatalysis. By simultaneously doping nitrogen and oxygen, the microstructure and band structure of the g-C<small><sub>3</sub></small>N<small><sub>4</sub></small> catalyst were significantly optimized, resulting in improved catalytic activity. The inherent differences in flow states between H<small><sub>2</sub></small>O and D<small><sub>2</sub></small>O, as well as the differences in binding energy between H–O and D–O, provide opportunities for the separation of hydrogen isotopes. The hydrogen production rate of the N–O–C<small><sub>3</sub></small>N<small><sub>4</sub></small> catalyst under visible light conditions is 7.439 mmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small> and the H/D separation factor is about 6.44. The photocatalytic strategy has mild and environmentally friendly reaction conditions, and this research work provides a reference for the development of efficient and advanced isotope separation systems.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"10 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600074","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}
With the rapid development of 5G communication technology and intelligent detection technology, electromagnetic shielding/infrared stealth fabrics with Joule/solar heating performance can meet the needs of wearable electronic devices for multi-application scenarios. Two-dimensional (2D) transition metal carbides and nitrides (MXenes) are ideal candidates for constructing efficient conductive networks in EMI SE fabrics due to their layered structure and high conductivity. However, it is difficult for MXene nanosheets to assemble into excellent interconnected conductive networks due to the irregular size and stacking of MXene sheets after MXene etching. Inspired by transport of nutrients by roots, a three-dimensional (3D) efficient conductive network was constructed by bridging one-dimensional (1D) Ag nanowires (AgNWs) into the highly conductive 2D MXenes, and a series of flexible multifunctional MXene@AgNW/cotton fabrics with excellent EMI SE performance was obtained. The average EMI SE value of MXene@AgNW/cotton fabrics can reach 70.6 dB in the X band. The oxidation resistance of the fabric is enhanced after spraying perfluorooctyltriethoxysilane (PFOTES) on the surface, and the surface water contact angle reaches 135.1°, providing excellent self-cleaning performance. MXene@AgNW/cotton fabric exhibits an average infrared emissivity of 0.25 (3–5 μm) and 0.17 (8–14 μm), showing excellent camouflage capability for infrared thermal signals under an infrared camera, generating a temperature difference of about 132.2 °C with a hot stage at 200 °C. MXene@AgNW/cotton fabric shows good electrical heating performance under low voltage loading (temperature reaches 150 °C at 3.5 V) and it also exhibits photothermal properties, showing a temperature of 120 °C under light density irradiation of 1900 W m−2 within 180 s, which can realize the functions of hot compress therapy and cold preservation. The limiting oxygen index (LOI) value of MXene@AgNW/cotton fabric is 27.5%, which proves that MXene@AgNW/cotton fabric exhibits fire safety in practical applications. This work provides a paradigm for the construction of flexible multifunctional EMI SE fabrics.
随着 5G 通信技术和智能检测技术的快速发展，具有焦耳/太阳能加热性能的电磁屏蔽/红外隐身织物可满足可穿戴电子设备的多应用场景需求。二维（2D）过渡金属碳化物和氮化物（MXenes）具有层状结构和高导电性，是在 EMI SE 织物中构建高效导电网络的理想候选材料。然而，由于 MXene 蚀刻后 MXene 片的尺寸和堆叠不规则，MXene 纳米片很难组装成出色的互连导电网络。受根部养分运输的启发，通过将一维（1D）银纳米线（AgNW）桥接到高导电性二维 MXene 中，构建了三维（3D）高效导电网络，并获得了一系列具有优异 EMI SE 性能的柔性多功能 MXene@AgNW/ 棉织物。MXene@AgNW/cotton 织物在 X 波段的平均 EMI SE 值高达 70.6 dB。在织物表面喷涂全氟辛基三乙氧基硅烷（PFOTES）后，织物的抗氧化性增强，表面水接触角达到 135.1°，具有优异的自清洁性能。MXene@AgNW/cotton 织物的平均红外发射率分别为 0.25（3-5 μm）和 0.17（8-14 μm），在红外摄像机下对红外热信号具有极佳的伪装能力，在 200 ℃ 的高温阶段可产生约 132.2 ℃ 的温差。MXene@AgNW/cotton 织物在低电压负载下具有良好的电加热性能（3.5 V 时温度达到 150 ℃），同时还具有光热特性，在光密度为 1900 W m-2 的照射下，180 秒内温度达到 120 ℃，可实现热敷治疗和冷藏保鲜功能。MXene@AgNW/cotton 织物的极限氧指数（LOI）值为 27.5%，证明了 MXene@AgNW/cotton 织物在实际应用中的防火安全性。这项工作为构建柔性多功能 EMI SE 织物提供了范例。
{"title":"Flexible multifunctional MXene@Ag nanowires/cotton fabric inspired by transport of nutrients by roots for electromagnetic shielding, infrared stealth, Joule/solar heating and flame retardancy","authors":"Jiatong Yan, Meimei Chen, Rui Tan, Chuanxi Lin, Shan Jiang, Weijie Wang, Songyue Pan, Hongyan Xiao, Erhui Ren, Ronghui Guo","doi":"10.1039/d4ta06712f","DOIUrl":"https://doi.org/10.1039/d4ta06712f","url":null,"abstract":"With the rapid development of 5G communication technology and intelligent detection technology, electromagnetic shielding/infrared stealth fabrics with Joule/solar heating performance can meet the needs of wearable electronic devices for multi-application scenarios. Two-dimensional (2D) transition metal carbides and nitrides (MXenes) are ideal candidates for constructing efficient conductive networks in EMI SE fabrics due to their layered structure and high conductivity. However, it is difficult for MXene nanosheets to assemble into excellent interconnected conductive networks due to the irregular size and stacking of MXene sheets after MXene etching. Inspired by transport of nutrients by roots, a three-dimensional (3D) efficient conductive network was constructed by bridging one-dimensional (1D) Ag nanowires (AgNWs) into the highly conductive 2D MXenes, and a series of flexible multifunctional MXene@AgNW/cotton fabrics with excellent EMI SE performance was obtained. The average EMI SE value of MXene@AgNW/cotton fabrics can reach 70.6 dB in the X band. The oxidation resistance of the fabric is enhanced after spraying perfluorooctyltriethoxysilane (PFOTES) on the surface, and the surface water contact angle reaches 135.1°, providing excellent self-cleaning performance. MXene@AgNW/cotton fabric exhibits an average infrared emissivity of 0.25 (3–5 μm) and 0.17 (8–14 μm), showing excellent camouflage capability for infrared thermal signals under an infrared camera, generating a temperature difference of about 132.2 °C with a hot stage at 200 °C. MXene@AgNW/cotton fabric shows good electrical heating performance under low voltage loading (temperature reaches 150 °C at 3.5 V) and it also exhibits photothermal properties, showing a temperature of 120 °C under light density irradiation of 1900 W m<small><sup>−2</sup></small> within 180 s, which can realize the functions of hot compress therapy and cold preservation. The limiting oxygen index (LOI) value of MXene@AgNW/cotton fabric is 27.5%, which proves that MXene@AgNW/cotton fabric exhibits fire safety in practical applications. This work provides a paradigm for the construction of flexible multifunctional EMI SE fabrics.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"2 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600066","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}
Gwan-Jin Ko, Tae-Min Jang, Daiha Shin, Heeseok Kang, Seung Min Yang, Sungkeun Han, Rajaram Kaveti, Chan-Hwi Eom, So Jeong Choi, Won Bae Han, Woon-Hong Yeo, Amay J. Bandodkar, Jiung Cho, Suk-Won Hwang
Rapid technological revolution produces a wide range of convenient tools, while, in particular, the production and consumption of batteries lead to various issues including environmental pollution. Although efforts to solve such problems increase interest in green and dissolvable batteries, their short service life is still recognized as a major obstacle due to limited options of materials. Here, we propose materials and system designs for eco-friendly and biodegradable magnesium alloy–tungsten (AZ31–W) batteries that offer long-term stability with enhanced corrosion resistance. Materials and electrochemical inspections confirm the superior electrochemical tolerance and stable, reliable potentials of the AZ31 anode and W cathode. The assembly of an individual cell into a commercially available pouch battery yields a high capacity of ∼430 mA h g−1, suitable for high-energy applications. The integration of alginate-based soft, elastic electrolytes with the electrodes enables the achievement of completely eco-resorbable solid-state batteries that maintain performance under diverse physical deformations. The results suggest potential for biomedical and eco-friendly applications where commercial batteries pose risks to the environment or human body.
快速的技术革命产生了各种便捷的工具，而电池的生产和消费尤其导致了包括环境污染在内的各种问题。尽管为解决这些问题所做的努力增加了人们对绿色可溶解电池的兴趣，但由于可供选择的材料有限，电池的短使用寿命仍被认为是一个主要障碍。在此，我们提出了可生物降解的环保型镁合金-钨（AZ31-W）电池的材料和系统设计，这种电池具有长期稳定性和更强的耐腐蚀性。材料和电化学检测证实，AZ31 阳极和 W 阴极具有卓越的电化学耐受性和稳定可靠的电位。将单个电池组装到市售的袋装电池中，可获得 ∼430 mA h g-1 的高容量，适用于高能量应用。将海藻酸软弹性电解质与电极整合在一起，可实现完全生态可吸收的固态电池，在各种物理变形情况下都能保持性能。研究结果表明，在商业电池对环境或人体构成风险的地方，这种电池具有生物医学和生态友好型应用的潜力。
{"title":"Long-lasting, flexible and fully bioresorbable AZ31–tungsten batteries for transient, biodegradable electronics","authors":"Gwan-Jin Ko, Tae-Min Jang, Daiha Shin, Heeseok Kang, Seung Min Yang, Sungkeun Han, Rajaram Kaveti, Chan-Hwi Eom, So Jeong Choi, Won Bae Han, Woon-Hong Yeo, Amay J. Bandodkar, Jiung Cho, Suk-Won Hwang","doi":"10.1039/d4ta06222a","DOIUrl":"https://doi.org/10.1039/d4ta06222a","url":null,"abstract":"Rapid technological revolution produces a wide range of convenient tools, while, in particular, the production and consumption of batteries lead to various issues including environmental pollution. Although efforts to solve such problems increase interest in green and dissolvable batteries, their short service life is still recognized as a major obstacle due to limited options of materials. Here, we propose materials and system designs for eco-friendly and biodegradable magnesium alloy–tungsten (AZ31–W) batteries that offer long-term stability with enhanced corrosion resistance. Materials and electrochemical inspections confirm the superior electrochemical tolerance and stable, reliable potentials of the AZ31 anode and W cathode. The assembly of an individual cell into a commercially available pouch battery yields a high capacity of ∼430 mA h g<small><sup>−1</sup></small>, suitable for high-energy applications. The integration of alginate-based soft, elastic electrolytes with the electrodes enables the achievement of completely eco-resorbable solid-state batteries that maintain performance under diverse physical deformations. The results suggest potential for biomedical and eco-friendly applications where commercial batteries pose risks to the environment or human body.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"216 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600067","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}
Aqueous electrolytes offer enhanced safety and environmental friendliness for next-generation energy storage systems, but their application is limited by a narrow electrochemical stability window. This study provides a comprehensive analysis of the relationship between water activity and the electrochemical stability window of aqueous electrolytes, critically examining current expansion strategies. Our investigation reveals that stability window expansion is primarily driven by kinetic factors rather than thermodynamic ones. We demonstrate that decreasing water activity predominantly affects the oxygen evolution reaction, with minimal impact on hydrogen evolution. This asymmetric effect is quantified through Tafel analysis, showing a significant decrease in exchange current density with reduced water activity. Notably, this study is the first to establish a direct correlation between water activity and the electrochemical stability window for aqueous electrolytes, providing fundamental insights into how water activity influences electrode reaction kinetics and overall system stability. We critically evaluate existing approaches to reducing water activity, including high-concentration electrolytes, water-in-salt systems, and hydrophobic ions. While these methods widen the electrochemical window, they lead to decreased ionic conductivity and increased viscosity. In "water-in-salt" electrolytes, conductivity drops to levels comparable to organic electrolytes, while viscosity increases exponentially. This work challenges the focus on maximizing stability windows at the expense of other crucial properties. We argue for a balanced approach in aqueous electrolyte design, considering factors such as ionic mobility, salt solubility, viscosity, and operational temperature range alongside electrochemical stability.
{"title":"Water activity: the key to unlocking high-voltage aqueous electrolytes?","authors":"Yaroslav Zhigalenok, Saken Abdimomyn, Mikhail Levi, Netanel Shpigel, Margarita Ryabicheva, Maxim Lepikhin, Alina Galeyeva, Fyodor Malchik","doi":"10.1039/d4ta06655c","DOIUrl":"https://doi.org/10.1039/d4ta06655c","url":null,"abstract":"Aqueous electrolytes offer enhanced safety and environmental friendliness for next-generation energy storage systems, but their application is limited by a narrow electrochemical stability window. This study provides a comprehensive analysis of the relationship between water activity and the electrochemical stability window of aqueous electrolytes, critically examining current expansion strategies. Our investigation reveals that stability window expansion is primarily driven by kinetic factors rather than thermodynamic ones. We demonstrate that decreasing water activity predominantly affects the oxygen evolution reaction, with minimal impact on hydrogen evolution. This asymmetric effect is quantified through Tafel analysis, showing a significant decrease in exchange current density with reduced water activity. Notably, this study is the first to establish a direct correlation between water activity and the electrochemical stability window for aqueous electrolytes, providing fundamental insights into how water activity influences electrode reaction kinetics and overall system stability. We critically evaluate existing approaches to reducing water activity, including high-concentration electrolytes, water-in-salt systems, and hydrophobic ions. While these methods widen the electrochemical window, they lead to decreased ionic conductivity and increased viscosity. In \"water-in-salt\" electrolytes, conductivity drops to levels comparable to organic electrolytes, while viscosity increases exponentially. This work challenges the focus on maximizing stability windows at the expense of other crucial properties. We argue for a balanced approach in aqueous electrolyte design, considering factors such as ionic mobility, salt solubility, viscosity, and operational temperature range alongside electrochemical stability.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"13 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600078","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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