Science China Chemistry最新文献_第9页

Solar-powered methanol synthesis from CO2 hydrogenation with high conversion and selectivity

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-09-23 DOI: 10.1007/s11426-024-2318-8

Lingzhen Zeng, Yongfang Sun, Tingting Wang, Zeyan Cen, Maolin Wang, Oriol Angurell, Meng Wang, Ding Ma

{"title":"Solar-powered methanol synthesis from CO2 hydrogenation with high conversion and selectivity","authors":"Lingzhen Zeng, Yongfang Sun, Tingting Wang, Zeyan Cen, Maolin Wang, Oriol Angurell, Meng Wang, Ding Ma","doi":"10.1007/s11426-024-2318-8","DOIUrl":"10.1007/s11426-024-2318-8","url":null,"abstract":"<div><p>Methanol synthesis via CO<sub>2</sub> hydrogenation stands as a pivotal avenue for CO<sub>2</sub> conversion and fixation, garnering extensive investigation. Diverse reactor configurations and energy supplies, alongside a spectrum of catalyst formulations, have been developed to enhance reaction metrics including conversion, selectivity, productivity, and stability. Integrating state-of-the-art Cu-based catalysts from thermal catalysis into a photothermal reactor yielded notable results, achieving an overall CO<sub>2</sub> conversion of 98% and methanol selectivity of 86%. Utilizing the liquid out/gas in concept (LOGIC) reactor, in which only the catalyst bed is irradiated to raise its temperature, facilitated the condensation of products (H<sub>2</sub>O and CH<sub>3</sub>OH), due to their low vapor pressure. The lower concentration of products in vapor phases ensured the continuous progress of the reaction. The synergistic integration of reactor design and catalyst fabrication could capitalize on the strengths of both components and lead to enhanced performance in methanol synthesis.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 2","pages":"513 - 519"},"PeriodicalIF":10.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The critical role of energetic fluctuations in charge separation for efficient molecular doping of organic semiconductors 电荷分离中的能量波动对有机半导体高效分子掺杂的关键作用

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-09-23 DOI: 10.1007/s11426-024-2141-9

Yan Zeng, Guangchao Han, Yuanping Yi

{"title":"The critical role of energetic fluctuations in charge separation for efficient molecular doping of organic semiconductors","authors":"Yan Zeng, Guangchao Han, Yuanping Yi","doi":"10.1007/s11426-024-2141-9","DOIUrl":"10.1007/s11426-024-2141-9","url":null,"abstract":"<div><p>Molecular doping is essential to improve the electrical conductivity of organic semiconductors for high-performance organic electronic devices. However, the doping efficiency is influenced by several factors, such as the energy levels, energetic fluctuations, dielectric properties, and molecular packing structures of the doped films, and the underlying mechanisms for high-efficiency doping are still unclear. Here, through multi-level theoretical simulations on a series of fullerene derivatives, we identify that the energetic fluctuations can play a decisive role in activating charge separation for molecular doping. In particular, the doping efficiency appears to be exponentially increased with the fluctuation of charge polarization energies. Therefore, although the charge mobility is somewhat decreased, the experimental electrical conductivity is improved with the increased energetic fluctuation. Moreover, it has been found that polarization energy fluctuation can be effectively enhanced by simply introducing side chains with greater flexibility into organic semiconductors. This article paves the way towards high-efficiency molecular doping of organic semiconductors.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"67 11","pages":"3675 - 3680"},"PeriodicalIF":10.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142518880","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Multicolor circularly polarized phosphorescence of axially chiral binuclear platinum(II) complexes 轴向手性双核铂(II)配合物的多色圆偏振磷光

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-09-23 DOI: 10.1007/s11426-024-2124-3

Jintong Song, Rui Zeng, Hui Xiao, Hailiang Ni, Zong-Xiang Xu, Haifeng Xiang

{"title":"Multicolor circularly polarized phosphorescence of axially chiral binuclear platinum(II) complexes","authors":"Jintong Song, Rui Zeng, Hui Xiao, Hailiang Ni, Zong-Xiang Xu, Haifeng Xiang","doi":"10.1007/s11426-024-2124-3","DOIUrl":"10.1007/s11426-024-2124-3","url":null,"abstract":"<div><p>D-A charge transfer, including through-bond charge transfer and through-space charge transfer between two different electron donors (D) and electron acceptors (A), is a fundamental and powerful tool to tune the optical properties of organic dyes. Herein, we demonstrate a unique strategy to tune phosphorescence and circularly polarized luminescence properties of axially chiral binuclear Pt(II) complexes through long-range charge transfer, even though these molecules have two totally identical segments on either side of the chiral core. The presence of axial chirality would break not only the symmetry of molecular structure and π-conjugation system but also the symmetry of charge distribution for long-range charge transfer. These binaphthyl-based Pt(II) complexes bearing coordinated atoms far away from chiral axis exhibit no Pt-Pt interactions but colorful concentration-dependent phosphorescence with quantum yield up to 86.4% and could be applied as emitters in highly efficient solution-processed organic light-emitting diodes to achieve luminance, luminance efficiency, power efficiency, external quantum efficiency, and asymmetry factor up to 8.94 × 10<sup>3</sup> cd m<sup>−2</sup>,41.9 cd A<sup>−1</sup>,18.8 lm W<sup>−1</sup>, 12.6% and 2.98 × 10<sup>−3</sup>, respectively. Therefore, the present work affords a new and simple way to utilize the inherently asymmetric advantage of chirality for the design of D-A-based organic dyes.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"67 11","pages":"3757 - 3766"},"PeriodicalIF":10.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142518882","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Benzoyl cyanide, a general radical acylating reagent for photoredox-catalyzed benzylic site-selective acylation reactions 苯甲酰腈，一种用于光氧化催化苄基位点选择性酰化反应的通用自由基酰化试剂

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-09-23 DOI: 10.1007/s11426-024-2309-5

Zhaodong Zhu, Jingjing Wu

引用次数: 0

Visible-light-responsive homologous heterostructure of oxynitrides constructed to boost charge separation and water splitting 用于促进电荷分离和水分裂的氮氧化物的可见光响应同源异质结构

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-09-23 DOI: 10.1007/s11426-024-2208-3

Hai Zou, Yunfeng Bao, Xueshang Xin, Yu Qi, Tengfeng Xie, Fuxiang Zhang

{"title":"Visible-light-responsive homologous heterostructure of oxynitrides constructed to boost charge separation and water splitting","authors":"Hai Zou, Yunfeng Bao, Xueshang Xin, Yu Qi, Tengfeng Xie, Fuxiang Zhang","doi":"10.1007/s11426-024-2208-3","DOIUrl":"10.1007/s11426-024-2208-3","url":null,"abstract":"<div><p>Constructing type II heterostructures represents a widely recognized strategy for enhancing charge separation and photocatalytic efficiency, but it remains challenging to fabricate homologous heterostructures based on visible-light-responsive semiconductors, especially for popularly investigated (oxy)nitrides with low thermal stability. Here, we synthesized a homologous heterostructure (denoted as YTON_H) based on the oxynitrides of YTaO<sub>4−<i>x</i></sub>N<sub><i>y</i></sub> and YTaON<sub>2</sub>. This heterostructure exhibits type II band structure alignment and intimate interface achieved through a magnesium (Mg) powder-assisted nitridation method. Compared with widely reported heterologous heterostructures, the as-obtained YTON_H homologous heterostructure could similarly exhibit enhanced charge separation as well as photocatalytic water splitting performance with respect to its counterparts (YTaO<sub>4−<i>x</i></sub>N<sub><i>y</i></sub> and YTaON<sub>2</sub>). Meanwhile, detailed structural characterizations and spectroscopy analysis have been made to confirm the formation of heterostructure and promotion of spatial charge separation.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 1","pages":"186 - 191"},"PeriodicalIF":10.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925606","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metal-organic polyhedra as dynamic cross-linker for recyclable mixed matrix membranes with promising dimension stability

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-09-23 DOI: 10.1007/s11426-024-2225-6

Linjie Lan, Mingxin Zhang, Haiyan Xiao, Wei Liu-Fu, Yuyan Lai, Jiadong Chen, Jia-Fu Yin, Panchao Yin

{"title":"Metal-organic polyhedra as dynamic cross-linker for recyclable mixed matrix membranes with promising dimension stability","authors":"Linjie Lan, Mingxin Zhang, Haiyan Xiao, Wei Liu-Fu, Yuyan Lai, Jiadong Chen, Jia-Fu Yin, Panchao Yin","doi":"10.1007/s11426-024-2225-6","DOIUrl":"10.1007/s11426-024-2225-6","url":null,"abstract":"<div><p>Mixed matrix membranes (MMMs) are designed by incorporating microporous inorganic fillers into polymer matrix for the integration of inorganics’ excellent gas separation performance with polymers’ promising flexibility. However, due to the complex interphase interaction, the prevention of long-term aging is still challenging and the poor processability/recyclability of MMMs hinders their extensive applications. Herein, a coordination assembly protocol is developed for the fabrication of MMMs with both excellent processability/recyclability upon thermal annealing and promising dimension stability even under high gas pressure. Polymers bearing isophthalic acid (IPA) as side chains are applied to coordinate with Cu<sup>2+</sup> and the assembled 2.5 nm microporous metal-organic polyhedra (MOP), {Cu<sub>24</sub>IPA<sub>24</sub>}, serves as multi-functional cross-linkers for the polymer network formation. The MOPs’ well-defined microporosity grants MMMs the capability for O<sub>2</sub>/N<sub>2</sub> separation while their activated dynamics at high temperatures (>120 °C) endows polymer networks with excellent processability. In contrast to conventional supramolecular units, the MOPs possess unique logarithmic ligand-exchange kinetics and they show nearly frozen bonding dynamics at room temperature, ensuring promising dimensional stability to overcome the long-term aging and high gas pressure effect. This work not only provides fundamental understanding of the unique relaxation dynamics of complex systems with intertwined dynamics of supramolecular bonds and polymer chains, but also paves new avenues for the fabrication of robust and recyclable MMMs and elastomers.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 2","pages":"705 - 713"},"PeriodicalIF":10.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11426-024-2225-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446560","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Why do CuAl catalysts outperform in CO2 electro-reduction to C2H4?

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-09-23 DOI: 10.1007/s11426-024-2292-3

Dongfang Cheng, Gong Zhang, Lulu Li, Xiangcheng Shi, Wenjin Zhu, Xintong Yuan, Lyudmila Moskaleva, Peng Zhang, Zhi-Jian Zhao, Jinlong Gong

{"title":"Why do CuAl catalysts outperform in CO2 electro-reduction to C2H4?","authors":"Dongfang Cheng, Gong Zhang, Lulu Li, Xiangcheng Shi, Wenjin Zhu, Xintong Yuan, Lyudmila Moskaleva, Peng Zhang, Zhi-Jian Zhao, Jinlong Gong","doi":"10.1007/s11426-024-2292-3","DOIUrl":"10.1007/s11426-024-2292-3","url":null,"abstract":"<div><p>Highly efficient CO<sub>2</sub> electroreduction (CO<sub>2</sub>RR) holds the promise of closing the carbon cycle. However, the strategies for enhancing activity and selectivity for single C<sub>2+</sub> products are still limited. This paper describes the oxophilicity of doped metals on copper (Cu) as a key descriptor for predicting the selectivity in the production of ethylene and ethanol in CO<sub>2</sub>RR. Our findings reveal a volcano-like relationship between the *O binding energy and catalytic activity, with aluminum (Al)-doped Cu alloys situated at the peak. The strong Al–O bond facilitates C–O bond cleavage, thereby promoting C<sub>2</sub>H<sub>4</sub> formation. Through grand canonical density functional theory (GCDFT) calculations, we elucidate the significance of strong oxygen affinity in enhancing *CO<sub>2</sub> adsorption, leading to its activation into a bidentate-adsorbed form. Moreover, our results demonstrate that Al doping promotes C–C coupling by altering the adsorption mode of the key intermediate *OCCO, shifting it from a less favorable boat-type to a more stable chair-type configuration. This modification significantly contributes to the improved catalytic activity for C<sub>2+</sub> products on CuAl catalysts. Our research provides a detailed mechanistic insight into the high activity and selectivity observed in CO<sub>2</sub>RR to ethylene on CuAl catalysts, underscoring the critical role of metal oxophilicity in enhancing CO<sub>2</sub>RR performance.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 2","pages":"763 - 771"},"PeriodicalIF":10.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11426-024-2292-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446562","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Establishing a new testing protocol of the electrochemical stability window for electric double-layer capacitors 建立了双层电电容器电化学稳定窗口的新测试方案

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-09-23 DOI: 10.1007/s11426-024-2216-7

Ruilin Hou, Xiaoxi Zhao, Tingting Liang, Qingyun Dou, Shan Xu, Xingbin Yan

{"title":"Establishing a new testing protocol of the electrochemical stability window for electric double-layer capacitors","authors":"Ruilin Hou, Xiaoxi Zhao, Tingting Liang, Qingyun Dou, Shan Xu, Xingbin Yan","doi":"10.1007/s11426-024-2216-7","DOIUrl":"10.1007/s11426-024-2216-7","url":null,"abstract":"<div><p>The electrochemical stability window (ESW) is crucial for determining the energy density of electric double-layer capacitors (EDLCs). However, current ESW testing protocols of EDLCs are strongly affected by artificial factors, thereby leading to unreliable result. To solve this problem, we first identify the key shortcomings of the traditional protocols by analyzing their test principles. Subsequently, taking an aqueous carbon-based EDLC as an example, we design a side reaction descriptor to represent the response difference in the charging capacitance to side reactions between the cyclic voltammetry and galvanostatic charge-discharge methods. With the aid of this descriptor, we propose a new ESW testing protocol, which is not only able to completely avoid the adverse influence of subjective factors but also fully consider the operating condition limitations. The protocol can be extended from the single electrode to the full device. This work proposes a more rigorous definition of ESW and provides a reliable protocol for evaluating the ESW of EDLCs.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 1","pages":"217 - 225"},"PeriodicalIF":10.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Intermolecular reductive coupling of aliphatic ketones with alkynes and alkenes by BCN photocatalysts BCN光催化剂催化脂肪族酮与炔烃和烯烃的分子间还原偶联

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-09-23 DOI: 10.1007/s11426-024-2226-5

Yanping Xia, Luyang Sun, Jiajia Cheng, Sibo Wang, Meifang Zheng, Xinchen Wang

引用次数: 0

Precise gradient separation of nanoparticles using reduced graphene oxide-polyoxomolybdate membranes 使用还原氧化石墨烯-多氧钼酸盐膜的纳米颗粒的精确梯度分离

IF 10.4 1区化学

Science China Chemistry Pub Date : 2024-09-20 DOI: 10.1007/s11426-024-2138-5

Yixin Yang, Wanlei Zhao, Ruoxuan Zheng, Hongqiang Li, Wei Chen, Yu-Fei Song

{"title":"Precise gradient separation of nanoparticles using reduced graphene oxide-polyoxomolybdate membranes","authors":"Yixin Yang, Wanlei Zhao, Ruoxuan Zheng, Hongqiang Li, Wei Chen, Yu-Fei Song","doi":"10.1007/s11426-024-2138-5","DOIUrl":"10.1007/s11426-024-2138-5","url":null,"abstract":"<div><p>The purification and size sieving of nanoparticles (NPs) represents a significant scientific challenge. Herein, the rGO-polyoxometalates (POMs = PMo<sub>12</sub>, Mo<sub>132</sub> and Mo<sub>368</sub>) membranes were fabricated successfully via a simple and scalable POMs-assisted <i>in-situ</i> photoreduction strategy. When the mass ratio of rGO to PMo<sub>12</sub> was 1:30, the resultant rGO-PMo<sub>12</sub> membranes with highly ordered and uniform nanochannels of 1.0 nm can be obtained, which showed an accurate carbon quantum dots (CQDs) separation with a cut-off size approximately 1.0 nm. Further increase of the size of the interlayered POMs from PMo<sub>12</sub> (1.0 nm), {Mo<sub>132</sub>} (2.9 nm) to {Mo<sub>368</sub>} (3.8 nm), the resultant rGO-PMo<sub>12</sub>, rGO-Mo<sub>132</sub> and rGO-Mo<sub>368</sub> exhibited precise gradient separation of CQDs and Au nanoparticles by size exclusion effect. The results pave a promising way to construct new two-dimensional (2D) membranes for highly efficient size-selective separation.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":"68 1","pages":"209 - 216"},"PeriodicalIF":10.4,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0