物理化学学报最新文献

{"title":"Atomically precise (AgPd)27 nanoclusters for nitrate electroreduction to NH3: Modulating the metal core by a ligand induced strategy","authors":"Lubing Qin ,&nbsp;Fang Sun ,&nbsp;Meiyin Li ,&nbsp;Hao Fan ,&nbsp;Likai Wang ,&nbsp;Qing Tang ,&nbsp;Chundong Wang ,&nbsp;Zhenghua Tang","doi":"10.3866/PKU.WHXB202403008","DOIUrl":"10.3866/PKU.WHXB202403008","url":null,"abstract":"<div><div>Electrochemical nitrate reduction reaction (eNO₃^–RR) to synthesize NH₃ is a sustainable method to convert environmental contaminants into valuables. Pd based bimetallic nanocatalysts have demonstrated great promise as efficient catalysts, yet modulating the composition and configuration to improve the catalytic performance and achieve comprehensive mechanistic understanding remains challenging. Herein, by employing two ligands with different electron functional groups, we successfully prepared two atomically precise (AgPd)₂₇ bimetallic clusters of Ag₁₈Pd₉(C₈H₄F)₂₄ (Ag₁₈Pd₉) and Ag₂₂Pd₅(C₉H₁₀O₂)₂₆ (Ag₂₂Pd₅). The two clusters possess markedly different metal core composition and configuration, where Ag₁₈Pd₉ has a sandwich metal core structure with 9 Pd atoms located in the middle layer and Ag₂₂Pd₅ has a rod-shaped metal core structure composed of the M₁₃ configuration with 5 Pd atoms located at the center and vertices of the M₁₃ configuration. Unexpectedly, Ag₂₂Pd₅ exhibited remarkably superior eNO⁻₃RR performance than Ag₁₈Pd₉. Specifically, the highest Faradaic efficiency of NH₃ (FE_NH3) and its yield rate can reach 94.42 % and 1.41 mmol h⁻¹ mg⁻¹ at −0.6 V <em>vs</em>. RHE for Ag₂₂Pd₅, but the largest FE_NH3 and NH₃ yield rate is only 43.86 % and 0.41 mmol h⁻¹ mg⁻¹ at −0.5 V <em>vs</em>. RHE for Ag₁₈Pd₉. The <em>in situ</em> attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) test provides the experimental evidence of the reaction intermediates hence revealing the reaction pathway, also shows that Ag₂₂Pd₅ has stronger capability for NO⁻₃ adsorption and NH₃ desorption than that of Ag₁₈Pd₉. Theoretical calculations indicate that the de-ligated clusters can expose the available AgPd bimetallic sites, synergistically serving as effective active sites and the different configurations result in significantly different catalytic activities, where the active sites in Ag₂₂Pd₅ are more favorable for NO⁻₃ adsorption and NH₃ desorption to accelerate the catalytic process.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 1","pages":"Article 100008"},"PeriodicalIF":10.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143154599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nucleation regulation and mechanism of precursors for nickel cobalt manganese-based cathode materials in lithium-ion batteries","authors":"Jiaxuan Zuo ,&nbsp;Kun Zhang ,&nbsp;Jing Wang ,&nbsp;Xifei Li","doi":"10.3866/PKU.WHXB202404042","DOIUrl":"10.3866/PKU.WHXB202404042","url":null,"abstract":"<div><div>Nickel cobalt manganese-based cathode materials (NCMs) have emerged as key representatives in lithium-ion power batteries due to their high energy and power densities. The layered crystal structure of NCMs undergoes topological transformation from hydroxide precursor materials crystals. Therefore, the electrochemical performance of NCMs is directly influenced by factors such as particle size distribution, sphericity, and morphology of primary and secondary particles of precursor materials. The co-precipitation method is widely employed in laboratory and industry to produce batch precursor materials with uniform composition, adjustable structure, and high tap density. However, the co-precipitation process involves numerous adjustable parameters, and there exist significant variations in the growth parameters of precursors with different compositions and even different particle sizes within the same composition, resulting in poor characteristics such as bad sphericity, poor crystallinity, and low tap density. Addressing the need for controlled co-precipitation of nickel cobalt manganese-based precursors, this review began with an exposition on the basic theory of co-precipitation, elaborating on the principle of regulating precipitation rate and uniformity of Ni–Co–Mn elements through complexation. The heterogeneous nucleation (growth), homogeneous nucleation (independent nucleation), and the coexistence of two nucleation modes induced by different supersaturation of precipitates were explained according to different nucleation dominant modes. The growth theory of hexagonal nanosheet and rod-shaped primary particles was introduced from the perspective of preferential growth, while analyzing the growth pattern of secondary particle aggregates in terms of minimizing surface energy and following dissolving-recrystallization. From the viewpoint of practical production and application, this study comprehensively investigated adjustable parameters of the co-precipitation reaction process, including pH value, total ammonia concentration, solid content, reaction time, reaction temperature, base solution volume, stirring rate, tank reactor structure, aging time, reaction atmosphere, and drying atmosphere. The impact of varying each parameter from low to high on the nucleation of the co-precipitation reaction process and the physicochemical properties of precursors was extensively discussed. This systematic review contributes to a deeper understanding of the precursor nucleation process, facilitating the further development of relevant theories towards the advancement of products such as lithium-rich manganese-based precursors, single crystal precursors, and radially arranged texture precursors.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 1","pages":"Article 100009"},"PeriodicalIF":10.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143154596","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sulfide solid electrolyte synthesized by liquid phase approach and application in all-solid-state lithium batteries","authors":"Mingyang Men ,&nbsp;Jinghua Wu ,&nbsp;Gaozhan Liu ,&nbsp;Jing Zhang ,&nbsp;Nini Zhang ,&nbsp;Xiayin Yao","doi":"10.3866/PKU.WHXB202309019","DOIUrl":"10.3866/PKU.WHXB202309019","url":null,"abstract":"&lt;div&gt;&lt;div&gt;Current commercialized lithium-ion batteries generally suffer from safety issues due to using flammable organic liquid electrolytes. All-solid-state lithium batteries employing solid electrolytes instead of organic liquid electrolytes and separators possess the advantages of both good safety and high energy density, which are expected to be the most promising energy storage devices for the next generation electric vehicles and smart grid. Sulfide solid electrolytes are regarded as crucial components for all-solid-state rechargeable batteries for the merits of their high room temperature ionic conductivities that approach or exceed liquid organic electrolytes and excellent mechanical ductility. The preparation methods of sulfide solid electrolytes are mainly divided into three categories, &lt;em&gt;i.e.&lt;/em&gt; solid-state sintering, ball milling and liquid-phase method. However, solid-state sintering and ball milling are time-consuming accompanied by high energy consumption. At the same time, the synthesized electrolyte particles are large in size, which seriously limits the practical application of sulfide solid electrolytes. In contrast, the liquid-phase method, using organic solvents as the medium, can synthesize sulfide solid electrolytes with controlled particle sizes, which is a simple and time-saving process and more suitable for large-scale production. In this review, we begin by introducing the crystal structures and ion transport mechanisms of major sulfide solid electrolytes including Li&lt;sub&gt;2&lt;/sub&gt;S–P&lt;sub&gt;2&lt;/sub&gt;S&lt;sub&gt;5&lt;/sub&gt; binary sulfide solid electrolytes, Li&lt;sub&gt;10&lt;/sub&gt;GeP&lt;sub&gt;2&lt;/sub&gt;S&lt;sub&gt;12&lt;/sub&gt; and Li&lt;sub&gt;6&lt;/sub&gt;PS&lt;sub&gt;5&lt;/sub&gt;X (X ​= ​Cl, Br, I) ternary systems, and summarize the progress of sulfide solid electrolytes prepared by liquid phase method in recent years. Based on the solubility state of the reagents in the solvent, the liquid-phase synthesis of sulfide solid electrolytes can be categorized into suspension type, solution type and mixed type, and their reaction mechanisms are discussed separately. Subsequently, we summarize the effect of solvents on the properties of liquid-phase synthesized sulfide solid electrolytes, such as purity, morphology, crystallinity and ionic conductivity. In addition, the application of liquid-phase synthesized sulfide solid electrolytes for all-solid-state lithium batteries is presented from six aspects: sulfide solid electrolytes coated on active materials, electrolyte-active material composites, electrolyte injection into porous electrodes, interfacial modification at solid-solid contact triple-interfaces within electrode layers, electrolyte elemental doping and electrolyte film preparation, which demonstrates the superior scalability of the liquid-phase method and the diverse application prospects. Finally, according to the current research status of the sulfide solid electrolytes synthesized by liquid phase method, the advantages and limitations of the liquid phase synthesis of su","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 1","pages":"Article 100004"},"PeriodicalIF":10.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143154608","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of interlayer anions in layered double hydroxides on the photothermocatalytic CO2 methanation of derived Ni–Al2O3 catalysts","authors":"Lina Guo ,&nbsp;Ruizhe Li ,&nbsp;Chuang Sun ,&nbsp;Xiaoli Luo ,&nbsp;Yiqiu Shi ,&nbsp;Hong Yuan ,&nbsp;Shuxin Ouyang ,&nbsp;Tierui Zhang","doi":"10.3866/PKU.WHXB202309002","DOIUrl":"10.3866/PKU.WHXB202309002","url":null,"abstract":"&lt;div&gt;&lt;div&gt;The concentration of carbon dioxide (CO&lt;sub&gt;2&lt;/sub&gt;) in the atmosphere is progressively increasing due to industrial development, leading to environmental concerns such as the greenhouse effect. Consequently, it is crucial to decrease dependence on the fossil fuels and mitigate the CO&lt;sub&gt;2&lt;/sub&gt; emissions. Photothermocatalysis technology facilitates the conversion of light energy into heat energy on the surface of catalysts, thereby driving chemical reactions. This catalytic approach effectively harnesses ample solar energy, consequently reducing non-renewable energy consumption. Solar-driven CO&lt;sub&gt;2&lt;/sub&gt; methanation is an important route to simultaneously mitigate excessive carbon emissions and produce fuels. Layered double hydroxides (LDH) can be reduced at high temperature in a reductive atmosphere of a hydrogen/argon (H&lt;sub&gt;2&lt;/sub&gt;/Ar) mixture to prepare metal-loaded oxide (MO) catalysts, which are widely used in CO&lt;sub&gt;2&lt;/sub&gt; hydrogenation reactions as excellent photothermal catalysts. However, there is limited study on how the interlayer anion type of LDH affects the activity of CO&lt;sub&gt;2&lt;/sub&gt; methanation. Herein, a series of LDH precursors, intercalated with various anions, were synthesized using a co-precipitation method. The LDH precursors were reduced in a H&lt;sub&gt;2&lt;/sub&gt;/Ar atmosphere to acquire a group of nickel (Ni) loaded on alumina (Al&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;3&lt;/sub&gt;) catalysts, referred to as NiAl-x-MO (x = CO&lt;sub&gt;3&lt;/sub&gt;, NO&lt;sub&gt;3&lt;/sub&gt;, Cl, and SO&lt;sub&gt;4&lt;/sub&gt;, which represents carbonate, nitrate, chloride, and sulfate anions, respectively). Energy dispersive spectrometer (EDS) elemental mapping and X-ray photoelectron spectroscopy (XPS) results revealed the presence of nitrogen (N), chlorine (Cl), and sulfur (S) species on the surfaces of NiAl–NO&lt;sub&gt;3&lt;/sub&gt;-MO, NiAl–Cl-MO, and NiAl–SO&lt;sub&gt;4&lt;/sub&gt;-MO catalysts, respectively. Photothermocatalytic tests were conducted on the catalysts to assess the potential influence of the residual species on CO&lt;sub&gt;2&lt;/sub&gt; methanation. Among them, the NiAl–CO&lt;sub&gt;3&lt;/sub&gt;-MO catalyst demonstrated a CO&lt;sub&gt;2&lt;/sub&gt; conversion of 50.1 %, methane (CH&lt;sub&gt;4&lt;/sub&gt;) selectivity of 99.9 %, along with a CH&lt;sub&gt;4&lt;/sub&gt; production rate of 94.4 mmol g&lt;sup&gt;−1&lt;/sup&gt; h&lt;sup&gt;−1&lt;/sup&gt;. The performance of the NiAl–NO&lt;sub&gt;3&lt;/sub&gt;-MO catalyst was found to be comparable to that of the NiAl–CO&lt;sub&gt;3&lt;/sub&gt;-MO catalyst. In contrast, the CO&lt;sub&gt;2&lt;/sub&gt; methanation activity of the NiAl–Cl-MO and NiAl–SO&lt;sub&gt;4&lt;/sub&gt;-MO catalysts were negligible. CO&lt;sub&gt;2&lt;/sub&gt; temperature programmed desorption (CO&lt;sub&gt;2&lt;/sub&gt;-TPD) analysis demonstrated that the presence of N, Cl, and S species had a negligible effect on the adsorption of CO&lt;sub&gt;2&lt;/sub&gt;. H&lt;sub&gt;2&lt;/sub&gt; temperature programmed desorption (H&lt;sub&gt;2&lt;/sub&gt;-TPD) and density functional theory (DFT) results suggested that the strong coordination bond between residual Cl or S species and metallic Ni impeded the absorption and activation of H&lt;sub&gt;2&lt;/sub&gt;, which was responsible for","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 1","pages":"Article 100002"},"PeriodicalIF":10.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143154601","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Design strategy for thermally activated delayed fluorescence materials with multiple resonance effect","authors":"Zehua Zhang,&nbsp;Haitao Yu,&nbsp;Yanyu Qi","doi":"10.3866/PKU.WHXB202309042","DOIUrl":"10.3866/PKU.WHXB202309042","url":null,"abstract":"<div><div>Since the initial report on multiple resonance thermally activated delayed fluorescence (MR-TADF) molecules, their narrow band emissions, high quantum yields and other characteristics have consistently fueled research interest in the realm of organic electronics, particularly organic light emitting diodes (OLED). These molecules swiftly ascended to the forefront of research, serving as a pivotal focus, giving rise to numerous high-performance devices and meticulously crafted molecules. Devices featuring MR-TADF molecules as the luminescent core continually redefine our comprehension of OLED, with some employing hyperfluorescence technology attaining peak performance in specific photochromic domains today. Presently, with the escalating demand for ultra-high-resolution displays, the international telecommunication union (ITU) has unveiled the next generation color gamut standard, BT.2020. This standard delineates the broadest display color gamut, mandating monochromatic primary color wavelengths of 467, 532, and 630 nm, constituting an exceptionally extensive color gamut. Simultaneously, achieving high-resolution displays with such an expansive color gamut imposes unprecedentedly stringent requirements on the color purity of device elements. Consequently, it imposes a formidable color purity target for display technology. In the past, traditional fluorescent materials struggled to meet these demands. The advent of BT.2020, however, has presented new opportunities for the advancement of MR-TADF molecules, leading to a surge in popularity in this field. In recent years, with copious research and practical applications, the MR-TADF molecular family has undergone rapid evolution. Nevertheless, discussions and summaries primarily centered on the field's development, with limited focus on molecular design strategies. This deficiency hinders adequate reference for researchers entering the field. Consequently, this article expounds upon the design principles of select MR-TADF molecules reported in the past three years. It delves into aspects such as the X-<em>π</em>-X principle, fast reverse intersystem crossing processes, narrow-band emission, and high oscillator strength. Additionally, it posits future design directions, including the incorporation of non-traditional structures into the MR-TADF domain. Finally, the article offers suggestions for the prospective development and industrialization of the MR-TADF field.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 1","pages":"Article 100006"},"PeriodicalIF":10.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143155047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photomultiplication-type all-polymer photodetectors and their applications in photoplethysmography sensor","authors":"Xingchao Zhao ,&nbsp;Xiaoming Li ,&nbsp;Ming Liu ,&nbsp;Zijin Zhao ,&nbsp;Kaixuan Yang ,&nbsp;Pengtian Liu ,&nbsp;Haolan Zhang ,&nbsp;Jintai Li ,&nbsp;Xiaoling Ma ,&nbsp;Qi Yao ,&nbsp;Yanming Sun ,&nbsp;Fujun Zhang","doi":"10.3866/PKU.WHXB202311021","DOIUrl":"10.3866/PKU.WHXB202311021","url":null,"abstract":"&lt;div&gt;&lt;div&gt;Photomultiplication-type all-polymer photodetectors (PM-APDs) based on structure of ITO/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/active layer/Al were developed with wide bandgap polymer poly(3-hexylthiophene) (P3HT) as donor and narrow bandgap polymer poly{2,2&lt;em&gt;ʹ&lt;/em&gt;-((2Z,2&lt;em&gt;ʹ&lt;/em&gt;Z)-((12,13-bis(2-decyltetradecyl)-6-(2-ethylhexyl)-4,8-dimethyl-6,8,12,13-tetrahydro-4&lt;em&gt;H&lt;/em&gt;-thieno[2&lt;em&gt;ʹʹ&lt;/em&gt;,3&lt;em&gt;ʹʹ&lt;/em&gt;:4&lt;em&gt;ʹ&lt;/em&gt;,5&lt;em&gt;ʹ&lt;/em&gt;]pyrrolo[2&lt;em&gt;ʹ&lt;/em&gt;,3&lt;em&gt;ʹ&lt;/em&gt;:4,5]pyrrolo[3,2-g]thieno[2&lt;em&gt;ʹ&lt;/em&gt;,3&lt;em&gt;ʹ&lt;/em&gt;:4,5]pyrrolo[3,2-b][1,2,3] triazolo[4,5-e]indole-2,10-diyl)bis(methaneylylidene))bis(5,5&lt;em&gt;ʹ&lt;/em&gt;-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile-alt-2,5-dithiophene} (PTz-PT) as acceptor. A series of binary PM-APDs were prepared with P3HT:PTz-PT weight ratios of 100 : 1, 100 : 4, 100 : 7, and 100 : 10. In the dark, the holes are difficultly injected from Al electrode into the active layer due to the 0.8 ​eV injection barriers from the work function of Al onto the highest occupied molecular orbital (HOMO) level of P3HT. The limited PTz-PT content in the active layer results in the absence of continuous electron transport channel, leading to poor electron transport ability. The photogenerated electrons are trapped in isolated PTz-PT under light illumination due to the scarce PTz-PT content in active layer and 0.84 ​eV difference between the lowest unoccupied molecular orbital (LUMO) of P3HT and PTz-PT. The trapped electrons near the Al electrode induce interfacial band bending for hole tunneling injection, leading to external quantum efficiency (EQE) values exceeding 100 ​%. The optimal binary PM-APDs based on P3HT:PTz-PT (100 : 4 ​wt/wt) exhibit a spectral response range from 300 to 1100 ​nm with EQE values over 100 ​% at −8 ​V bias. The EQE spectral shape of PM-APDs is determined by the distribution of trapped electrons near the Al electrode. The shape of EQE spectra is further flattened by introducing polymer poly(2-(4,8-bis(4-(2-ethylhexyl)cyclopenta-1,3-dien-1-yl)benzo[1,2-b:4,5-b']dithiophen-2-yl)-5,5-difluoro-10-(5-(2-hexyldecyl)thiophen-2-yl)-3,7-dimethyl-5&lt;em&gt;H&lt;/em&gt;-4λ4,5λ4-dipyrrolo[1,2-c:2&lt;em&gt;ʹ&lt;/em&gt;,1&lt;em&gt;ʹ&lt;/em&gt;-f][1,3,2]diazaborinine) (PMBBDT) as the third component. A series of ternary PM-APDs with P3HT:PMBBDT:PTz-PT weight ratios of 90 : 10: 4 and 80 : 20: 4 were prepared. The EQE values of ternary PM-APDs are increased in the range from 420 to 600 ​nm and decreased in the range from 630 to 870 ​nm. The flatter EQE spectra of ternary PM-APDs are derived from more uniform distribution of trapped electrons near the Al electrode. Furthermore, the ternary PM-APDs exhibit higher stability under continuous illumination and applied bias than the optimal binary PM-APDs. The optimal ternary PM-APDs exhibit EQE values of 3500 ​% at 350 ​nm, 1250 ​% at 550 ​nm and 1500 ​% at 900 ​nm under −12 ​V bias, as well as specific detectivity (&lt;em&gt;D&lt;/em&gt;∗&lt;sub&gt;shot&lt;/sub&gt;) values of 3.7 ​× ​10&lt;sup","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 1","pages":"Article 100007"},"PeriodicalIF":10.8,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143154600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Research progress on carbon-based catalysts for catalytic dehydrogenation of liquid organic hydrogen carriers","authors":"Xuejie Wang ,&nbsp;Guoqing Cui ,&nbsp;Congkai Wang ,&nbsp;Yang Yang ,&nbsp;Guiyuan Jiang ,&nbsp;Chunming Xu","doi":"10.1016/j.actphy.2024.100044","DOIUrl":"10.1016/j.actphy.2024.100044","url":null,"abstract":"<div><div>Hydrogen energy is a widely available, flexible and efficient secondary energy source, and it is also an important energy medium. The development of low-cost, high-density hydrogen storage technology is a significant issue for the industrial application of hydrogen energy. Liquid organic hydrogen storage has attracted extensive attention due to advantages such as high mass hydrogen storage density, safe storage and transportation, as well as ease of long-distance transportation. However, compared with the relatively mature hydrogenation process, the dehydrogenation of liquid organic hydrogen carriers (LOHCs) still suffers from high reaction temperature and low efficiency. The key to solving these problems is the development of efficient dehydrogenation catalysts. In recent years, carbon-based catalysts have shown excellent reaction performance in the dehydrogenation of LOHCs due to their advantages of high dispersion of active components, tunable composition structure and surface physicochemical properties, and outstanding electrical and thermal conductivity, etc. In this review, we initially analyze the thermodynamics and kinetics of dehydrogenation, as well as the physicochemical properties of LOHCs, including cyclohexane, methylcyclohexane, decalin, and perhydro-<em>N</em>-ethylcarbazole. The special features of carbon supports are then outlined in terms of the activated carbon, carbon nanotubes, carbon fibers, and reduced graphene oxide. In addition, the structural characteristics, catalytic performance, structure-property relationship, and dehydrogenation mechanism of carbon-supported metal catalysts are summarized and analyzed. Based on this, we point out the main challenges of liquid organic hydrogen storage. Furthermore, future opportunities in this field are envisioned, with an emphasis on the modification and structuration of carbon support, the study of catalytic mechanisms and chemical process intensification.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100044"},"PeriodicalIF":10.8,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164162","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Highly efficient, targeted, and traceable perovskite nanocrystals for photoelectrocatalytic oncotherapy","authors":"Jian Li ,&nbsp;Yu Zhang ,&nbsp;Rongrong Yan ,&nbsp;Kaiyuan Sun ,&nbsp;Xiaoqing Liu ,&nbsp;Zishang Liang ,&nbsp;Yinan Jiao ,&nbsp;Hui Bu ,&nbsp;Xin Chen ,&nbsp;Jinjin Zhao ,&nbsp;Jianlin Shi","doi":"10.1016/j.actphy.2024.100042","DOIUrl":"10.1016/j.actphy.2024.100042","url":null,"abstract":"&lt;div&gt;&lt;div&gt;Metal halide perovskites have emerged as highly promising materials in optoelectronics, owing to their unique multidimensional crystal structures that impart exceptional optical and electronic properties. These materials exhibit remarkable fluorescence imaging and tracking capabilities, as well as efficient photoelectric conversion, making them suitable for a broad range of applications. Nevertheless, despite their significant potential, their poor water stability has posed a major challenge, particularly in biomedical fields such as drug delivery systems, biological imaging, and photoelectrocatalytic oncotherapy. This limitation has hindered their practical use in medical treatments and diagnostics. In this study, we address the water stability issue by successfully synthesizing CsSn&lt;sub&gt;0.5&lt;/sub&gt;Pb&lt;sub&gt;0.5&lt;/sub&gt;Br&lt;sub&gt;3&lt;/sub&gt; perovskite nanocrystals (PeNCs) and conjugating them with methotrexate-chitosan-folic acid (MTX-CS-FA), resulting in innovative green light-emitting PeNCs@MTX-CS-FA nanoparticles. These nanoparticles exhibited remarkable water stability, maintaining their structural and functional integrity for up to 228 days, a significant improvement that enables their application in complex biological environments. Under visible light illumination, the nanoparticles demonstrated a dual-action therapeutic mechanism. The perovskites effectively generated electrons and reactive oxygen species (ROS), inducing oxidative stress in tumor cells. At the same time, photogenerated holes oxidized glutathione (GSH), a molecule that is typically overexpressed in tumor cells to protect against oxidative damage. By depleting GSH, the nanoparticles weakened the tumor cells' defense mechanisms, thereby enhancing the oxidative damage caused by ROS. In addition, methotrexate (MTX), a chemotherapeutic agent integrated into the system, inhibited dihydrofolate reductase (DHFR) activity. This inhibition disrupted tumor cell metabolism, particularly nucleotide synthesis, leading to lipid peroxidation and subsequent cell death. Together, these mechanisms generated a potent, synergistic therapeutic effect. The therapeutic efficacy of the PeNCs@MTX-CS-FA nanoparticles was validated through in vivo antitumor experiments in mice. A total dose of 2.4 ​mg of nanoparticles resulted in a 63.68 ​% reduction in tumor volume and a 63.26 ​% decrease in tumor weight, demonstrating significant tumor growth suppression. Biological safety evaluations further confirmed the nanoparticles' biocompatibility. Notably, they were excreted from the mice in their fluorescent form without decomposition, ensuring minimal long-term toxicity. This safe excretion pathway underscores the feasibility of repeated use of these nanoparticles in clinical applications. Overall, this study highlights the transformative potential of metal halide perovskites in cancer treatment. By overcoming the water stability limitations that have previously constrained their biomedical applications, the ","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100042"},"PeriodicalIF":10.8,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143369068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Interfacial electrical double layer in electrocatalytic reactions: Fundamentals, characterizations and applications","authors":"Xueting Cao,&nbsp;Shuangshuang Cha,&nbsp;Ming Gong","doi":"10.1016/j.actphy.2024.100041","DOIUrl":"10.1016/j.actphy.2024.100041","url":null,"abstract":"<div><div>The interfacial electrical double layer (EDL) is the interfacial space filled with a complex and dynamic reaction network formed by catalyst's surface atoms, reactants, intermediates, products, solvent molecules, ions, and other components. EDL has a profound impact on electrocatalytic reactions, affecting both the thermodynamics and kinetics of these processes. Manipulating the composition and structure of the EDL microenvironment sets an additional level of tuning toward the electrocatalysis, to the traditional catalyst optimization. It resembles the delicate manipulation of the environment around the active sites by protein scaffold in enzymes. However, the rational optimization of the EDL demands a deep understanding of its structure and dynamics. Problems lie in the complexities of interfacial EDL, which include complicated multi-body interactions, few molecular-level characterization techniques, and scarce EDL modification strategies.</div><div>In this tutorial, we delve into the intricacies of the interfacial EDL in electrocatalytic reactions and seek to provide those who are new to this field a thorough summary of the theory, characterization, history, recent progress within the regime of EDL for electrocatalysis. We begin by discussing the theoretical models that describe the structure and properties of EDL, including 4 classical EDL models, their applications in electrocatalytic analysis and modifications, and relevant calculation modulation methods. These models are arranged chronologically, such that a historical summary of how the EDL theory evolves from simple models to complicated details is provided. We then provide an overview of cutting-edge techniques in electrochemical measurement methods, <em>in situ</em> spectroscopic characterization techniques, and scanning probe microscopy methods. Specifically, we aim to summarize the advantages and disadvantages of each technique, with an emphasis on their capability of probing the EDL region. The summary table can provide junior students with a quick overview and a useful tool for selecting the appropriate techniques toward addressing the EDL properties for electrocatalysis. Furthermore, by combining the theory and characterization techniques, we list several pivotal studies from the past five years emphasizing the “electrode side interfacial modification” approach and the “solution side interfacial modification” approach, toward modulating the EDL to optimize the electrocatalytic properties. These examples not only show the recent progress in this field and offer fundamental details about how researchers in this field address the problems from the aspect of EDL. With these combined theory, characterization and research samples, we hope that the newcomers can gain interest in this field, sense the enormous opportunities and understand the general principles of EDL toward electrocatalysis.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100041"},"PeriodicalIF":10.8,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143102963","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recent progress of microstructure-regulated g-C3N4 in photocatalytic NO conversion: The pivotal roles of adsorption/activation sites","authors":"Hui Wang ,&nbsp;Abdelkader Labidi ,&nbsp;Menghan Ren ,&nbsp;Feroz Shaik ,&nbsp;Chuanyi Wang","doi":"10.1016/j.actphy.2024.100039","DOIUrl":"10.1016/j.actphy.2024.100039","url":null,"abstract":"<div><div>Photocatalytic nitric oxide (NO) conversion technology has the characteristics of high efficiency, economy, and environment friendly to remove NO using g-C₃N₄. Introducing new adsorption sites on the surface of g-C₃N₄ through microstructure control can alter the structure-activity relationship between g-C₃N₄ and gas molecules, thereby improving photocatalytic NO conversion activity and inhibiting NO₂ generation. However, few review articles have focused on the microscopic effects of microstructural changes in g-C₃N₄ based materials on the adsorption and activation of NO and O₂. This has important guiding significance for material design work in the field of NO conversion and strategies to fundamentally improve NO conversion activity and selectivity. Therefore, our work systematically summarizes the strategy of introducing adsorption and activation sites through microstructure control, and emphasizes the role of these sites in the photocatalytic NO conversion process. The aim is to clarify the influence of adsorption and activation sites on adsorption behavior and the correlation between these sites and reaction paths. Finally, the development trend and future prospects of increasing the level of g-C₃N₄ adsorption and activation in the field of photocatalytic NO conversion are introduced, which is expected to provide an important reference for the development and practical application of g-C₃N₄-based photocatalytic materials.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100039"},"PeriodicalIF":10.8,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143102413","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}