物理化学学报最新文献

{"title":"Boron-containing MFI zeolite: Microstructure control and its performance of propane oxidative dehydrogenation","authors":"Pei Li,&nbsp;Yuenan Zheng,&nbsp;Zhankai Liu,&nbsp;An-Hui Lu","doi":"10.3866/PKU.WHXB202406012","DOIUrl":"10.3866/PKU.WHXB202406012","url":null,"abstract":"<div><div>Boron-containing zeolites can catalyze the oxidative dehydrogenation of propane (ODHP) to produce propylene. Enhancing the quantity of active boron-oxygen species and regulating the positioning of these species within the zeolite are the main challenges in developing efficient boron-based catalysts. In this study, a boron-containing zeolite catalyst with exposed (010) crystal facets, referred to as the MFI-type boron-containing zeolite (BMFI), was synthesized using a urea-assisted hydrothermal method. The research indicates that the addition of an appropriate amount of urea can regulate the morphology of the zeolite, with its short-axis flake-like structure enhancing the accessibility of active boron sites and anchoring a higher content of active boron-oxygen species through hydrogen bonding, which significantly improves the ODHP activity and olefin selectivity of the catalyst. The propane conversion rate reached 20 %, with a propylene selectivity of 62.3 % and a total olefin selectivity of 81.3 % at 520 °C. Compared to the ellipsoidal boron-containing catalyst formed without urea, the sheet-like BMFI catalyst exhibited nearly a 20-fold increase in the reaction rate of propane. The flake-like BMFI possesses a greater number of framework tetrahedrally coordinated boron (B[4]) and defective boron species (B[3]^a and B[3]^b), and active boron structural evolution occurred during the reaction process, with B[3]^a and B[3]^b being the active sites for the catalytic reaction. This study provides a reference for the structural design and regulation of boron-based catalysts for the oxidative dehydrogenation of light alkanes.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 4","pages":"Article 100034"},"PeriodicalIF":10.8,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093636","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":"Preparation of high density activated carbon by mechanical compression of precursors for compact capacitive energy storage","authors":"Qiqi Li ,&nbsp;Su Zhang ,&nbsp;Yuting Jiang ,&nbsp;Linna Zhu ,&nbsp;Nannan Guo ,&nbsp;Jing Zhang ,&nbsp;Yutong Li ,&nbsp;Tong Wei ,&nbsp;Zhuangjun Fan","doi":"10.3866/PKU.WHXB202406009","DOIUrl":"10.3866/PKU.WHXB202406009","url":null,"abstract":"<div><div>Activated carbons are widely used as the electrode material for supercapacitors owing to their large surface area, moderate conductivity, and outstanding electrochemical stability. However, large-surface-area activated carbons usually show low density and poor volumetric energy storage performance, which is difficult to meet the development of devices miniaturization. Mechanical compression is a simple and effective method to improve the density of the activated carbons. However, most of the studies focus on mechanical compression of the as-prepared porous carbon materials. Preparation of high-density activated carbons by mechanical compression of the carbon precursors has been proposed. But the surface area and porous structure evolution, and the possible mechanism have rarely investigated. Herein, we propose a universal method to improve the density of the activated carbons by mechanical compression of the precursors before activation. The influence of mechanical compression on the surface area, porous structure, and capacitive energy storage performance of the activated carbons prepared by two typical methods, outside-in activation (carbon powder/KOH mixture) and homogeneous ion activation (pyrolysis of potassium-containing salts), are studied. Mechanical compression of the precursors can generally improve the activation reaction efficiency, as well as the density and volumetric capacitive performance of the activated carbons. However, the surface area and porous structure evolution mainly depend on the carbon precursor and pore-forming process. For outside-in activation, the surface area and porosity of the activated carbons show a first increasing and then decreasing trend with the increase of mechanical pressure. This is because mechanical compression enhances the contact between the carbon precursors and activator through eliminating the voids between particles, significantly improves the activation efficiency. For homogeneous ion activation, the surface area and porosity of activated carbons show a trend of decreasing first and then increasing. The reason is deduced as compressed precursors inhibit the rapid release of active gas molecules (H₂O, CO₂ <em>etc</em>.) produced during pyrolysis. These gas molecules further participate in the activation etching reaction and promote the activation efficiency. The optimized sample shows high gravimetric and volumetric capacitances of 316 F g⁻¹/291 F cm⁻³ and 131 F g⁻¹/92 F cm⁻³ at 1 A g⁻¹ in aqueous and organic electrolytes, respectively. This work provides a simple way for design and preparation of activated carbons with large surface area and high density.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 3","pages":"Article 100028"},"PeriodicalIF":10.8,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143181297","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":"NbSe2 nanosheets improved the buried interface for perovskite solar cells","authors":"Pengyu Dong ,&nbsp;Yue Jiang ,&nbsp;Zhengchi Yang ,&nbsp;Licheng Liu ,&nbsp;Gu Li ,&nbsp;Xinyang Wen ,&nbsp;Zhen Wang ,&nbsp;Xinbo Shi ,&nbsp;Guofu Zhou ,&nbsp;Jun-Ming Liu ,&nbsp;Jinwei Gao","doi":"10.3866/PKU.WHXB202407025","DOIUrl":"10.3866/PKU.WHXB202407025","url":null,"abstract":"<div><div>Organic-inorganic metal halide perovskite solar cells (PSCs) are favorable candidates for next-generation solar cells, due to their excellent photovoltaic performance and promising low-cost fabrication process. Particularly, tin oxide (SnO₂), with excellent charge mobility and extraction efficiency, is widely used as electron transport layers (ETLs), and the efficiency of the corresponding n-i-p-type perovskites has been certified as high as 26.21 ​% in single-junction devices. The SnO₂ layer serves as the substrate for the growth of perovskite films, determining the crystalline quality and the buried interface of perovskite films. However, due to the different thermal expansion coefficient of SnO₂ and perovskite, the subsequent perovskite annealing process leads to the residual stress at the buried interfaces and lattice distortion in the perovskite films, which seriously affects their optoelectronic performance and stability. To release this interfacial stress, researchers have made some progress by applying different polymers and small molecules to the SnO₂/perovskite interface as a buffer layer. Among these, two-dimensional (2D) nanosheets with high carrier mobility, a wide bandgap range, and excellent optical absorption properties are promising, especially 2D NbSe₂ nanosheets showing the advantages of solution-processability, high intrinsic conductivity and clean smooth surface, namely without dangling bonded atoms. Herein, 2D NbSe₂ nanosheets have been introduced at the SnO₂/perovskite interface to release the undesired residual tensile strain in perovskite films and to form a more matched interfacial energy level alignment. As a result, we have obtained a high-quality perovskite film and further an improved photovoltaic performance. The PCE has been increased from 21.81 ​% to 24.05 ​%. The unencapsulated cell maintained 91 ​% of the initial efficiency after aging over 1000 ​h under atmospheric condition.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 3","pages":"Article 100029"},"PeriodicalIF":10.8,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143181298","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":"Potential of zero charge-mediated electrochemical capture of cadmium ions from wastewater by lotus leaf-derived porous carbons","authors":"Ping Ye ,&nbsp;Lingshuang Qin ,&nbsp;Mengyao He ,&nbsp;Fangfang Wu ,&nbsp;Zengye Chen ,&nbsp;Mingxing Liang ,&nbsp;Libo Deng","doi":"10.3866/PKU.WHXB202311032","DOIUrl":"10.3866/PKU.WHXB202311032","url":null,"abstract":"<div><div>With the growth of batteries, electroplating, and mining industries, heavy metal ions such as cadmium (Cd²⁺) are being discharged on a massive scale, thus posing a severe threat to the environment. Conventional techniques for removing Cd²⁺ from wastewater with low concentrations still suffer from slow kinetics and secondary pollution. A carbon-based capacitive deionization (CDI) system is highly desired but encounters a severe co-ion expulsion effect. Herein, we developed CDI systems based on surface charge-modulated porous carbon and an asymmetric configuration. This was achieved by first preparing porous carbons through facile microwave pyrolysis of lotus leaf followed by KOH activation. The morphology, pore structure, heteroatom content, surface charge, and electrochemical behavior of porous carbons were investigated by adjusting the mass ratio of KOH to carbon. The lotus leaf-derived carbons show a morphology of nanosheet-like thin carbon (NSTC), with their specific surface areas increasing with the amount of KOH used for activation. In contrast, the heteroatom (<em>i.e</em>., nitrogen and oxygen) contents decrease with the increase in the mass ratio of KOH to carbon, resulting in a more positive surface charge. Notably, the NSTC with a mass ratio of 3 for KOH/carbon (NSTC-3) displays an ultrahigh specific surface area of 3705.0 m² g⁻¹, and a specific capacitance of 92.5 F g⁻¹ at a current density of 0.5 A g⁻¹ when coupled with a commercial activated carbon in an asymmetric YP-50F//NSTC-3 supercapacitor. Consequently, the CDI cell equipped with a YP-50F as the anode and a NSTC-3 as the cathode exhibits a high specific adsorption capacity of 88.6 mg_Cd·g_cathode⁻¹ at 1.2 V in a 100 mg L⁻¹ Cd²⁺ solution, which is about 36.3 % higher than that of the symmetrical configuration NSTC-3//NSTC-3. Furthermore, 71 % of the initial removal capacity of the YP-50F//NSTC-3 system is retained after 7 cycles of charging and discharging. Characterizations of the cathode after the adsorption process indicate that the Cd²⁺ is captured by both electrical-double-layer and pseudocapacitive mechanisms. Additionally, CdCO₃ precipitate is also responsible for Cd²⁺ removal, which might be ascribed to the reaction of dissolved CO₂ in aqueous media with Cd²⁺ under the electrified action. The high removal performance and excellent cycling stability are attributed to the tunability of the surface charge properties and the asymmetric configuration, which minimizes the co-ion expulsion and modulates potential distribution. This study provides a novel avenue to design biochar-based configurations for electrified water treatment.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 3","pages":"Article 100023"},"PeriodicalIF":10.8,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143181307","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":"Tailoring electrode-electrolyte interfaces via a simple slurry additive for stable high-voltage lithium-ion batteries","authors":"Aoyu Huang ,&nbsp;Jun Xu ,&nbsp;Yu Huang ,&nbsp;Gui Chu ,&nbsp;Mao Wang ,&nbsp;Lili Wang ,&nbsp;Yongqi Sun ,&nbsp;Zhen Jiang ,&nbsp;Xiaobo Zhu","doi":"10.3866/PKU.WHXB202408007","DOIUrl":"10.3866/PKU.WHXB202408007","url":null,"abstract":"<div><div>5 ​V-class LiNi_0.5Mn_1.5O₄ (LNMO) cathode material is emerging as a promising cobalt-free alternative to meet the growing demand for affordable, high-performance lithium-ion batteries (LIBs). However, LNMO faces significant electrochemical challenges, particularly interfacial instability with commercial electrolytes due to its high operating potentials. This instability leads to the dissolution of transition metals and consequently electrode crosstalk, which severely deteriorates electrochemical performance. Surface coating is extensively investigated to reduce interfacial side reactions for enhanced cycling stability. Traditional methods typically require multiple steps, including dispersion, mixing, drying, and calcination, which can be time-consuming and complex. Additionally, the resulting ceramic coatings are often rigid and unevenly distributed due to lattice mismatches, potentially leading to poor interfacial contact and increased resistance. In this study, tetraethyl orthosilicate (TEOS) is proposed as a streamlined slurry additive to <em>in situ</em> form an ethoxy-functional polysiloxane (EPS) film on the surface of LNMO particles during electrode preparation. Post-mortem X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) analyses reveal the crucial role of the EPS film in addressing interfacial instability issues. First, the EPS film serves as an artificial cathode-electrolyte interface (CEI) with a robust Si–O–Si bonding network, which is less vulnerable under high potentials. Second, the remaining ethoxy-functional groups in EPS scavenge HF by forming stable Si–F bonds, thereby suppressing the detrimental transition metal dissolution and crosstalk. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) further confirm the stability of the EPS film and the enhanced structural stability of the modified LNMO. Galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) results demonstrate that EPS reduces the overall impedance and improves ion diffusion kinetics by forming stable electrode-electrolyte interfaces. As a result, compared to the baseline, the optimized LNMO cathode exhibits significantly improved cycling stability in both half cells (84.6 ​% <em>vs.</em> 51.4 ​% capacity retention after 1000 cycles) and full cells when paired with commercial graphite anodes (83.3 ​% <em>vs.</em> 53.4 ​% retention after 500 cycles). This strategy, further validated under elevated temperatures of 50 ​°C and in pouch-type cells, is expected to pave the way for the development of next-generation high-performance LIBs.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 4","pages":"Article 100037"},"PeriodicalIF":10.8,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093637","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":"Rational Design of Bismuth Based Photocatalysts for Solar Energy Conversion","authors":"Yuanyin Cui ,&nbsp;Jinfeng Zhang ,&nbsp;Hailiang Chu ,&nbsp;Lixian Sun ,&nbsp;Kai Dai","doi":"10.3866/PKU.WHXB202405016","DOIUrl":"10.3866/PKU.WHXB202405016","url":null,"abstract":"<div><div>Semiconductor photocatalysis makes full use of solar energy, serving as a potent tactic to solve the worldwide energy deficit and safeguard the environment. Bismuth-based photocatalysts stand out among various photocatalysts as a significant area, due to their unique crystal structure, favorable mixed electron band structure, diverse composition, and huge potential for solar catalytic conversion. This document reviews the rational design of Bi-based photocatalysts for solar energy. Recent advancements in diverse Bi-based photocatalysts such as Layered Bi, Bismuth element, BiVO₄, Bi₂S₂, and Bi₂O₃ are highlighted. Secondly, the synthesis strategies of Bi-based catalysts, including hydrothermal/solvothermal, chemical precipitation, and solid-state reaction, are summarized. Third, various structural regulation methods to improve the photocatalytic performance, including defect regulation, heteroatom doping, morphology, SPR effect utilization, and heterojunction construction, are systematically introduced. Additionally, a focus is given to the exclusive applications of Bi-based photocatalysts, including CO₂ reduction, water decomposition, N₂ fixation, NO_<em>x</em> removal, H₂O₂ production, and selective organic synthesis, followed by an introduction of advanced <em>in situ</em> characterization techniques of the Bi-based photocatalysts. Ultimately, the forthcoming obstacles are underscored, and a future outlook for Bi-based photocatalysts is anticipated. This review aims to offer detailed instructions for comprehensively understanding and logically crafting effective bismuth-based photocatalysts, while also encouraging novel ideas and advances in energy and environmental fields, contributing to the goals of green chemistry and sustainable development.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (122KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 12","pages":"Article 2405016"},"PeriodicalIF":10.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143128039","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":"Revealing Photoinduced Charge Transfer Mechanism of SnO2/BiOBr S-Scheme Heterostructure for CO2 Photoreduction","authors":"Yuejiao An ,&nbsp;Wenxuan Liu ,&nbsp;Yanfeng Zhang ,&nbsp;Jianjun Zhang ,&nbsp;Zhansheng Lu","doi":"10.3866/PKU.WHXB202407021","DOIUrl":"10.3866/PKU.WHXB202407021","url":null,"abstract":"<div><div>S-scheme heterojunctions can preserve strong redox capacity on the basis of achieving spatial separation of photogenerated carriers. Therefore, a deep comprehension of the photoinduced charge transfer dynamics in S-scheme heterostructures is vital to enhancing photocatalytic properties. Herein, SnO₂/BiOBr S-scheme heterojunctions with tight contact are fabricated with <em>in situ</em> hydrothermal method. The optimal SnO₂/BiOBr exhibits excellent photocatalytic performance for CO₂ reduction, with yields of CO and CH₄ of 345.7 and 6.7 μmol∙g^–1∙h^–1, which are 5.6 and 3.7 times higher than those of the original BiOBr. The photoinduced charge transfer mechanism and dynamics of SnO₂/BiOBr S-scheme heterostructure are characterized by <em>in situ</em> X-ray photoelectron spectrum (XPS) and femtosecond transient absorption spectroscopy (fs-TA). A new fitted lifetime of photogenerated carriers are observed, which could be attributed to interfacial electron transfer of S-scheme heterojunction, further illustrating an ultrafast transfer channel for photoelectrons from SnO₂ conduction band to BiOBr valence band. As a result, the powerful reduced electrons in BiOBr conduction band and the powerful oxidation holes in SnO₂ valence band are retained. This work provides profound comprehension of photoinduced charge transfer mechanism of S-scheme heterojunction.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (85KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 12","pages":"Article 2407021"},"PeriodicalIF":10.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143128709","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":"Constructing Covalent Triazine Frameworks/N-Doped Carbon-Coated Cu2O S-Scheme Heterojunctions for Boosting Photocatalytic Hydrogen Production","authors":"Kaihui Huang ,&nbsp;Dejun Chen ,&nbsp;Xin Zhang ,&nbsp;Rongchen Shen ,&nbsp;Peng Zhang ,&nbsp;Difa Xu ,&nbsp;Xin Li","doi":"10.3866/PKU.WHXB202407020","DOIUrl":"10.3866/PKU.WHXB202407020","url":null,"abstract":"<div><div>The development of efficient photocatalysts for hydrogen production is crucial in sustainable energy research. In this study, we designed and prepared a Covalent Triazine Framework (CTF)-Cu₂O@NC composite featuring an S-scheme heterojunction structure aimed at enhancing the photocatalytic hydrogen production. The light absorption capacity, electron-hole separation efficiency and H₂-evolution activity of the composite were significantly enhanced due to the synergistic effects of the nitrogen-doped carbon (NC) layer and the S-scheme heterojunction. Structural and photoelectrochemical characterization of the system reveal that the S-scheme heterojunctions not only enhance the separation efficiency of photogenerated carriers but also maintain the strong redox capabilities to further promote the photocatalytic reactions. Moreover, the NC layer could simultaneously reduce the photocorrosion of Cu₂O and promote the electron transfer. Experimental results demonstrate that the CTF-7% Cu₂O@NC composite shows outstanding hydrogen-production performance under visible light, achieving 15645 μmol∙g⁻¹∙h⁻¹, significantly surpassing the photocatalytic activity of pure CTF (2673 μmol∙g⁻¹∙h⁻¹). This study introduces a novel approach to the development of efficient and innovative photocatalytic materials, strongly supporting the advancement of sustainable hydrogen energy.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (131KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 12","pages":"Article 2407020"},"PeriodicalIF":10.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127804","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":"In Situ Assembled ZnWO4/g-C3N4 S-Scheme Heterojunction with Nitrogen Defect for CO2 Photoreduction","authors":"Jianyu Qin,&nbsp;Yuejiao An,&nbsp;Yanfeng Zhang","doi":"10.3866/PKU.WHXB202408002","DOIUrl":"10.3866/PKU.WHXB202408002","url":null,"abstract":"<div><div>Reforming CO₂ into storable solar fuels <em>via</em> semiconductor photocatalysis is considered an effective strategy to solve the greenhouse effect and resource shortage. Unfortunately, the problem of rapid photogenerated carriers severely limits the CO₂ reduction capability of one-component catalysts. The fabrication of S-scheme heterojunctions with defects can result in efficient spatial separation of photo-generated charge carriers and increase adsorption and activation of nonpolar molecules. Herein, ZnWO₄/g-C₃N₄ S-scheme heterojunctions with defects are constructed through <em>in situ</em> growth method. The experiments show that the generation rate of CO from CO₂ reduction is up to 232.4 μmol∙g⁻¹∙h⁻¹ with a selectivity close to 100%, which is 11.6 and 8.5 times higher than those of pristine ZnWO₄ and g-C₃N₄, respectively. <em>In situ</em> XPS and work function analyses demonstrate the S-scheme charge transport pathway, which facilitates the spatial segregation of photogenerated carriers and promotes CO₂ reduction. <em>In situ</em> ESR illustrates that CO₂ molecules are adsorbed by nitrogen vacancies, which act as photoelectron acceptors during the photocatalytic reaction and are favorable for charge trapping and separation. The S-scheme charge transport mode and nitrogen vacancy work together to stimulate the efficient conversion of CO₂ to CO. This work presents significant insights to the cooperative influence of the S-scheme charge transport mode and defects in regulating CO₂ reduction activity.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (65KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 12","pages":"Article 2408002"},"PeriodicalIF":10.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143128710","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":"Photocatalytic CO2 Reduction by Modified g-C3N4","authors":"Xuejiao Wang ,&nbsp;Suiying Dong ,&nbsp;Kezhen Qi ,&nbsp;Vadim Popkov ,&nbsp;Xianglin Xiang","doi":"10.3866/PKU.WHXB202408005","DOIUrl":"10.3866/PKU.WHXB202408005","url":null,"abstract":"<div><div>The use of carbon-based fuels causes a significant increase in CO₂ emissions, posing a serious threat to the environment. This review explores the potential application of graphitic carbon nitride (g-C₃N₄) in photocatalytic CO₂ reduction as a strategy to mitigate global warming. The effectiveness of g-C₃N₄ (gCN) in this process is hindered by several factors, including rapid exciton recombination, limited solar light absorption, and a lack of active sites for conducting the reduction. To address these challenges, various amendment techniques have been executed, such as adjusting the morphology of g-C₃N₄, doping it with different atoms, and forming heterojunctions with other semiconductors. This review highlights the role of S-scheme heterojunctions in expanding the photocatalytic activity of g-C₃N₄ and emphasizes that, despite its potential as a photocatalyst for CO₂ reduction, further research and innovation are essential to overcome its current limitations.</div><div><span><figure><span><img><ol><li><span><span>Download: <span>Download high-res image (108KB)</span></span></span></li><li><span><span>Download: <span>Download full-size image</span></span></span></li></ol></span></figure></span></div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 12","pages":"Article 2408005"},"PeriodicalIF":10.8,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143128018","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}