Most Download
Most Download
-
ArticleMonodispersed SWNTs Assembled Coating Layer as an Alternative to Graphene with Enhanced Alkali-Ion Storage Performance
Chaoying Wang, Qianqian Yao, Yanmei Gan, Qixin Zhang, Lunhui Guan and Yi Zhao*
Chin. J. Struct. Chem. 2022, 41, 2201040-2201046 DOI: 10.14102/j.cnki.0254-5861.2021-0050
January 13, 2022
single-walled carbon nanotubes, graphene, Fe3O4, FeSe2, alkali-ion batteries
ABSTRACT
Graphene coating is commonly used to improve the performance of electrode materials, while its steric hindrance effect hampers fast ion transport with compromised rate capability. Herein, a unique single-walled carbon nanotubes (SWNTs) coating layer, as an alternative to graphene, has been developed to improve the battery behavior of iron-based anodes. Benefiting from the structure merits of mesoporous SWNTs layer for fast electron/ion transport and hollow Fe3O4 for volume accommodation, as-prepared Fe3O4@SWNTs exhibited excellent lithium storage performance. It delivers a high capacity, excellent rate capability, and long lifespan with capacities of 582 mA·h·g-1 at 5 A·g-1 and 408 mA·h·g-1 at 8 A·g-1 remained after 1000 cycles. Such performance is better than graphene-coated Fe3O4 and other SWNT-Fe3O4 architectures. Besides, SWNTs coating is also used to improve the sodium and potassium storage performance of FeSe2. The kinetics analysis and ex-situ experiment further reveal the effect of SWNTs coating for fast electron/ion transfer kinetics and good structure stability, thus leading to the superior performance of SWNTs-coated composites. -
ArticleHighly Efficient Photocatalytic CO2 Methanation over Ru-Doped TiO2 with Tunable Oxygen Vacancies
Zheyue Li†, Di Wu†, Wanbing Gong*, Jiayi Li, Shuaikang Sang, Hengjie Liu, Ran Long and Yujie Xiong*
Chin. J. Struct. Chem. 2022, 41, 2212043-2212050 DOI: 10.14102/j.cnki.0254-5861.2022-0212
December 2, 2022
photocatalysis, CO2 methanation, metal doping, titanium oxide, oxygen vacancies
ABSTRACT
Solar-driven CO2 methanation is an imperative and promising approach to relieve the global warming and environmental crisis, yet remains a great challenge due to the low reaction efficiency, unsatisfactory selectivity and poor stability. In this work, we demonstrate a facile and efficient strategy to prepare Ru-doped TiO2 photocatalyst with tunable oxygen vacancies using the ascorbic acid as a reducing agent for the CO2 methanation reaction. The optimal Ru-TiO2-OV-50 exhibits a remarkable CH4 production rate of 81.7 mmol g-1 h-1 with a 100% CH4 selectivity under a 1.5 W cm-2 light illumination, which is significantly higher than commercial Ru/TiO2 and other reported catalysts. We reveal that the superior photocatalytic CO2 methanation performance is mainly due to the synergistic effect of Ru doping and TiO2 with tunable oxygen vacancies. Impressively, the light rather than thermal effect is confirmed as the main influencing factor by experimental studies. In addition, in situ spectroscopic technology is performed to investigate the CO2 methanation reaction pathway. This work will open an avenue to design and prepare highly efficient photocatalyst with tunable oxygen vacancies for CO2 conversion and other related applications. -
ArticleExplicating the Role of Metal Centers in Porphyrin-Based MOFs of PCN-222(M) for Electrochemical Reduction of CO2
Mengjie Liu, Mengting Peng, Baoxia Dong*, Yunlei Teng, Ligang Feng and Qiang Xu*
Chin. J. Struct. Chem. 2022, 41, 2207046-2207052 DOI: 10.14102/j.cnki.0254-5861.2022-0057
July 18, 2022
PCN-222, electrochemical reduction of CO2, DFT calculation, MOFs
ABSTRACT
The porphyrin-based MOFs formed by combining Zr6 clusters and porphyrin carboxylic acids with clear M-N4 active centers show unique advantages in electrocatalytic reduction of CO2 (CO2RR). However, its conductivity is still the bottleneck that limits its catalytic activity due to the electrical insulation of the Zr cluster. Therefore, the porphyrin-based MOFs of PCN-222(M) (M = Mn, Co, Ni, Zn) with explicit M-N4 coordination were combined with the highly conductive material carbon nanotube (CNT) for discussing the influence of metal centers on the CO2RR performance based on theoretical calculations and experimental observations. The results show that the PCN-222(Mn)/CNT, PCN-222(Co)/CNT, and PCN-222(Zn)/CNT all exhibit high selectivity to CO (FECO > 80%) in the range of -0.60 to -0.70 V vs. RHE. The FECOmax of PCN-222(Mn)/CNT (-0.60 V vs. RHE), PCN-222(Co)/CNT (-0.65 V vs. RHE), and PCN-222(Zn)/CNT (-0.70 V vs. RHE) are 88.5%, 89.3% and 92.5%, respectively. The high catalytic activity of PCN-222(Mn)/CNT and PCN-222(Co)/CNT comes from the excellent electron mobility of their porphyrin rings and their low ΔG*COOH (0.87 and 0.58 eV). It reveals that the strength of backbonding π of the transition metal and its influence on the electron mobility in the porphyrin ring can affect its CO2RR activity. -
ArticleUltrathin ZnIn2S4 Nanosheets-Supported Metallic Ni3FeN for Photocatalytic Coupled Selective Alcohol Oxidation and H2 Evolution
Mengqing Li, Weiliang Qi, Jiuyang Yu, Lijuan Shen, Xuhui Yang, Siqi Liu* and Min-Quan Yang*
Chin. J. Struct. Chem. 2022, 41, 2212015-2212024 DOI: 10.14102/j.cnki.0254-5861.2022-0147
December 2, 2022
transition metal nitrides, cocatalyst, ultrathin 2D nanosheets, electrostatic self-assembly, interfacial contact, selective alcohol oxidation, H2 evolution
ABSTRACT
Photocatalytic anaerobic organic oxidation coupled with H2 evolution represents an advanced solar energy utilization strategy for the coproduction of clean fuel and fine chemicals. To achieve a high conversion efficiency, the smart design of efficient catalysts by the right combination of semiconductor light harvesters and cocatalyst is highly required. Herein, we report a composite photocatalyst composed of noble metal-free transition metal nitride Ni3FeN decorated on 2D ultrathin ZnIn2S4 (ZIS) nanosheets for selective oxidation of aromatic alcohols to aldehydes pairing with H2 production. In the composite, ultrathin ZIS serves as a light harvester that greatly shortens the diffusion length of photogenerated charges, while the metallic nitride Ni3FeN acts as an advanced cocatalyst which not only captures the photoelectrons generated from the ultrathin ZIS to promote the charge separation, but also provides active sites to lower the overpotential and accelerate the H2 reduction. The best photocatalytic performance is found on ZIS/1.5% M-Ni3FeN, which shows a H2 generation rate of 2427.9 μmol g-1 h−1 and a benzaldehyde (BAD) production rate of 2460 μmol g-1 h-1, about 7.8-fold as high as that of bare ZIS. This work is anticipated to endorse the exploration of transition metal nitrides as high-performance cocatalysts to promote the coupled photocatalytic organic transformation and H2 production. -
S-scheme Porous g-C3N4/Ag2MoO4 Heterojunction Composite for CO2 Photoreduction
Zhongliao Wang, Ruilian Liu, Jinfeng Zhang* and Kai Dai*
Chin. J. Struct. Chem. 2022, 41, 2206015-2206022 DOI: 10.14102/j.cnki.0254-5861.2022-0108
June 20, 2022
S-scheme, g-C3N4, Ag2MoO4, heterojunction, CO2 photoreduction
ABSTRACT
Utilizing solar energy to achieve artificial photosynthesis of chemical fuel is prevalent in tackling excessive CO2 emission and fossil fuel depletion. Grievous charge recombination and weak redox capability aggravate the CO2 photoreduction performance. Engineering tailored morphology and constructing matched heterostructure are two significant schemes to ameliorate the CO2 photoconversion efficiency of g-C3N4-based composite. Herein, a novel S-scheme ultrathin porous g-C3N4 (UPCN)/Ag2MoO4 (AMO) composite was designed by in-situ growing tetragonal α-AMO nanoparticles (NPs) (5-30 nm) on UPCN nanosheets (NSs). The S-scheme charge transfer route endows UPCN/AMO with fast charge separation and strong redox capability, demonstrated by X-ray photoelectron spectroscopy (XPS), photoelectrochemical tests, steady-state and time-resolved photoluminescence (PL) spectra, and DFT calculations. The UPCN/AMO composite exhibits elevated CO2 photoreduction performance with CO and CH4 yield rates of 6.98 and 0.38 μmol g-1 h-1, which are 3.5 and 2.9 folds higher than that of pristine UPCN, respectively. Finally, the CO2 photoreduction intermediates are analyzed, and the CO2 photoreduction mechanism is discussed. This work provides a reference for various g-C3N4-based composites applied in artificial photosynthesis. -
Short CommunicationFlexible Organic Single Crystal with Elastic Bending and Plastic Twisting Capabilities
Jiang Peng†*, Wanjun Zhao†, Jing Zhang, Chuchu Han, Junhui Jia, Tingting Feng and Jiawen Sun
Chin. J. Struct. Chem. 2022, 41, 2212004-2212006 DOI: 10.14102/j.cnki.0254-5861.2022-0217
December 2, 2022
flexible crystal, elastic bending, plastic twisting, elastoplastic deformation, waveguide
ABSTRACT
-
ArticleBoosting Stable and Fast Potassium Storage of Iron Sulfide through Rational Yolk-Shell Design and Ni Doping
Yanmei Gan, Jiajie Zhu, Qixin Zhang, Chaoying Wang, Lunhui Guan and Yi Zhao*
Chin. J. Struct. Chem. 2022, 41, 2205030-2205036 DOI: 10.14102/j.cnki.0254-5861.2022-0044
May 20, 2022
FeS2, Ni-doping, yolk-shell structure, anode, potassium-ion batteries
ABSTRACT
Metal sulfides have been regarded as promising anodes for potassium-ion batteries (PIBs) due to their high theoretical capacities, while the performance is limited by their intrinsic poor conductivity and large volume fluctuation during the insertion/extraction of large potassium ion. Herein, the battery performance of iron sulfide anode is significantly enhanced through yolk-shell (Y-S) structure design and nickel doping, aiming to realize good structure stability and superior electron/ion transportation. For potassium storage, as-prepared Y-S Ni-FeS2@C shows excellent cyclic performance and sustains high capacities of 328 mA h g-1 after 100 cycles at 0.2 A g-1 and 226 mA h g-1 after 1000 cycles at 1 A g-1 . Especially, it displays a superior rate capacity of 200 mA h g-1 at 20 A g-1, higher than that of Y-S FeS2@C and most as-reported metal sulfide anodes for PIBs. The experimental analysis and theoretical calculation illuminate the effect of Ni-doping on decreasing the particle size of iron sulfide and enhancing the ion/electron transport ability, thus accounting for the exceptional rate capability of Y-S Ni-FeS2@C composite. -
ArticleEngineering the Interface and Interaction Structure on Highly Coke-Resistant Ni/CeO2-Al2O3 Catalyst for Dry Reforming of Methane
Sha Li, Xin Wang, Min Cao, Jingjun Lu, Li Qiu and Xiaoliang Yan*
Chin. J. Struct. Chem. 2022, 41, 2212007-2212014 DOI: 10.14102/j.cnki.0254-5861.2022-0113
December 2, 2022
metal-support interaction, interface, Ni catalysts, CeO2, dry reforming of methane
ABSTRACT
Designing and tailoring metal-support interaction in Ni-based catalysts with plentiful interfacial sites is of significant interest for achieving a targeted catalytic performance in dry reforming of methane (DRM), but remains as a challenging task. In this work, Ni/Al2O3 and Ni/CeO2-Al2O3 catalysts with the same strong metal-support interaction (SMSI) but distinct interface structure are developed by an improved evaporation-induced self-assembly method using pseudobohemite gel as aluminum source. Ni/CeO2-Al2O3 exhibits superior catalytic activity and stability in DRM in comparison with Ni/Al2O3. The highest CH4 and CO2 conversion reaches at 71.4% and 82.1% for Ni/CeO2-Al2O3, which are higher than that of 64.3% and 75.6% for Ni/Al2O3 at 700 °C. The SMSI effect in Ni/CeO2-Al2O3 provides more active interfacial sites with less coke deposition, and promotes the generation of active formate species which are the key intermediates for DRM. The findings of the present work could possibly pave the way for fabricating catalysts with SMSI strategy for efficient heterogeneous catalysis. -
ArticleLayer-by-Layer Grafting Dye on Chiral MOF Thin Films for Circularly Polarized Luminescence
Rui Zhai, Yindi Zhu, Limei Chang, Zhigang Gu* and Jian Zhang*
Chin. J. Struct. Chem. 2022, 41, 2209074-2209079 DOI: 10.14102/j.cnki.0254-5861.2022-0023
September 22, 2022
metal-organic frameworks, liquid-phase epitaxy, thin film, circularly polarized luminescence
ABSTRACT
Metal-organic frameworks with chiral feature (chirMOFs) are attracting great attention on circularly polarized luminescence (CPL). However, developing new efficient strategy to achieve or improve CPL properties is an urgent task. Herein, new chiral MOF thin films prepared by liquid-phase epitaxial layer by layer (lbl) growth method (SURchirMOF) are composed of D- or L-camphorate (D/Lcam) and aminopyrazine (Pr-NH2) by using liquid phase epitaxial layer by layer (lbl) method. The resulted Zn2(D/Lcam)2Pr-NH2 SURchirMOF shows strong chirality and luminescence but weak CPL emission at 390 nm. After lbl modifying a dye molecule FluoresceinIsothiocyanate (FITC), the chiroptical Zn2(D/Lcam)2Pr-NH-FITC SURchirMOFs with ~7 times CPL signal improvement and ~3 times glum value amplification are obtained. This work provides a new strategy to develop chiral MOF thin films for CPL improvement using lbl grafting approach. -
ArticleUnraveling the Dynamic Structural Evolution of Phthalocyanine Catalysts during CO2 ElectroreductionJianing Mao, Bingbao Mei*, Ji Li, Shuai Yang, Fanfei Sun, Siyu Lu, Wei Chen, Fei Song* and Zheng Jiang*
Chin. J. Struct. Chem. 2022, 41, 2210082-2210088 DOI: 10.14102/j.cnki.0254-5861.2022-0133
October 25, 2022
CO2 electrochemical reduction, HERFD-XAS, model catalysts, difference spectra, structural evolution
ABSTRACT
Understanding the atomic and electronic changes of active sites promotes the whole new sight into electrochemical carbon dioxide reduction reaction (CO2RR), which provides a feasible strategy to achieve carbon neutrality. Here we employ operando high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS) to track the structural evolution of Ni(II) phthalocyanine (NiPc), considered as the model catalysts with uniform Ni-N4-C8 moiety, during the CO2RR. The HERFD-XAS method is in favor of elucidating the interaction of the reactant/catalyst interface from the atomic electronic structure dimension, facilitating the establishment of the catalytic mechanism and the dynamic structure changes. Based on operando measurement, surface sensitive difference spectra (∆µ) and spectroscopy simulation, the interfacial interactions between the active sites of NiPc and reactants are monitored and the Ni species gradually reduced by increasing the applied potential is discovered. HERFD-XAS method offers an advanced and powerful tool for elucidating the complex catalytic mechanism in further various systems. -
ArticleMolecular Engineering of g-C3N4 with Dibenzothiophene Groups as Electron Donor for Enhanced Photocatalytic H2-ProductionShanren Tao, Sijie Wan, Qinyang Huang, Chengming Li, Jiaguo Yu and Shaowen Cao*
Chin. J. Struct. Chem. 2022, 41, 2206048-2206054 DOI: 10.14102/j.cnki.0254-5861.2022-0068
June 20, 2022
carbon nitride, donor-acceptor, photocatalysis, charge transfer
ABSTRACT
The construction of donor-acceptor (D-A) molecular structure is an attractive strategy to enhance the photocatalytic performance of polymeric semiconductors. Herein, dibenzothiophene (DBT)-4-carbaldehyde as the precursor is introduced into g-C3N4 (TCN) prepared by two-step thermal polymerization to construct an intramolecular D-A type copolymer (TCN-DBTx). DFT calculation and experimental results reveal that DBT plays the role of electron donor unit to modify g-C3N4. The incorporation of DBT not only adjusts the band gap to improve reduction ability, but also induces an internal electric field with extending π-conjugated system for effective charge transfer. As a result, TCN-DBTx exhibits much better photocatalytic performance with an optimal hydrogen production rate of 3334 μmol h-1 g-1, which is 2.5 times that of TCN. This work provides a protocol for preparing high-performance g-C3N4-based photocatalysts toward various applications. -
ReviewRecent Developments of Dinitrogen Activation on Metal Complexes and Clusters
Xue-Lu Ma, Meng Li, Jun-Bo Lu, Cong-Qiao Xu and Jun Li*
Chin. J. Struct. Chem. 2022, 41, 2212080-2212088 DOI: 10.14102/j.cnki.0254-5861.2022-0197
December 2, 2022
dinitrogen activation, binding mode, dinitrogen complex, metal cluster, synergistic mechanism
ABSTRACT
Dinitrogen (N2) is the major component of the atmosphere and many factors bring about dinitrogen inertness with low reactivity. Dinitrogen activation on metal complexes and clusters under ambient condition is the long-standing goal in the modern chemistry. In this review, an attempt has been made to survey the mechanistic aspects of dinitrogen activation and functionalization based on different coordination binding modes of dinitrogen. Our goal is to provide a comprehensive survey of dinitrogen activation in order to guide the relevant research in the future.
-
ArticleCo-Construction of Sulfur Vacancies and Heterogeneous Interface into Ni3S2/MoS2 Catalysts to Achieve Highly Efficient Overall Water SplittingZhaoyang An, Hui Xue*, Jing Sun, Niankun Guo, Tianshan Song, Jiawen Sun, Yi-Ru Hao and Qin Wang*
Chin. J. Struct. Chem. 2022, 41, 2208037-2208043 DOI: 10.14102/j.cnki.0254-5861.2022-0130
July 25, 2022
sulfur vacancies, heterostructures, transition metal chalcogenides, overall water splitting
ABSTRACT
Integrating the advantages of anion vacancies and heterostructures into the catalytic materials may increase the binding affinities to intermediates, provide more active sites, and significantly promote the activity of overall water splitting. However, the successful assembly of anion vacancies and heterostructures for high-efficiency water splitting performance is still challenging. In this work, we ingeniously present the co-construction of sulfur vacancies and heterogeneous interface into Ni3S2/MoS2 catalysts on nickel foam (NF). The introduction of sulfur vacancies and Ni3S2/MoS2 heterostructures can significantly improve electron and ion transport, effectively improve structural stability, and enhance overall water splitting activity. The obtained VS-Ni3S2/MoS2 catalysts (VS stands for sulfur vacancies) exhibit superior OER and HER activities, and the overpotentials for OER and HER are 180 and 71 mV at 10 mA·cm-2, respectively. Furthermore, a low water splitting voltage of 1.46 V is required at 10 mA·cm-2 for the VS-Ni3S2/MoS2 catalysts, which is considerably lower than most of the water splitting electrocatalysts currently reported. This work offers an effective mean for the preparation of catalysts with both anion vacancies and heterostructures for achieving high-performance alkaline overall water splitting. -
ArticleP-Ni4Mo Catalyst for Seawater Electrolysis with High Current Density and Durability
Gai Li, Suyang Feng, Jing Li*, Peilin Deng, Xinlong Tian, Chongtai Wang and Yingjie Hua*
Chin. J. Struct. Chem. 2022, 41, 2207068-2207073 DOI: 10.14102/j.cnki.0254-5861.2022-0110
July 18, 2022
seawater electrolysis, electrodeposition, hydrogen evolution reaction, phosphorus doping
ABSTRACT
Rational design of highly efficient and durable electrocatalysts with low cost to replace noble-metal based catalysts for seawater electrolysis is extremely desirable, but challenging. In this work, we demonstrate a rapid electrodeposition method by growing P-Ni4Mo on the surface of the copper foam (CF) substrate to synthesize an efficient seawater electrolysis catalyst (P-Ni4Mo/CF). The catalyst exhibited considerable HER performance and stability in alkaline seawater, with the overpotential as low as 260 mV at a current density of 100 mA cm-2. The P-Ni4Mo/CF is capable of achieving 1.0 A cm-2 with an overpotential of 551 mV, which is slightly worse than that of the Pt/C catalyst (453 mV). Moreover, P-Ni4Mo/CF demonstrates robust durability, with almost no activity loss after the durability test for more than 200 h. This work not only reports a new catalyst for seawater electrolysis, but also presents a strategy for the performance enhancement of seawater electrolysis. -
CommunicationStrong High Entropy Alloy-Support Interaction Enables Efficient Electrocatalytic Water Splitting at High Current DensityHongdong Li, Yue Pan, Jianping Lai*, Lei Wang* and Shouhua Feng
Chin. J. Struct. Chem. 2022, 41, 2208003-2208011 DOI: 10.14102/j.cnki.0254-5861.2022-0125
July 25, 2022
high entropy alloy, metal-support interactions, microwave heating, water splitting, activity and durability
ABSTRACT
In electrocatalysis, the stability issue between catalyst and support still needs great attention. Here, a series of high- entropy alloy nanoparticles (HEA-NPs) embedded in carbon cloth (CC) were synthesized by using the scalable strategy-microwave heating. Among them, PtRhCoNiCu/CC exhibits outstanding hydrogen evolution reaction (HER) activity (19 and 170 mV overpotential at 10 and 1000 mA cm-2) and stability (150 h), outperforming other recently reported HEAs catalysts. IrRuCoNiCu/CC displays superior oxygen evolution reaction (OER) activity (166 and 354 mV overpotential at 10 and 1000 mA cm-2) and stability (150 h), and shows a lower overpotential than recently reported HEA catalysts. In water splitting, IrRuCoNiCu/CC(+)//PtRhCoNiCu/CC(-) electrolyzer achieves 500 mA cm-2 (1000 mA cm-2) high current density at 1.76 V (1.88 V) and exhibits excellent stability, which is one of the best catalysts currently. Therefore, the novel supported HEA catalyst with high stability is expected to be a promising candidate material for industrialized water splitting. -
ArticleTwo Bisligand-Coordinated Luminescent Zn(II)-Coordination Polymers for Sensing of Ions and Pesticides in Aqueous Solutions
Zhao-Di Zhou, Zi-Long Xu, Dan Wang, Lin-Fang Jia, Han-Qing Zhao, Bao-Yi Yu* and Chong-Chen Wang*
Chin. J. Struct. Chem. 2022, 41, 2209087-2209093 DOI: 10.14102/j.cnki.0254-5861.2022-0077
September 22, 2022
coordination polymer, fluorescence sensing, heavy metal ions, pesticides, X-ray crystallography
ABSTRACT
Two coordination polymers (CPs) [Zn(PTA)(DTP)(H2O)2]·(DMF) (CP-1) and [Zn(BTC)(DTP)]·(CH3CN)1.5·(H2O)4 (CP-2) with one- and two-dimensional architectures were synthesized from Zn(II) ion and different organic linkers like tere- phthalic acid (H2PTA), benzene-1,3,5-tricarboxylic acid (H3BTC), and 3,5-di(1,2,4- triazol-1-yl) pyridine (DTP). The fluorescent sensing experiments showed that the two CPs displayed effective, sensitive, and selective abilities towards Fe3+ and Cr2O72-. For sensing the pesticides, CP-1 outperforms in sensing of metamitron (MMT) and CP-2 is ultrasensitive towards imidacloprid (IMI). The possible mechanisms involved in the quenching of the fluorescence intensity include the inner filter effect (IFE) and the fluore- scence resonance energy transfer (FRET) effect. -
ArticlePyrene-Benzothiadiazole-Based Polymer/CdS 2D/2D Organic/Inorganic Hybrid S-scheme Heterojunction for Efficient Photocatalytic H2 Evolution
Ruiqi Gao, Huan He, Junxian Bai, Lei Hao, Rongchen Shen*, Peng Zhang, Youji Li and Xin Li*
Chin. J. Struct. Chem. 2022, 41, 2206031-2206038 DOI: 10.14102/j.cnki.0254-5861.2022-0096
June 20, 2022
photocatalytic hydrogen evolution, pyrene-benzothiadiazole-based conjugated polymers, S-scheme heterojunction, CdS
ABSTRACT
Nowadays, conjugated polymers have garnered numerous attention as a new class of organic photocatalysts due to their tunable electronic properties, low cost, excellent stability and sufficient light-absorption performance. In particular, pyrene-benzothiadiazole-based conjugated polymer (PBBP) has been considered to be a new type of conjugated polymers for photocatalytic H2 evolution. However, the poor charge separation seriously limits its practical application in H2 evolution. In this work, a PBBP-based polymer/CdS 2D/2D organic/inorganic S-scheme heterojunction photocatalyst with a strong internal electric field is, for the first time, prepared for efficient photocatalytic hydrogen evolution. The pyrene-benzothiadiazole-based conjugated polymers (PBBP) are synthesized by the Suzuki-Miyaura reactions. Then, the hybrid heterojunction photocatalysts are fabricated by coupling CdS with it through the ultrasonic mixing method. As a result, the highest H2-production rate of 15.83 mmol h-1 g-1 is achieved on 20% PBBP/CdS composite under visible-light irradiation, nearly 2.7 times higher than that of pure CdS. The apparent quantum efficiency (AQE) of 20% PBBP/CdS composite could reach 8.66% at λ = 420 nm. The enhanced activity could be attributed to the construction of S-scheme heterojunction, which accelerates the recombination of carriers with weaker redox ability and maintains the strong reducibility of electrons in CdS. This work provides a protocol for pyrene-benzothiadiazole-based conjugated polymers to prepare S-scheme heterojunction photocatalysts based on organic/inorganic coupling. -
ArticleOne-Pot Synthesis of Bismuth Basic Nitrate-Bi2MoO6 Photocatalyst for Selective Oxidation of TolueneTian-Qin Zeng, Lang Chen*, Bing-Hao Wang, Sheng Tian, Zhang-Jun Bai, Xiong Wang, Jun-Kang Guo* and Shuang-Feng Yin*
Chin. J. Struct. Chem. 2022, 41, 2212025-2212032 DOI: 10.14102/j.cnki.0254-5861.2022-0149
December 2, 2022
Bi2MoO6, basic bismuth nitrate, heterojunction, photocatalysis, selective oxidation of toluene
ABSTRACT
The key issues to improve the performance of photocatalysts for selective oxidation of toluene are promoting the migration and separation of charge carrier, and enhancing the generation of active oxygen species. It is known that the construction of compact heterojunction is an efficient protocol to inhibit photogenerated electron-hole recombination. In this work, a 2D-2D [Bi6O6(OH)3](NO3)3·1.5H2O-Bi2MoO6 (denoted as BBN-BMO) composite heterojunction has been prepared by one-step hydrothermal method for the first time. The tetragonal phase BBN in the composite plays the role of transferring electrons from the visible light activated orthorhombic phase BMO and promoting the generation of active •O2-, the holes left in BMO are used to activate toluene and produce benzyl radical, thus greatly improving the photocatalytic performance for selective oxidation of toluene. The toluene conversion rate of BBN-BMO is 3466 μmol·g-1·h-1, which is three times that of pure BMO. The selectivity to benzaldehyde is 94.2%. In addition, reasonable mechanism has been speculated based on a series of control experiments. -
ArticleCeO2 Particles Anchored to Ni2P Nanoplate for Efficient Photocatalytic Hydrogen Evolution
Teng Yan, Xiaojie Zhang, Hua Liu* and Zhiliang Jin*
Chin. J. Struct. Chem. 2022, 41, 2201047-2201053 DOI: 10.14102/j.cnki.0254-5861.2021-0057
January 13, 2022
CeO2, Ni2P, photocatalysis, hydrogen evolution
ABSTRACT
Photocatalytic hydrogen evolution can convert intermittent and dispersive solar energy into hydrogen with high energy density, which is expected to fundamentally solve the problems of environmental pollution and energy shortages. In this experiment, the performance of the catalyst is modified by introducing cocatalyst and morphology control. Ni(OH)2 nanoflowers are used as substrates to derive nanoplate stack Ni2P by high-temperature phosphating method, and a great many of CeO2 nanoparticles are anchored in the Ni2P. This unique 3D/0D combination effectively inhibits the agglomeration of CeO2 nanoparticles and shortens the electron transfer path. Secondly, the introduction of metal-like performance of Ni2P broadens the light absorption range of the catalyst and reduces the overpotential of the catalyst, which is a key factor in enhancing the catalytic activity. The design ideas of this experiment have reference significance for the design of efficient and environmentally friendly photocatalysts. -
ArticleCoupling of NiFe-Based Metal-Organic Framework Nanosheet Arrays with Embedded Fe-Ni3S2 Clusters as Efficient Bifunctional Electrocatalysts for Overall Water Splitting
Xianbiao Hou, Tianyuan Jiang, Xiujuan Xu, Xingkun Wang, Jian Zhou, Huimin Xie, Zhicheng Liu, Lei Chu* and Minghua Huang*
Chin. J. Struct. Chem. 2022, 41, 2207074-2207080 DOI: 10.14102/j.cnki.0254-5861.2022-0145
July 18, 2022
metal-organic frameworks, metal sulfides, nanosheet arrays, electrocatalysts, water splitting
ABSTRACT
Developing highly efficient, easy-to-make and cost-effective bifunctional electrocatalysts for water splitting with lower cell voltages is crucial to producing massive hydrogen fuel. In response, the coupled hierarchical Ni/Fe-based MOF nanosheet arrays with embedded metal sulfide nanoclusters onto nickel foam skeleton (denoted as Fe-Ni3S2 @NiFe-MOF/NF) are fabricated, in which the Fe-Ni3S2 clusters could effectively restrain the aggregation of the layer metal-organic frameworks (MOF) nanosheets and adjust the local electronic structures of MOFs nanosheets. Benefiting from the rapid charge transfer and the exposure of abundant active sites, the well-designed Fe-Ni3S2@NiFe-MOF/NF displays excellent oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance. More importantly, when equipped in the alkaline water electrolyzer, the Fe-Ni3S2@NiFe-MOF/NF enables the system with a mere 1.6 V for achieving the current density of 10 mA cm-2. This work offers a paradigm for designing efficient bifunctional HER/OER electrocatalysts based on the hybrid materials of nanostructured metal sulfide and MOF.
- Address: Fuzhou High & New Technology Industrial Zone, Shangjie, Minhou, Fuzhou, Fujian 350108, China
- Tel: (86)-591-63173769, 63173770
- E-mail: cjsc@fjirsm.ac.cn