Chinese Journal of Structural Chemistry
Chinese Journal of Structural Chemistry
主管 : 中国科学院
刊期 : 月刊
主编 : 洪茂椿
语种 : 英文
主办 : 中国科学院福建物质结构研究所、中国化学会
ISSN : 0254-5861 CN : 35-1112/TQ展开 >The Chinese Journal of Structural Chemistry, founded in 1982 by Prof. Jiaxi Lu, is an international peer-reviewed journal published in English. It publishes original research works about the structure and property of matter, including but not limited to coordination chemistry, organometallic chemistry, catalysis, energy, nanomaterial, theory/computation, structural characterization, pharmacy and life science. Published monthly by Fujian Institute of Research on the Structure of Matter, CAS, in the form of Articles, Communications, Reviews, Perspectives, and News & Views.
- 影响因子: 2.2
The creation of anodic ethanol oxidation reaction catalysts with superior all-around performance for direct ethanol fuel cells (DEFCs) has continued to attract the attention of researchers. An ultrathin trimetallic PtAuBi aerogel with branching, rough-surfaced 1D nanowires that self-assemble into a 3D porous network structure has been created in this study. It has a mass activity (MA) of 8045 mA mgPt-1 in an alkaline medium, which is 7.56 times greater than that of commercial Pt/C (1064 mA mgPt-1). Notably, the catalytic activity and resistance to CO poisoning of PtAuBi aerogels were improved by the addition of an efficient "active additive" Au. The results analysis reveals that the increased performance of PtAuBi aerogel is mostly attributable to the integrated function of the 3D porous network structure, the downward shift of the Pt d-band center, and the synergistic effect of the "Pt- Bi" and/or "Pt- Au" dual active sites.
Bismuth (Bi)-based nanomaterials are highly efficient electrocatalysts for carbon dioxide reduction (CO2RR), which still have huge scope for synthesis optimization and performance improvement. In this work, we develop a fast ultrasound-assisted galvani replacement reaction to synthesize two-dimensional metallic Bi metallene (Bi ML) with an ultrathin thickness of 1.5 nm, high surface area, and abundant atomic defects. The electrochemical characterization shows that Bi ML can achieve a faradaic efficiency of ~94% for the CO2RR to formate, accompanied by good stability. Density functional theory calculations show that the atomic vacancy can change the electronic structure of the surrounding atoms, which contributes to the selectivity enhancement of the CO2RR for formate production. This work provides an efficient method for the rapid large-scale preparation of high-performance Bibased two-dimensional nanomaterials for the CO2RR.
DFT calculations have been performed to explore the defective structures and oxidation properties of Janus AsP. By comparing the structural stabilities of these defective structures, the SW-I possesses the smallest formation energy of only 0.103 eV, which is easy to form on the Janus AsP surface, while DV-555777 defects have relatively high formation energies due to the larger structural distortion. The SV defects induce the electronic defect states near the Fermi level, but SW and DVs defects do not. Different from BP, where the O2 molecule will dissociate spontaneously on its surface, the dissociation of O2 molecule on Janus AsP needs to overcome a large barrier, i.e., 0.98 eV for SW-I and 0.93 eV for SV-5566-I. Our work has indicated that the Janus AsP possesses better oxidation resistance than BP, and even with surface defects, they provide wide applications in electronic and optical devices.
In the active Mn4CaO5 cluster of the natural water oxidation system, one of the dangling Mn atom is surrounded by water molecules through coordination and hydrogen bonding. It means that the enrichment of water molecules around the Mn catalysts has a positive effect on the water oxidation catalysis. Inspired by nature photosynthesis, the hydrophilic surfaces are believed to be able to capture water molecules to assist water oxidation. Herein, we report MnO2@PFANI nanowires with improved mass transfer efficiency and conductivity for electrocatalytic water oxidation. The as-prepared nanowires are synthesized by coating hydrophilic polymers on MnO2 nanowires. The hydrophilic surface captures water molecule and promote mass transfer processes, and the conductivity of the polymer can also increase charge transfer processes. To reach a current density of 10 mA cm-2, a low overpotential of 440 mV is required in a 1.0 M KOH solution for the MnO2@PFANI nanowires. The hydrophilicity and conductivity are systematically investigated by both physical and electrochemical measurements. This study provides a surface engineering idea for the fabrication of efficient electrocatalysts.
Chiral metal surfaces of CO2 electro-reduction catalysts could significantly influence CO2 reduction product species, even able to product amino acids. On the other hand, CISS effects have been started to be applicated in electrocatalysts, which significantly enhances the catalytic activity on OER. Thus, it is a promising future for CO2 electro-reduction that employs chiral materials with both chiral surface and CISS effects to enhance the catalytic activity of catalysts. In order to achieve this goal, the most critical issue to be addressed is the synthesis of copper materials with highly oriented and ordered chiral helical structures.
Ternary sulfide solid solutions have garnered great attention in photocatalytic water splitting due to their tunable electronic property, low cost, and sufficient light-absorption performance. Herein, a series of MnxCd1-xS samples with different Mn/Cd molar ratios were synthesized by solvothermal method and used for photocatalytic hydrogen production under visible light. The Mn0.2Cd0.8S and Mn0.4Cd0.6S were demonstrated to be the solid solutions, while Mn0.6Cd0.4S and Mn0.8Cd0.2S consist of MnxCd1−xS solid solution and MnS. In addition, the Mn0.4Cd0.6S exhibited the highest photocatalytic performance with the H2 production rate of 185.95 μmol·h-1, which was 4.7 times higher than that of CdS. Without the cocatalyst, the quantum efficiency of Mn0.4Cd0.6S reached 2.04% at 400 nm. In addition, the Mn0.4Cd0.6S solid solution also showed high stability during the photocatalytic H2 production reaction. The effect of the Mn/Cd molar ratio on the microstructure, band gap structure, and photocatalytic hydrogen production performance of MnxCd1−xS was revealed systematically. The excellent photocatalytic H2 production performance of the Mn0.4Cd0.6S solid solution is mainly due to its enhanced reducing potential and high charge separation efficiency.
A new 2D van der Waals material MnTeMoO6, which is obtained by the facile mechanical exfoliation technique. This material is very durable in the air, as confirmed by the unchanged Raman spectra. Polarization-dependent angle-resolved Raman tests show that MnTeMoO6 flake displays significant in-plane anisotropy.
Lattice distortion represents the fundamental factor of crystalline materials and contributes significantly to structural-related properties. Herein, we discover an unexpected temperature-induced lattice distortion in CuGeO3 nanocrystals, resulting in color changes of CuGeO3. The structural distortions in CuGeO3 nanocrystals are characterized by Rietveld analysis in detail, where its cell parameter b and cell volume reveal firstly decrease and then increase characteristics and correspond well with the XRD patterns and Raman spectra. Besides, both the experimental characterizations and theoretical calculations confirm that the optical and band structural changes mainly arise from the twisted octahedral field of [CuO6], where the lattice distortions regulate the crystal field splitting energy of [CuO6] and account for its changed d-d transition. Furthermore, tetracycline photodegradation is employed as an example to evaluate the effect of lattice distortion on photocatalytic performance, which also highlights the importance of modulating lattice distortion in photocatalysis. This work provides an approach to simply regulating the lattice distortion for nanorods by manipulating calcination temperatures.
We have successfully synthesized a series of Pd/ZnCo2O4 supported catalytic materials with low noble metal loading and high activity by the impregnation method. The Pd/ZnCo2O4 catalysts containing 0.2% Pd have superior performance for oxidizing CO at 80°C, achieving 100% conversion. There is also no loss of activity after four cycles of tests, with the conversion remaining approximately 100%. Aside from that, various advanced physicochemical characterizations indicate that this excellent catalytic performance stems from the interaction between metal Pd and carrier ZnCo2O4. Pd provides a higher degree of accessibility to the active site, while ZnCo2O4 as a carrier can better stabilize Pd nanoparticles. The 0.2% Pd/ZnCo2O4 exhibits higher levels of of Pd2+ species as the electronic interaction between Pd and ZnCo2O4 improves, thus improving CO oxidation catalytic efficiency. Furthermore, the low loading of Pd is crucial for reducing the cost of noble metal catalysts and ameliorating their practicality in industrial applications.
Porous ceramics with a pore size of 60 μm * 20 μm was printed using the multi-materials printing method. The pore size was the smallest known ceramic pore size that can be directly printed, especially the pore height of 20 μm in the longitudinal direction, which cannot be achieved by other ceramic additive manufacturing technologies. The feasibility of multi-materials 3D printing method was verified by sample printing and sintering. Further, the fiber-like effect in resin and ceramic material multi-materials printing was proposed, which enlarged the transverse pore size of the porous ceramics. This method can manufacture porous ceramics with a pore size of < 100 μm and the pore distribution and structure can be designed. This can benefit product performance and expand application fields. In addition, the proposed printing method is expected to be applied in micro-chemical industries to manufacture ceramic mixers, dispersers, reactors, heat exchangers, ceramic microfluidic chips, and micro-ceramic scaffolds.
In the context of green development, the use of solar cells with renewable and environment-friendly characteristics has been rapidly growing. There has been a continuous search for materials that can enhance their performance. Black phosphorus, a new type of semiconductor material, has garnered significant attention due to its distinctive properties, particularly its direct band gap with tunable layers and high optoelectronic efficiency. This review summarizes the properties of black-phosphorus-based materials and focuses on their use as doping materials in various components of solar cells, such as the electron transport layer, hole transport layer, active layer, etc. The current challenges faced by black phosphorus materials and outlook on their future development have also been discussed.
Structure features play an important role in machine learning models for the materials investigation. Here, two topology-based features for the representation of material structure, specifically structure graph and algebraic topology, are introduced. We present the fundamental mathematical concepts underlying these techniques and how they encode material properties. Furthermore, we discuss the practical applications and enhancements of these feature made in specific material predicting tasks. This review may provide suggestions on the selection of suitable structural features and inspire creativity in developing robust descriptors for diverse applications.
This work transfers the basic concept of functionalization reaction in organic chemistry to inorganic chemistry, which promotes the fusion of organic and inorganic synthetic chemistry. It opens the door for the bottom-up synthesis of organic-inorganic hybrid materials from hybrid molecules, pushing forward the control of hybrid material structures at molecular precision. The molecular scale covalent-ionic bicontinuous network suggests a new hybrid structure to combine paradoxical properties within one material, which broke the performance compromise in conventional composites. As Nature senior editor Kristina Kareh said, “The paper is a true demonstration of a new class of material”. Maybe in the near future, the hybrid molecules generated by the functionalization of inorganic ionic oligomers are expected to be used for the bottom-up design of more hybrid materials and these materials with new properties may open new application fields.
The controllable transformation of metal nanoclusters remains highly desirable for the preparation of new clusters with novel structures and the elucidation of cluster conversion mechanisms. Here, we present the reversible transformation between two high-nuclearity silver cluster homologs, Ag32S3(StBu)16(CF3COO)9(CH3CN)4(NO3) (abbreviated as monomer-Ag32) and [Ag32S3(StBu)16(CF3COO)9(CH3CN)(NO3)]2 (abbreviated as dimer-(Ag32)2). Triggered by the solvent effect, the reversible conversion between monomer-Ag32 and dimer-(Ag32)2 nanoclusters has been accomplished. For dimer-(Ag32)2, two CF3COO- linkers were bound onto the symmetrical edges of adjacent Ag32 subunits, giving rise to the dimeric existence form of the final cluster. The optical properties, including optical absorptions and emissions, of the cluster monomer and dimer were then compared. This work offered an interesting case for constructing self-assembled cluster structures with the assistance of certain solvents and multidentate ligands.
The search for new degrees of freedom in photoelectric functional crystals is a promising area of research that has the potential to revolutionize the development of advanced optoelectronic materials and devices. Searching for new degrees of freedom is the key to designing photoelectric functional crystals. By coupling the multiple degrees of freedom of the molecules, the contributions of the crystal properties can be clearly identified, and multi-scale quantum design of photoelectric functional crystals can be achieved from the origin of functionality. Through exploring novel phenomena and mechanisms, researchers can potentially discover materials with unprecedented photoelectric functionalities and superior performance. The synergy between experimental and theoretical studies is crucial for the discovery and optimization of these materials, as it enables researchers to accurately predict the behavior of materials and guide experimental efforts. The development of new photoelectric functional crystals has significant implications for the fields of optoelectronics and solar energy conversion technologies. The discovery of new materials with enhanced photoelectric functionalities has the potential to increase the efficiency and reliability of solar cells, leading to more widespread adoption of solar energy. Furthermore, the development of novel optoelectronic devices based on photoelectric functional crystals could lead to breakthroughs in areas such as data storage and communication. Overall, continued research and development in this area will pave the way for the next generation of optoelectronics and solar energy conversion technologies.