The 40th DICP Symposium on Oxide Surfaces was held at DICP on Jan. 10-11, 2016. Prof. Xinhe Bao (DICP) and Prof. Qikun Xue (Tsinghua University), as co-chairs, organized this event. On behalf of DICP, Prof. Tao Zhang attended the opening ceremony and delivered the opening speech. This symposium has attracted more than 90 scientists from 12 countries around the world with 20 invited talks, 33 oral presentations and 20 posters.
　　The 40th DICP Symposium on Oxide Surfaces Successfully Held in DICP (Photo by Wansheng LIU)
　　Oxide surfaces play an important role in various scientific fields, including physics, chemistry, engineering, materials and biology. The scientific theme of this symposium focused on Surface and Interface, Two-dimensional Materials and Energy Conversion and Storage. Eight specific sessions were covered: 1. Structure and Theory; 2. Surface and Interface; 3. Catalysis; 4. Electrochemistry; 5. Two-dimensional Materials; 6.Novel Physical Phenomena; 7. Oxides on Metals; 8. Oxides under Ambient Pressure.
　　The two-day symposium has successfully promoted the in-depth collaboration between Chinese scientists and oversea researchers in oxide community. (Text by Peng Jiang, Photo by Wansheng Liu)
　　

　　Nowadays, the scarcity of fresh water resources and the ever-growing environmental pollution have been attracting increased concern. The Fenton-like process has been widely investigated due to its high efficiency in removing persistent organic contaminants by in-situ production of SO4·- or HO· radicals. However, limited mechanism understanding hinders any significant advances in Fenton chemistry. In the past two years, Prof. Junhu Wang from the State Key Laboratory of Catalysis and the Mossbauer Effect Data Center has made a series of progress in investigating the mechanism of Fenton-like reaction, by using Mossbauer technique determine the coordination environment, Spin state and oxidation state of iron ions.
　　In 2014, the team developed a series of Prussian blue/TiO2 (PB/TiO2) nanocomposites as heterogeneous photo-Fenton catalyst to increase the FeII recovery in degrading organic contaminants in water. The Mossbauer spectra provided evidence that the excited electrons of TiO2 by UV irradiation could accelerate the cycle of low spin FeIII to FeII in PB and then led to the higher activity (Catal. Sci. Technol., 2015, 5, 504-514. doi: 10.1039/C4CY00947A). Then, two kinds of Fe-Co Prussian blue analogues (Fe-Co PBAs) with different iron valence state, Fe3[Co(CN)6]2·12H2O and Fe[Co(CN)6]·2H2O, were developed as novel photo-Fenton catalysts for in-depth investigation of the heterogeneous Fenton reaction mechanism. The efficient redox cycling of iron species in the Fe-Co PBAs photo-Fenton process was deeply explored by Mossbauer spectroscopy. The excellent photo-Fenton activities of these Fe-Co PBAs were ascribed to the existence of highly dispersed water coordinated iron sites and abundant vacancies in the metal-organic-frameworks. In collaboration with Prof. Hongxian Han from the State Key Laboratory of Catalysis, singlet oxygen (O1 2) produced indirectly from HOO· and HO· was found to participate directly in the degradation of RhB (Appl. Catal. B 2016, 181, 788-799. doi:10.1016/j.apcatb.2015.05.033 2015/07-09 Top 25 Hottest Articles: 25/25). To further study the reaction intermediates and pathway of active iron species during the Fe-Co PBA catalyzed Fenton-like process, hydrazine (Hz) was newly introduced to enhance the oxidation performance of the Fenton system. Combining the XPS and M?ssbauer spectroscopy results, the Hz coordinated iron site (H2NH2N-Fe), which is evolved from the original water coordinated iron site (H2O-Fe), was identified as a more active site which largely increased the reaction rate (Catal. Commun., 2016, doi: 10.1016/j.catcom.2016.01.004).
　　DICP Researchers find the Mechanism of Fenton-like Reaction by Using Mossbauer Technique (Photo by Xuning LI)
　　Based on the deeply understanding the Fenton-like reaction mechanism as well as the structural features of the Fe-Co PBAs, the team successfully prepared a series of porous FexCo3-xO4 nanocages via a facile strategy by heating FeyCo1-y-Co PBAs nanospheres with tunable size and morphology. The prepared FexCo3-xO4 nanocages were found to be efficient to activate PMS into radicals, which could further degraded BPA to small organic compounds or even inorganic carbon forms. Mossbauer and XPS techniques were applied to illustrate the catalytic mechanism and B-site CoII on the surface of FexCo3-xO4 nanocages was determined as the main factor for PMS activation (Appl. Catal. B 2016, 181, 788-799. doi:10.1016/j.apcatb.2015.08.050 2015/07-09 Top 25 Hottest Articles: 15/25). Meanwhile, the team has successfully synthesized series of MnyFe1-y-Co PBAs nano-dices with well-controlled morphology and composition through simply modulating the relative content of Mn. Based on the fact of that three series of MyFe1-y-Co PBAs (M = Co, Mn and Zn) with well-controlled morphology have been successfully prepared through this novel and scalable strategy, a “copolymer-co-morphology” conception was unprecedentedly proposed. In collaboration with Prof. Luhua Jang from Dalian National Laboratory for Clean Energy, the octahedral-site MnIII/MnIV content in MnxFe1.8-xCo1.2O4, mainly determined by sensitive 57Fe Mossbauer and XPS techniques, was discovered to be directly correlated with the oxygen reduction/evolution reaction (ORR/OER) activity (Nanoscale, 2016, doi: 10.1039/C5NR07193C).
　　The series of research not only opens a new way for the general use of PBAs in photo-Fenton process, but also gives a deeper insight into the heterogeneous Fenton reaction mechanism which is nowadays very limited. In addition, the “copolymer-co-morphology” conception will be beneficial for morphologically controlled syntheses of other types of CPs and spinel oxides.
　　The above-mentioned research work has been financially supported by the National Natural Science Foundation of China and the Chinese Academy of Sciences Visiting Professorships for Senior International Scientists. (Text/Photo by Xuning LI)
　　

　　The monodisperse micron silica packing production line was successfully operated. This production line could manufacture narrow pore size distribution and high uniformed monodisperse mesoporous micron Silica, which researched and designed independently by the team of Prof. Shudong Wang and Dr. Hongjiu Su in the clean energy national laboratory. The particle size of 2 μm, 3.5 μm, 5 μm and 10μm microsilica sphere was successfully prepared as well as the particles size dimension between the 2 to 10 μm could be controllable synthesized. After a series of tests, the physical properties such as mechanical strength, homogeneity and spherical degree perfectly meet the requirements of chromatographic packing material.
　　 
　　The Monodisperse Micron Silica Packing Production Line is Successfully Operated (Photo by Diannan GAO)
　　High performance liquid chromatographic (HPLC) is not only used in efficient analysis and detection technique, but also in separation field especially for traditional Chinese medicine, natural products, synthetic drugs and components etc. The core of HPLC technique is chromatographic column packing. Among today’s appropriate packing materials, silica accounted for 80%. Then, in the process of the preparation of silica filler, the bottleneck is how to control the characters of the packing material in pore size, concentration, micron scale, spherical degree and uniformity. However a few large foreign companies monopolized the high-end silica packing and domestic production is difficult to meet the requirements of HPLC. Therefore, the preparation of monodisperse silica micro silica gel technology greatly limits HPLC in the applications of analysis, detection and separation of drugs in China. Using a new chemical engineering method which based on the theory of existing catalyst design and synthesis, the team of Energy and Environment Engineering put forward the new technology of synthesis of the monodisperse micron silica packing and successfully synthesis the narrow pore size distribution and high uniformed monodisperse mesoporous micron silica packing. The micro silica packing on the column pressure, column efficiency and wide spectrum wholly meet the requirement of chromatographic packing materials. (Photo by Diannan GAO, Text by Hongjiu SU)
　　

　　Recently, Professor Jie Xu and Professor Fang Lu of organic catalysis group have developed a novel synthetic route to directly obtain diethyl terephthalate (DET) from biomass-derived muconic acid through a cascade process combining esterification, Diels-Alder cycloaddition, and dehydrogenation reaction. This work is now online published in the journal of Angewandte Chemie International Edition as hot paper (Angew. Chem. Int. Ed. 2016, 55, 249-253).
　　The annual nameplate capacity of purified terephthalic acid (PTA), a large-volume commodity chemical used to produce polyesters (PET, PTT and PBT), was over 46 million tons in China, 2014. Currently, industrial production of PTA is mainly through the oxidation of petroleum-based para-xylene (PX), and Xu’s group has a long-term research accumulation in the oxidation route for the production of PTA. This study has important scientific significance and application prospects to utilize renewable biomass resources to synthesis PTA and its derivatives.
　　Muconic acid can be produced from glucose and lignin by microbial synthesis. It contains a conjugated diene and two carboxylic acid moieties, which render it an attractive candidate for the synthesis of PTA. However, the solubility of muconic acid is very poor in many solvents, and its molecular structure contains two electron-withdrawing carboxylic acid groups, rendering its reaction with a dienophile difficult. To solve these problems, a synthetic route to diethyl terephthalate (DET), using muconic acid, ethanol, and ethylene as the reactants, through a cascade process combining esterification, Diels–Alder cycloaddition, and dehydrogenation has been proposed. The key esterification reaction improves the solubility of the reaction products in ethanol and modulates the electronic properties of muconic acid, thus promoting the Diels–Alder reaction with ethylene. The total yield of diethyl terephthalate reached 80.6% based on the amount of muconic acid used in the two-step synthetic process. This work provides an example of producing high-value aromatic chemicals by fully utilizing the existing specific structures of biomass-derived feedstock. By rational design of the functional groups, the utilization of biomass can thus become more economic and environmentally friendly.
　　This work was financially supported by the National Natural Science Foundation of China. (Text/Photo by Rui LU and Weiqiang YU)
　　

　　Nano and interfacial research group in the State Key Laboratory of Catalysis (SKLC) has recently made a new progress in confined growth of two-dimensional (2D) atomic crystal heterostructures and in-situ dynamic surface characterization. These new results have been published in the recent issue of ACS Nano (2015, 9, 11589-11598, http://pubs.acs.org/doi/abs/10.1021/acsnano.5b05509).
　　2D atomic crystal heterostructures have attracted increasing attentions recently. However, the controlled construction of the heterostructures remains as a challenge. A team lead by Prof. Qiang Fu and Prof. Xinhe Bao makes use of the newly developed photoemission electron microscopy (PEEM)/low energy electron microscopy (LEEM) system in SKLC and other surface science instruments to study chemistry at the interfaces between 2D materials and solid surfaces. They found that the interface can be regarded as a nanosized reactor. Accordingly, a concept “Chemistry under Cover” has been developed illustrating the 2D confinement effect on surface chemistry (Angew Chem Int Ed 2012, 51, 4856; PNAS 2014, 111, 17023; Nano Lett 2015, 15, 3616). Guided by this concept, they have explored the growth of one kind of 2D atomic crystal under the cover of the other kind of 2D atomic crystal, and succeed in construction of 2D atomic crystal heterostructures. These results suggest that the vertical stacking of 2D atomic crystals can be achieved through the confined growth under the cover, which provides a new route towards the growth of heterostructures. In the same issue, editor has highlighted this work with “Room to grow beneath h-BN” (http://pubs.acs.org/doi/full/10.1021/acsnano.5b07283）.
　　DICP Researchers Confine Growth of Two-Dimensional (2D) Atomic Crystal Heterostructures and In-situ Dynamic Surface Characterization (Photo by Ying SHI)
　　This work is supported by the Natural Science Foundation of China, the Ministry of Science and Technology, the Chinese Academy of Sciences, the Ministry of Finance, and the iChEM program. (By Ying Shi)
　　

　　The program of “Energy Storage Technology of Megawatt-scale Vanadium Flow Battery System”, carried by Dalian Rongke Power Co. Ltd and the group of Energy Storage Division (DNL 17, acting minister: Li Xianfeng) Dalian Institute of Chemical Physics (DICP) has won the second prize in “2015 China machinery industry science and technology” on the Chinese mechanical engineering society annual meeting, held in Nanning, 20th November, 2015. Lead researcher Zhang Huamin of DICP was the first completer of the program.(Text/Photo by RONG Qian)
　　 
　　The “Energy Storage Technology of Megawatt-scale Vanadium Flow Battery System” from wins the “China Machinery Industry Science and Technology Award”(Photo by RONG Qian)