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个人资料 部门：化学工程学院 部门：化学工程学院 职务： 研究方向： (1)原子解析、催化剂的电子结构和量子力学计算方面的研究。(2)含覆盖度的微观动力学模型研究。(3)费托反应，双氧水合成，甲烷选择性氧化，炔烃衍生物半加氢（氘）等催化反应机理研究。 {"data":[{"fieldValue":"(1)原子解析、催化剂的电子结构和量子力学计算方面的研究。(2)含覆盖度的微观动力学模型研究。(3)费托反应，双氧水合成，甲烷选择性氧化，炔烃衍生物半加氢（氘）等催化反应机理研究。"}]} 联系电话：18368829688 电子邮箱：yaozihao@zjut.edu.cn 办公地址： 浙江工业大学莫干山校区2-220,个人资料 部门：化学工程学院 部门：化学工程学院 职务： 研究方向： (1)原子解析、催化剂的电子结构和量子力学计算方面的研究。(2)含覆盖度的微观动力学模型研究。(3)费托反应，双氧水合成，甲烷选择性氧化，炔烃衍生物半加氢（氘）等催化反应机理研究。 {"data":[{"fieldValue":"(1)原子解析、催化剂的电子结构和量子力学计算方面的研究。(2)含覆盖度的微观动力学模型研究。(3)费托反应，双氧水合成，甲烷选择性氧化，炔烃衍生物半加氢（氘）等催化反应机理研究。"}]} 联系电话：18368829688 电子邮箱：yaozihao@zjut.edu.cn 办公地址： 浙江工业大学莫干山校区2-220,个人简介       2013-10 至 2014-7，Queen's University Belfast，化学工程，本科交流。   2014-10 至 2018-7，Queen‘s University Belfast，化学, 博士。（导师：Professor P. Hu）   2018-12 至 2021-5，浙江工业大学, 化学工程，师资博士后。   2021-7 – 至今，浙江工业大学，化学工程，讲师。   研究方向：（1）原子解析、催化剂的电子结构和量子化学计算方面的研究。（2）非均相催化剂，含覆盖度影响的微观动力学模型研究。（3）费托反应，双氧水合成，甲烷选择性氧化，炔烃衍生物半加氢（氘）等反应。英国女王大学博士。目前就职于浙江工业大学国家杰出青年获得者王建国教授课题组进行研究工作，担任2023级健行学院分子化学实验班班主任。主要从事催化反应模拟和催化剂理论的第一性原理的研究，涉及到利用密度泛函理论和微观动力学模型阐明复杂化学反应机理，费托反应、炔烃半加氢（氘）及双氧水直接合成等机理的研究,含有覆盖度影响的微观动力学模型的研究。现主持一项国家青年基金项目（环境影响下Pd基催化双氧水直接合成理论模拟）。在ACS Catalysis（5 篇），Nature Communications（2篇），Advanced Functional Materials（1篇），Journal of Catalysis（1篇），Small （1篇）等国内外理论催化领域期刊发表学术论文50余篇。 About me Short biographyZihaoYao is a theoretical chemistry scientist from the Zhejiang. He was awarded Doctor of Philosophy in 2018 at the Queen’s University of Belfast Under the supervision of Professor Peijun Hu. His research involves the quantitative determination of C–C coupling mechanisms and detailed Analyses on the activity and selectivity for Fischer–Tropsch synthesis using microkinetic modeling with coverage effects. Currently, he is employed as a university researcher at the Zhejiang University of Technology. Research Gate Website: https://www.researchgate.net/profile/Zihao-Yao/researchOrcid: https://orcid.org/0000-0001-5259-6609Curriculum VitaeNameZihao YaoDay of BirthNovember, 1991Websitehttp://www.homepage.zjut.edu.cn/zyao01/E-mail addresszyao01@outlook.comEducation2014-2018Queen's University Belfast, PhD in Chemistry, supervisor: Prof. Peijun Hu2013-2014Chemical Engineering and Chemistry(Exchange), Queen's University Belfast2010-2013Bachelor of Science in Polymer Chemistry, NingBoTech University 2007-2010Hangzhou No.4 high schoolWork Experience and Current Employment2021-nowLecturer at the Zhejiang University of  technology2018-2021University Researcher at the Zhejiang University of technology2010-2014Ph.D. student at the Queen's University BelfastSkillsQuantumchemical simulationsVASP, GaussianTeachingExperience with teaching at MSc level in theoretical courses in chemistryLanguagesEnglish, Ou language, MandarinInstrumentPiano Selected Publications 1. Quantitative Determination of C–C Coupling Mechanisms and Detailed Analyses on the Activity and Selectivity for Fischer–Tropsch Synthesis on Co(0001): Microkinetic Modeling with Coverage Effects. ACS Catalysis, 2019, 9(7): 5957-5973. Zihao Yao; Chenxi Guo; Yu Mao; P. Hu* DOI: https://doi.org/10.1021/acscatal.9b01150      The Fischer−Tropsch synthesis plays a significant role in re-forming natural resources to meet global demand for commodities, while there is ongoing oil depletion and population growth. Mechanisms have long been investigated, but they are still a heavily debated issue. In this work, all of the possible elementary reaction steps on a flat cobalt surface were calculated using density functional theory (DFT) with van der Waals interactions. Kinetic simulations using standard DFT data (free energies and barriers at low coverages), the so-called non-coverage-dependent kinetic model commonly used in the literature, are compared to those from a coverage-dependent kinetic model for the system. We show that the coverage-dependent kinetic model gives rise to a TOF which is approximately 6 orders of magnitude larger than the TOF calculated using the noncoverage-dependent kinetic model. Furthermore, it is found that Co(0001) is highly selective to olefin production, and it is very likely to produce long-chain hydrocarbons. Both models demonstrate that the CO insertion mechanism is the dominant mechanism on Co(0001). Our calculations also reveal that high coverage of CHx leads to the carbide mechanism being significant and low coverage of CHx results in the CO insertion mechanism being more favored. Direct CO dissociation is difficult on Co(0001), which leads to monomers CHx being unable to occupy a certain amount of surface coverage, causing the carbide mechanism to be inhibited. The reaction pathway through CO + H → CHO, CHO + H → CHOH, and CHOH → CH + OH is the main channel to form the monomer CH on the basis of the coverage-dependent kinetic model simulations. The temperature considerably affects the surface coverage and the total reaction rate, leading to the selectivity being highly temperature dependent. Our coverage-dependent kinetic model predicts that the selectivity of oxygenates is high in comparison to methane in the low-temperature region from 425 and 475 K. From 475 to 525 K, the selectivity toward CH4 increases. From 525 to 700 K, the selectivity of C2 decreases significantly and the selectivity of CH4 increases remarkably.2. Quantitative Insights into the Reaction Mechanism for the Direct Synthesis of H2O2 over Transition Metals: Coverage-Dependent Microkinetic Modeling. ACS Catalysis 2021,11 (3), 1202-1221. Zihao Yao, JinYan Zhao, Rhys J. Bunting, Chenxia Zhao, P. Hu, and Jianguo Wang *DOI：https://doi.org/10.1021/acscatal.0c04125The direct synthesis is the most promising alternative method for the production of hydrogen peroxide, and the bottleneck is still unsolved. The breakthrough lies in elusive reaction mechanism issues. In this work, advanced coverage-dependent kinetic modeling is combined with the energetics from first principles calculations to investigate the formation of H2O2 over transition metals. We show that the adsorbate−adsorbate interactions considerably affect the reaction mechanism of synthesis of hydrogen peroxide on Pd(111). Without the coverage effect, O2 is likely to go through the direct dissociation mechanism, and water is the major product. When the coverage effects are included, the dissociations of O−O and O−OH bonds are significantly inhibited, and on the contrary, the hydrogenations of O2 and OOH are promoted, leading to the production of H2O2. We demonstrate that the reaction temperature induces strong variations in the coverage of intermediates, which in turn causes changes in product selectivity. Being consistent with the operando experiment, our kinetic simulations indicate that the H2/O2 partial pressure ratio has great effects on H2O2 selectivity and the reaction rate of H2O2 is lower under hydrogen-rich (oxygen-lean) and oxygen-rich (hydrogen-lean) conditions, which is highly related to the intermediate coverage. The same approach is also applied to other important relevant metals, i.e., Cu(111), Au(111), PdAu, and PdHg alloys, and the trends of activity and selectivity have been obtained.3. A first-principles study of reaction mechanism over carbon decorated oxygen-deficient TiO2 supported Pd. Chinese Journal of Chemical Engineering 2021, 31, 126-134. Zihao Yao; JinYan Zhao; Chenxia Zhao; Shengwei Deng; Guilin Zhuang; Xing Zhong; Zhongzhe Wei; Yang Li; Shibin Wang; Jianguo Wang* DOI：https://doi.org/10.1016/j.cjche.2020.11.016The choice of support is one of the most significant components in the direct synthesis of H2O2. Aiming to improvement of activity and selectivity of H2O2 on Pd/TiO2 surface, we systematically investigated the important elementary steps on Pd/TiO2-Vo@C, Pd/TiO2-Vo, Pd/TiO2-2Vo, Pd/TiO2, and Pd/C using the first-principles calculations. The Bader charge analysis and charge density difference of O2 adsorption elucidate the relationship between the electronic distribution and chemisorption energy. The effective barrier analysis further enables to quantitatively estimate the reactivity of H2O2 and H2O. We demonstrate unambiguously that the selectivity of H2O formation is boosted as the oxygen vacancy concentration raised. Moreover, the introduction of C into a TiO2 with appropriate oxygen vacancies can slightly reduce the effective barrier for H2O2 formation and increase the effective barrier for H2O formation leading to a higher activity and selectivity of H2O2 formation. Our finding suggests that carbon-doped oxygen vacancy TiO2 supported Pd is potential alternative catalyst compared with the Pd/TiO2.4. Optimizing Alkyne Hydrogenation Performance of Pd on Carbon in Situ Decorated with Oxygen-Deficient TiO2 by Integrating the Reaction and Diffusion. ACS Catalysis 2019,9 (12), 10656-10667. Zhongzhe Wei#; Zihao Yao#; Qiang Zhou; Guilin Zhuang; Xing Zhong; Shengwei Deng; Xiaonian Li; Jianguo Wang* (# Equal contribution)DOI：https://doi.org/10.1021/acscatal.9b03300The reaction/diffusion kinetics are fundamentally determined by the electronic properties of supported Pd catalysts and further govern the catalytic activity and selectivity in the partial hydrogenation of alkynes. However, how the electronic metal−support interactions and the tradeoff between reaction and diffusion affect the catalytic performance still remain elusive. Here, the optimized catalyst Pd supported on carbon decorated with oxygen-deficient TiO2(Pd/TiO2VO@C) features a remarkable enhancement in performance for semihydrogenation of 2-methyl-3-butyn-2-ol with a TOF 31-fold higher than that of Lindlar catalyst. The improved performance of Pd/TiO2-VO@C benefits from the fact that TiO2VO@C subtly modulates the electronic properties of Pd, and an appropriate amount of TiO2-VO allows a decrease in the reaction barrier and C promotes the diffusion ability of the catalyst, achieving the balance between reaction and diffusion. By using microkinetic modeling, the reactivity difference of various catalysts is quantitatively predicted and the calculated turnover frequency volcano curve is rationalized as a function of reaction barrier and diffusion ability, which agrees well with the experimental results. The quantitative regulation of catalytic performance by tuning the support properties is a general strategy, which provides a basis to design robust catalysts for diverse reactions.5. Oxo dicopper anchored on carbon nitride for selective oxidation of methane. Nature Communications, 2022, 13(1)  Pengfei Xie#*, Jing Ding#, Zihao Yao#, Tiancheng Pu#, Peng Zhang,  Zhennan Huang, Canhui Wang, Junlei Zhang, Noah Zecher-Freeman, Han Zong, Dashui Yuan, Shengwei Deng, Reza Shahbazian-Yassar, Chao Wang* (# Equal contribution)DOI: https://doi.org/10.1038/s41467-022-28987-1Selective conversion of methane (CH4) into value-added chemicals represents a grand challenge for the efficient utilization of rising hydrocarbon sources. We report here dimeric copper centers supported on graphitic carbon nitride (denoted as Cu2@C3N4) as advanced catalysts for CH4 partial oxidation. The copper-dimer catalysts demonstrate high selectivity for partial oxidation of methane under both thermo- and photocatalytic reaction conditions, with hydrogen peroxide (H2O2) and oxygen (O2) being used as the oxidizer, respectively. In particular, the photocatalytic oxidation of CH4 with O2 achieves >10% conversion, and >98% selectivity toward methyl oxygenates and a mass-specific activity of 1399.3 mmol g Cu−1 h−1 . Mechanistic studies reveal that the high reactivity of Cu2@C3N4 can be ascribed to sym-phonic mechanisms among the bridging oxygen, the two copper sites and the semi-conducting C3N4 substrate, which do not only facilitate the heterolytic scission of C-H bond, but also promotes H2O2 and O2 activation in thermo- and photocatalysis, respectively.6. Synergistic Effect of Size-Dependent PtZn Nanoparticles and Zinc Single-Atom Sites for Electrochemical Ozone Production in Neutral Media. Journal of Energy Chemistry,Volume 51, December 2020, Pages 312-322. Bowen Yuan#, Zihao Yao#, Chenlong Qiu, Haiyang Zheng, Yilong Yan, Qiaoqiao Zhang，Xiang Sun, Yu Gu, Xing Zhong*, Xiaonian Li, and Jianguo Wang* (# Equal contribution)DOI: https://doi.org/10.1016/j.jechem.2020.03.066Electrochemical ozone production (EOP) via water electrolysis represents an attractive method for the generation of high-purity O3. However, to date, efficient EOP electrocatalysis in neutral media has rarely been achieved. Herein, the X-PtZn/Zn-N-C electrocatalysts show a strong structural sensitive behavior depends on the size of the PtZn nanoparticles and their EOP activity exhibits a volcano-type dependence for the O3 performance in neutral media. The 7.7-PtZn/Zn-N-C sample shows the prominent performance in the production of gaseous O3 with a value of 1647 ppb at 30 min, which is almost 4-fold compared to 2.2-PtZn/Zn-N-C. Based on the experiments and theoretical calculations, the performance of the EOP process was determined by considering the nanoparticle size-effect and the synergistic effect between the PtZn nanoparticles and atomically dispersed Zn-N-C. Furthermore, the five-membered cyclic structure of O3 can be stabilized between the PtZn nanoparticle and the Zn-N-C support, indicating that O3 is produced at the interface. The results on the size-effect and synergistic effect reported in this work pave the way for the rational design of highly active and durable electrocatalysts for the electrochemical generation of ozone in environmental and energy-related applications.7. Biomass Valorization via Paired Electrosynthesis Over Vanadium Nitride-Based Electrocatalysts. Adv. Funct. Mater. 2019, 1904780. Suiqin Li#, Xiang Sun#, Zihao Yao#, Xing Zhong,* Yongyong Cao, Yulin Liang, Zhongzhe Wei, Shengwei Deng, Guilin Zhuang, Xiaonian Li, and Jianguo Wang* (# Equal contribution)DOI: https://doi.org/10.1002/adfm.201904780Paired electrosynthesis is a promising technology with the potential to generate value-added products at both electrodes in a cost-effective manner. Herein, 3D vanadium nitride (VN) and Pd/VN hollow nanospheres are successfully fabricated and coupled to carry out simultaneous electrocatalytic oxidation (ECO) and electrocatalytic hydrogenation (ECH) of 5-hydroxymethylfurfural (HMF) into 2, 5-furandicarboxylic acid (FDCA) and 2,5-bishydroxymethyl-tetrahydrofuran (DHMTHF), respectively. VN shows excellent ECO performance with high HMF conversion (≥98%), FDCA selectivity (≥96%), and faradaic efficiency (≥84%) after a stability test, and Pd/VN achieves high ECH selectivity for DHMTHF at ≥88% and an HMF conversion of ≥90%, with a faradaic efficiency of ≥86%. VN and Pd/VN incorporated into a membrane electrode assembly in a paired electrolysis system shows potential for large-scale biomass conversion and upgrading. Theoretical calculations reveal that the higher performance of VN for the production of ECO can be attributed to its lower d-band center level relative to the Fermi level compared to that of V2O5, which favors HMF chemisorption and activation. This study paves the way for developing paired electrosynthesis technologies with the potential for biomass utilization and energy conversion.8. Synergistic Effect of Doped Nitrogen and Oxygen-containing Functional Groups for Electrochemical Synthesis of Hydrogen Peroxide. J.Mater.Chem,A, 2022,10,4749 Zhikang Bao#, Jinyan Zhao#, Shijie Zhang, LeiDing, Xiaoge Peng, Guoliang Wang, Zijiang Zhao, Xing Zhong, Zihao Yao*, Jianguo Wang* (# Equal contribution)DOI: 10.1039/d1ta09915a9. Geometric and electronic effects on the performance of a bifunctional Ru2P catalyst in the hydrogenation and acceptorless dehydrogenation of N‐heteroarenes. Chinese Journal of Catalysis 42 (2021) 1185–1194. Fangjun Shao#, Zihao Yao#, Yijing Gao, Qiang Zhou, Zhikang Bao, Guilin Zhuang, Xing Zhong, Chuan Wu, Zhongzhe Wei*, Jianguo Wang (# Equal contribution)DOI: 10.1016/S1872‐2067(20)63747‐0It is a challenge to develop bifunctional catalysts for the efficient hydrogenation and acceptorless dehydrogenation of N-heterocycles. In this work, Ru2P/AC achieved the reversible transformations between unsaturated and saturated N-heterocycles, affording up the yield of 98% and 99%, respectively. Moreover, a remarkable enhancement in reusability of Ru2P/AC was observed compared with other Ru-based catalysts. By density functional theory calculations, the superior performance of Ru2P/AC was ascribed to the specific synergistic effects, which is geometric and electronic effects induced by P. The doped P greatly diluted the large Ru−Ru ensembles and finely modified the electronic structures, leading to the low reaction barrier and high diffusion ability of the catalysts, and further boosting the hydrogenation and acceptorless dehydrogenation process.10. Formation Mechanism of Monocyclic Aromatic Hydrocarbons during Pyrolysis of Styrene Butadiene Rubber in Waste Passenger Car Tires. ACS Omega 2022, 7, 47, 42890-42900. Jiayuan Li, Dahai Zheng, Zihao Yao*, Shixin Wang, Ruinian Xu*, Shengwei Deng*, Biaohua Chen, and Jianguo WangDOI: https://doi.org/10.1021/acsomega.2c04994The production of aromatic hydrocarbons from the waste tire pyrolysis attracts more and more attention because of its tremendous potential. Based on styrene-butadiene rubber (SBR), which is the main rubber in the waste passenger car tires, this work studies the temperature influence on primary pyrolysis product distribution by experimental techniques (Py-GC/MS, TG–MS), and then, the formation mechanism of monocyclic aromatic hydrocarbons (MAHs) observed in the experiment was analyzed by first-principles calculations. The experimental results show that the MAHs during the pyrolysis mainly include styrene, toluene, and xylene, and subsequent calculations showed that these compounds were formed through a series of primary and secondary reactions. The formation pathways of these typical MAHs were studied via the reaction energy barrier analysis, respectively. It shows that the MAHs were not only derived from the benzene ring in the SBR chain but also generated from short-chain alkenes through the Diels–Alder reaction. The obtained pyrolysis reaction mechanism provides theoretical guidance for the regulation of the pyrolysis product distribution of MAHs.11. Unravelling the functional complexity of oxygen-containing groups on carbon for the reduction of NO with NH3. Journal of the Taiwan Institute of Chemical Engineers, 2022, 133: 104261. Yuejin Li, Shijie Zhang, Xiang Sun, Yijing Gao, Xiangyu Kong, Lele Zhang, Xing Zhong, Shangpeng Zhai*, Zihao Yao*, JianguoWang*DOI: https://doi.org/10.1016/j.jtice.2022.104261Oxygen-containing groups on carbon materials play a crucial role in thermocatalytic and electrocatalytic reactions. A series of carbon-based catalysts with various oxygen-containing groups were synthesized by hydrogen peroxide oxidation for selective catalytic reduction (SCR) of NO with NH3. The textural properties and oxygen-containing groups types were measured by N2 adsorption-desorption and spectroscopic characterization, respectively. Denitrification experiment results show the denitrification efficiency is correlated with the oxygen contents. The density functional theory (DFT) calculations demonstrate that oxygen-containing groups can promote the chemisorption for NO and NH3, thus resulting in high performance for NO reduction. The carboxyl and phenol groups on carbon materials facilitate the catalytic performance of denitrification. Furthermore, based on mechanism analysis that the formation of CO (NH4) and C(NO) on surface oxides is considered significant steps for NO reduction with NH3. Our finding paves a new strategy for the design and synthesis of SCR catalysts with excellent activity for oxygen-containing carbon material at a relatively low temperature.12. A first-principles study of the interaction between TDI-TMP-T313 and AP. CIESC Journal, 2022, Vol. 73, Issue (8): 3511-3517. Xiaqi Yu*, Ge Feng, Jinyan Zhao, Jiayuan Li, Shengwei Deng, Jingnan Zheng, Wenwen Li, Yaqiu Wang, Lan Shen, Xu Liu, Weiwei Xu, Jianguo Wang, Shibin Wang, Zihao Yao*, Chengli Mao*DOI: 10.11949/0438-1157.20220262Density functional theory (DFT) is used to study the surface energies of four crystal planes of oxidant-ammonium perchlorate (001), (210), (011), (201), and the surfaces' stability is tested by ab initio molecular dynamics (AIMD) simulation. The adsorption energies of the matrix components-toluene diisocyanate (TDI), trihydroxymethyl propane (TMP) and boron trifluoride tritylamine complex (T313) on the crystal planes of oxidizing agent are also calculated by DFT. The interaction between matrix and oxidizing agent is analyzed theoretically. Eventually, the T313-AP (201) system with the strongest interaction between adsorbent and crystal plane is selected for bader charge analysis to simulate its molecular electronic structure and observe the charge transfer between atoms. The mechanism of interaction between bonding agent (T313) and oxidizing agent (AP) is revealed on a molecular scale by various theoretical methods. The sources of critical products produced in the ageing process are confirmed.13. Microkinetic Simulations of Acetylene (Acetylene-d2) Hydrogenation (Deuteration) on Ag Nanoparticles. Molecule Catalysis. Volume 535, 15 January 2023, 112845. Jiayuan Li, Zihao Yao*, Jinyan Zhao, Shengwei Deng, Shibin Wang, Jianguo Wang*DOI: https://doi.org/10.1016/j.mcat.2022.112845The semi-hydrogenation(deuteration) of alkynes plays an essential role in high-value chemical production, and the reaction mechanism between H and D remains elusive. In this work, advanced microkinetic modeling is combined with the energetics from the first principles calculation to investigate the activity and selectivity of acetylene hydrogenation (acetylene-d2 deuteration) on Ag nanoparticles. By constructing a polyhedral model, it can be found that the olefin production on Ag nanoparticles converged when the size was at the diameter of 6 nm. Furthermore, it is found that the effective production rates are contributed by Ag(100) and Ag55 (corner site). The temperature considerably affects the free reaction energy (ΔG) between hydrogenation and deuteration. Consistent with the experiment, our kinetic simulations indicate that hydrogenation gives rise to a reaction rate approximately 3 times larger than the TOF of deuteration. 14. Subsurface Ru-triggered hydrogenation capability of TiO2-x overlayer for poison-resistant reduction of N-heteroarenes. ACS Catalysis. 2023, 13, 1, 757–765. Shurui Fan#, Zihao Yao#, Wei Cheng, Xian Zhou, Yao Xu, Xuetao Qin, Siyu Yao, Xi Liu*, Jianguo Wang*, Xiaonian Li*, Lili Lin*. (# Equal contribution)DOI: https://doi.org/10.1021/acscatal.2c04270Transition metal-based catalysts are applied widely in the hydrogenation reaction of different organic compounds. However, serious deactivation occurs when the substrate contains strong coordinating functional groups or impurities. In this paper, we reported that the TiO2-x overlayer formed over the Ru NPs (Ru@TiO2-x/TiO2) under reduction condition worked as the chemoselective, durable and sulfur resistant catalyst for the partial hydrogenation of quinoline and other N-heteroarenes. Mechanism studies revealed that the inhibitation of quinoline and its reduced product on the H2 activation and hydrogenation reaction over the Ru NPs was eliminated on the active non-metal overlayer of Ru@TiO2-x. The oxygen vacancies of the Ru@TiO2-x overlayer was determined as the active sites for H2 activation. The synergy between the TiO2-Ov (TiO2-x) active sites with the subsurface Ru particles effectively reduced the barriers of H2 dissociation and H addition steps, enabling the non-metal TiO2-Ov shell catalyze the hydrogenation reaction at mild condition with remarkable stability and poisoning resistance.15. Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation. Nature Communications. Volume 14, P: 1-11. Zhongzhe Wei#, Zijiang Zhao#, Chenglong Qiu, Songtao Huang, Zihao Yao*, Mingxuan Wang, Yi Chen, Yue Lin, Xing Zhong, Xiaonian Li*, Jianguo Wang* (# Equal contribution)DOI: https://doi.org/10.1038/s41467-023-36378-32D metallene nanomaterials have spurred considerable attention in heterogeneous catalysis by virtue of sufficient unsaturated metal atoms, high specific surface area and surface strain. Nevertheless, the strong metallic bonding in nanoparticles aggravates the difficulty in the controllable regulation of the geometry of metallenes. Here we propose an efficient galvanic replacement strategy to construct Pd metallenes loaded on Nb2C MXenes at room temperature, which is triggered by ultra-strong metal-support interaction based on MD simulations. A combination of electron microscopy, synchrotron X-ray absorption spectroscopy characterizations and theoretical calculations confirm that the Pd metallenes feature a chair structure of six-membered ring with the coordination number of Pd as low as 3. The tripodal Pd metallenes promote the diffusion of alkenes as the effective Pd atoms directly bonded with alkenes decreased compared with traditional Pd (111). As a consequence, the Pd/Nb2C delivers an outstanding turnover frequency of 10372 h-1 and a high selectivity of 96% at 25 oC in the semihydrogenation of alkynes without compromising the stability. In this work, advanced coverage-dependent kinetic modeling is combined with the energetics from first-principles calculations to investigate the hydrogenation of CHCR over Pd(111) and Nb2C/Pd. With the coverage effect, the better diffusion ability of CH2CHR on Pd/Nb2C was observed compared to that on Pd (111). The high selectivity of CH2CHR on Pd/Nb2C can be explained by higher hydrogenation barrier of CH2CHR+H→CH2CH2R and CH2CH2R+H→CH3CH2R. This strategy is general and scalable considering the plentiful members of the MXene family, which can set a foundation for the design of novel supported-metallene catalysts for demanding transformations.16. Coherent Sub-Nanometer Interface between Crystalline and Amorphous Materials Boosts Electrochemical Synthesis of Hydrogen Peroxide. Small 2023. Zhikang Bao#, Zihao Yao#, Chongzhi Zhu, Yikuan Liu, Shijie Zhang, Jinyan Zhao, Lei Ding, Zaixiang Xu, Xing Zhong,* Yihan Zhu,* and Jianguo Wang*(# Equal contribution)DOI: 10.1002/smll.202302380There are enormous yet largely underexplored exotic phenomena and properties emerging from interfaces constructed by diverse types of components that may differ in composition, shape, or crystal structure. It remains poorly understood the unique properties a coherent interface between crystalline and amorphous materials may evoke, and there lacks a general strategy to fabricate such interfaces. It is demonstrated that by topotactic partial oxidation heterostructures composed ofcoherently registered crystalline and amorphous materials can be constructed. As a proof-of-concept study, heterostructures consisting ofcrystalline P3N5 and amorphous P3N5Ox can be synthesized by creating amorphous P3N5Ox from crystalline P3N5 without interrupting the covalent bonding across the coherent interface. The heterostructure is dictated by nanometer-sized short-range-ordered P3N5 domains enclosed by amorphous P3N5Ox matrix, which entails simultaneously fast charge transfer across the interface and bicomponent synergistic effect in catalysis. Such a P3N5/P3N5Ox heterostructure attains an optimal adsorption energy for *OOH intermediates and exhibits superior electrocatalytic performance toward H2O2 production by adopting a selectivity of 96.68% at 0.4 VRHE and a production rate of 321.5 mmol h−1 gcatalyst−1 at −0.3 VRHE. The current study provides new insights into the synthetic strategy, chemical structure, and catalytic property of a sub-nanometer coherent interface formed between crystalline and amorphous materials.17. Solid propellants: A first-principles study of nitrous oxide generation from A3. Propellants, Explosives, Pyrotechnics. 2023. Lan Shen, Zihao Yao*,Shengwei Deng, Shibin Wang, Chengli Mao, Jianguo Wang.DOI: 10.1002/prep.202300103Density functional theory (DFT) is used to calculate and study the reaction mechanism of the four equations of nitrous oxide generation from plasticizer A3 (BDNPF: BDNPA=1:1). The optimal pathway is found for each equation, and finally, an optimal total pathway is found. At the same time, HONO is generated from A3 degradation. The stability is evaluated through ab-initio molecular dynamics simulation (AIMD), and the electronic structure is analyzed to determine the active sites. The decomposition of A3 accelerates the aging of solid rocket propellant. Therefore, the mechanism of nitrous oxide generation from A3 can be revealed through various theoretical methods, which is of great significance for the subsequent slowing down of the aging of solid propellant.18. Tailoring crystal facet microenvironments for simultaneous electrochemical ozone and hydrogen peroxide production. AIChe Journal. 2023. Xiaosha Wang#, Jiayuan Li#, Lei Ding, Huaijie Shi, Jia Liu, Xinyu Yang, Min Li, Xing Zhong*, Zihao Yao*, Jianguo Wang*(# Equal contribution)DOI: https://doi.org/10.1002/aic.18152Developing a bifunctional electrocatalyst that can effectively produce O3 and H2O2 is significant for the electrochemical synthesis of O3 and H2O2 for the synergistic oxidative degradation of organic pollutants. In this study, SnO with various exposed facets was synthesized by tailoring the crystal facet microenvironment for oxygen intermediates adsorption for electrochemical ozone production (EOP) and two-electron oxygen reduction reaction (2e− ORR). The Faraday efficiency of SnO-1 with a high (110) facet ratio for O3 was 22.0%, while SnO-4 with a high (002) facet ratio achieved a selectivity of 93.6% for H2O2. The theoretical calculation indicates that their excellent performances originated from the strong adsorption of the (110) facet on O* and O2* and the suitable adsorption and desorption strength of the (002) facet on OOH*, respectively. This study provides an attractive strategy for the development of a bifunctional electrocatalyst for advanced electrochemical oxidation by tailoring the crystal facet microenvironment.19. A Microkinetic Modeling with Size-dependent and Adsorbate-adsorbate Interactions for the Direct Synthesis of H2O2 over Pd Nanoparticles. ACS Catalysis, 2023, 13, 15054-15073, Jinyan Zhao#, Zihao Yao#*, Rhys J. Bunting, P. Hu*, Jianguo Wang* (# Equal contribution)DOI: https://doi.org/10.1021/acscatal.3c03893 As the bottleneck in the direct synthesis of hydrogen peroxide, the development of the efficient palladium-based catalyst has garnered great attention. However, elusive active centres and reaction mechanism issues inhibit further optimizing its performance. In this work, an advanced microkinetic modeling with the adsorbate-adsorbate interaction and nanoparticle size effect based on first-principles calculations is developed. A full mechanism uncovering the significance of adsorbate-adsorbate interaction is determined on Pd nanoparticles.We demonstrate unambiguously that Pd(100) with main coverage species of O2 and H is beneficial to H2O2 production, being consistent with experimental operando observation, while H2O forms onPd(111) covered by O species and Pd(211)covered by O and OH species.Kinetic analyses further enable the quantitative estimate of the influence of temperature, pressure, and particle size. Large-size Pd nanoparticles are found to achieve the high H2O2 reaction rate when the operating conditions are moderate-temperature and higher oxygen partial pressure.We reveal that specific facets of the Pd nanoparticles are crucial factors for the selectivity and activity. Consistent with the experiment, the production of H2O2 is discovered to be more favourable on Pd nanoparticles containing Pd(100) facets. The ratio of H2/O2 induces substantial variations in the coverage of intermediates of O2 and H on Pd(100), resulting in changing in product selectivity.20. Unravelling the reaction mechanism for H2 production via formic acid  decomposition over Pd: Coverage-Dependent microkinetic modeling. Chemical Engineering Science, 2024, 291:119959. Zihao Yao*#, Xu Liu#, Rhys J. Bunting, Jianguo Wang*. (# Equal contribution)DOI: https://doi.org/10.1016/j.ces.2024.119959 As a key liquid organic hydrogen carrier, investigating the decomposition of formic acid (HCOOH) on the Pd  (111) transition metal surface is imperative for harnessing hydrogen energy. Despite a multitude of studies, the  major mechanisms and key intermediates involved in the dehydrogenation process of formic acid remain a great  topic of debate due to ambiguous adsorbate interactions. In this research, we develop an advanced microkinetic  model based on first-principles calculations, accounting for adsorbate–adsorbate interactions. Our study unveils  a comprehensive mechanism for the Pd (111) surface, highlighting the significance of coverage effects in formic  acid dehydrogenation. Our findings unequivocally demonstrate that H coverage on the Pd (111) surface renders  formic acid more susceptible to decompose into H2 and CO2 through COOH intermediates. Consistent with  experimental results, the selectivity of H2 in the decomposition of formic acid on the Pd (111) surface approaches 100 %. Considering the influence of H coverage, our kinetic analysis aligns perfectly with experimental  values at a temperature of 373 K.21. Unravelling the Reaction Mechanism for the AP Decomposition over MgO: A Density Functional Theory Study and Microkinetic Simulation.Material Today Communications, Volume 39, June 2024, 108658.Yaqiu Wang, Zihao Yao*, Shengwei Deng, Chengli Mao, Jianguo Wang.DOI: https://doi.org/10.1016/j.mtcomm.2024.108658The detailed reaction pathways for the decomposition of ammonium perchlorate (AP), an essential component in solid composite propellants, are poorly understood due to the ultrafast and complex reactions. In this work, density functional theory and kinetic simulation are utilized to calculate the decomposition reaction of AP on the surface of magnesium oxide and present a detailed decomposition network. Using a proton transfer mechanism, NH3 and HClO4 are the major production at low-temperature decomposition of AP, involving two elementary steps. AP is completely decomposed in the high-temperature reaction stage.We find that the decomposition of NH3 is mainly in the form of oxidative dehydrogenation, while HClO4 proceeds along the pathway HClO4→ClO3→ClO2→ClO→Cl, and the final nitrogen oxides, chlorine oxides are formed. These simulations provide an atomic insight into the complex reaction kinetics of AP and can be extended to the reaction mechanisms of other metal oxides. 育人成果 （1）担任2023级健行学院分子化学实验班班主任。《新生破冰行动》主题班会Your user agent does not support the HTML5 Video element. Honor (1) 中国化工学会科学技术奖（2022年度）奖种：基础研究成果奖获奖项目：纳米催化剂的微观作用机制及工业应用获奖人：王建国、钟兴、卢春山、姚子豪、魏中哲、邓声威获奖等级：一等奖证书编号：2022-YJ-01-04-R04 MCE课题组主页 Laboratory of Molecular Catalysis and Computational MaterialsMCE课题组主页http://www.mccm.zjut.edu.cn/aspx/index.aspx新闻速递：（1）浙江工业大学ACS Catal.: 含覆盖度影响的微观动力学模型探究双氧水直接合成反应机理Quantitative Insights into the Reaction Mechanism for the Direct Synthesis of H2O2 over Transition Metals: Coverage-Dependent Microkinetic Modeling第一作者：姚子豪；通讯作者：王建国教授；通讯单位：浙江工业大学论文链接: https://pubs.acs.org/doi/10.1021/acscatal.0c04125摘要:氢气(H2)和氧气(O2)反应直接合成过氧化氢(H2O2)是最有希望替代蒽醌法(AO process)的工艺，然而瓶颈问题目前仍未解决。突破口在于晦涩难懂的反应机理问题。在这项工作中，我们将先进的含覆盖度影响的微观动力学模型与第一性原理计算中的得到的能量相结合，用以研究H2O2在过渡金属上的形成。微观动力学结果表明，吸附物(adsorbate)和吸附物(adsorbate)的相互作用极大地影响了过氧化氢在Pd(111)上的反应机理。在模型忽略空间位阻的物理作用时，O2倾向于直接解离，从而导致H2O是主要的产物。当考虑覆盖度的作用时，O-O和O-OH键的直接解离被显著抑制；相反，促进了O2和OOH的加氢能力，强化了H2O2的生成速率。我们证明了反应温度能够引起中间体的表面浓度强烈变化，进而影响产物的选择性。研究结论与原位实验结果趋势自洽，H2/O2的分压比例对H2O2的选择性具有显著的影响。动力学模拟结果表明在富氢（贫氧）和富氧（贫氢）条件下，双氧水产生的速率较低，这一奇特现象与中间体在表面的覆盖度浓度相关。同样的方法也适用于其它重要过渡金属，例如Cu(111)，Au(111)，PdAu和PdHg合金，并且我们成功预测了活性和选择性的趋势。文章亮点：（1）含覆盖度影响的微观动力学模型(真实条件下反应机理的近似)在利用密度泛函理论结合微观动力学探究双氧水合成机理方面，我们对过氧化氢合成的可能发生的基元反应进行一个总的探究。在研究过程之中，利用过渡态理论，常微分方程以及密度泛函理论计算能量数据，已经成功模拟出催化剂的活性和选择性数据。在此基础上，研究之中考虑了反应的温度，氢气氧气分压以及覆盖度的影响。在研究过程之中发现覆盖度对反应活性和选择性的巨大影响。如图1(a-b)所示，在不考虑覆盖度，以及H2/O2为1的双氧水微观动力学模拟中，中间体O*堵塞表面所有的活性位点，导致催化剂中毒，这违背了在真实条件下，各种中间体相互影响的事实。而当反应模型考虑了覆盖度的影响之后，将不再是催化剂中毒的现象,而是中间体H*和O*产生了竞争。为了验证原位实验中，不同比例H2/O2会导致催化剂的相变，我们进一步利用含覆盖度的微观动力学模型，对表面中间体的覆盖度进行了预测，如图1(c)所示，表面中间体的覆盖度随环境气氛的改变动态波动。在富氧情况下，催化剂表面主要由O*和空穴构成而H*占有极低的比例，高覆盖度的氧的形成直接导致氧化物的形成。而在富氢情况下，催化剂表面主要被H*占据，而O*处于低覆盖度，意味着氢化钯形成的高度可能性。含覆盖度的微观动力学和原位实验结果自洽(ACS Catalysis 2018, 8 (3), 2546-2557)，而不含覆盖度的微观动力学模型在对原位机理预测上有一定的偏差。图(1): (a) 不含覆盖度影响的微观动力学模型对表面中间体覆盖度的预测；(b) 含覆盖度影响的微观动力学模型对表面中间体覆盖度的预测；(c) 在不同H2/O2比例下，含覆盖度影响的微观动力学模型对表面中间体覆盖度的预测。（2）爆炸界限的理论模拟我们采用理论模拟确立了爆炸界限的范围（图2）。在爆炸区域中双氧水的选择性随着氢气压力的上升急剧提升，却还未达到双氧水最高选择性的极值。同时我们预测了最优反应区域：既满足了双氧水具有最高选择性又具有安全性操作的条件。我们的工作为实验提供了坚实的指导意义。图(2): 二维热图描述选择性与氢气压力和温度的关系