天津大学彭文朝课题组--通过多孔工程和掺杂策略微调石墨烯上自由基/非自由基途径

使用ZnCl2，KOH和CO2活化了氮和硫共掺杂石墨烯（N，S-G），开发了不同种类的缺陷和功能性。这里，改性的碳催化剂被用来活化过一硫酸盐（PMS），用于苯酚降解。与掺氮石墨烯（N-G）相比，N，S-G表现出更好的催化活性，并且使用KOH活化会进一步增强氧化效率。自由基淬火实验，电化学表征和电子顺磁共振表征揭示N-G通过非自由基途径激活了PMS。二次硫掺杂剂将反应途径转变为自由基主导的氧化反应（SO4·和·OH）。不同于局限于催化剂表面的非自由基物质，自由基氧化会在本体溶液中产生，并保护碳催化剂免受腐蚀，从而确保碳催化剂更好的结构完整性和稳定性。基于结构-活性关系，该工作采用了一种简便的策略，设计了一种高性能的可扩展碳催化剂，即KOH活化和N，S共掺杂的石墨烯（N，S-G-rGO-KOH），有望用于实际应用。

Figure 1. 通过不同策略合成碳催化剂的过程示意图。

Figure 2. （a-d）不同样品的扫描电子显微镜（SEM）图像。（e-f）不同样品的投射电子显微镜（TEM）图像。（g）N，S-G-CO2的HRTEM图像。（h和i）N，S-G-KOH的TEM图像。

Figure 3（a）不同碳催化剂的X射线衍射（XRD）谱图，和（b）拉曼光谱。

Figure 4不同碳催化剂的（a）吸附和（b）降解曲线，以及（c）反应速率常数。

Figure 5（a）N，S-G，N，S-G-KOH和N，S-G-CO2的降解性能，以及（b）菲的化学结构。反应条件：菲的浓度为1 ppm，催化剂的浓度为100 mg/L，PMS的浓度为3.2 mM，温度为25°C。（c）DMPO-OH和DMPO-SO4，以及（d）TEMP-O2·−加合物的电子顺磁共振（EPR）谱。

该研究工作由天津大学Wenchao Peng课题组联合澳大利亚阿德莱德大学Xiaoguang Duan于2021年发表在ACS Catalysis期刊上。原文：Fine-Tuning Radical/Nonradical Pathways on Graphene by Porous Engineering and Doping Strategies。

彭文朝副教授

（天津大学化工学院）

研究方向：

1. 碳材料为基础的催化剂合成；

2. 电催化及光电催化；

3.化学氧化处理废水中有机污染物。

合作交流：

1.学术报告：Synergy of nitrogen doping and structural defects on hierarchically porous carbons toward catalytic oxidation via a non-radical pathway IZC' 19, Perth, Australia.

2. 学术报告：CdS-MoS2/GR的合成与光催化应用，ISPlasma2014/IC-PLANTS2014，Nagoya，Japan.

3. 学术报告：泡沫石墨负载混合相态硫化钨的合成及电催化析氢应用，2016 AIChE Annual Meeting，San Francisco , American.

科研情况介绍：

主要从事纳米材料制备新技术、功能陶瓷材料、纳米催化新材料等方面的研究。曾负责和参与了国家重大攻关项目、863、国家自然科学基金、教育部重大科技项目、北京自然科学基金、北京市科委重大科技项目、企业合作项目等。在Adv. Energy Mater.、Green Chem.、 Electrochimica Acta、ACS Appl. Mater. Interfaces、ACS Sustainable Chem. Eng.等刊物上发表论文100余篇；获国家发明专利授权20余件。以主要完成人获中国科学院科技进步一等奖1项。主持承担获得北京化工大学教改项目一等奖和二等奖各1项。材料科学与工程学院学术委员会委员、教授指导委员会委员和教学委员会委员，北京化工大学工会副主席，超细材料与先进陶瓷研究室主任，常州先进材料研究院纳米超净材料研究室主任。荣获2004年教师节北京化工大学优秀教师的光荣称号。现任中国化工学会会员。Green Chem.、Electrochimica Acta、ACS Appl. Mater. Interfaces、ACS Sustainable Chem. Eng、 Chemical Engineering Journal等期刊特约审稿人。主讲《材料化学》、《新型陶瓷材料》两门本科课程和材料前沿课程《材料与文明》。主讲研究生课程《陶瓷材料》和博士生材料前沿课程。指导的博士生和毕业硕士获得国家奖学金4人次。

代表性论文：

1.Wen Zhang1, Yang Li1, Xiaobin Fan1, Fengbao Zhang1, Guoliang Zhang1, Yi-An Zhu3, Wenchao Peng*, Shaobin Wang2 and Xiaoguang Duan*, Synergy of nitrogen doping and structural defects on hierarchically porous carbons toward catalytic oxidation via a non-radical pathway, Carbon 2019, DOI: 10.1016/j.carbon.2019.08.071.

2. Qianqian Jia1, Yuan Gao1, Yang Li1, Xiaobin Fan1, Fengbao Zhang1, Guoliang Zhang1, Wenchao Peng1* and Shaobin Wang2, Cobalt Nanoparticles Embedded in N-doped Carbon on Carbon Cloth as Free-standing Electrodes for Electrochemically-Assisted Catalytic Oxidation of Phenol and Overall Water splitting, Carbon 2019, DOI: 10.1016/j.carbon.2019.08.031.

3. Di Wu1,‡, Weiyu Song2,‡, Lulu Chen2, Xiaoguang Duan3, Qing Xia1, Xiaobin Fan1, Yang Li1, Fengbao Zhang1, Wenchao Peng1* and Shaobin Wang3, High-Performance Porous Graphene from Synergetic Nitrogen Doping and Physical Activation for Advanced Nonradical Oxidation, Journal of Hazardous Materials 2019, DOI: 10.1016/j.jhazmat.2019.121010, Accepted.

4. Xintong Li1,‡, Xiaoguang Duan2,‡, Chen Han3, Xiaobin Fan1, Yang Li1, Fengbao Zhang1, Guoliang Zhang1, Wenchao Peng1* and Shaobin Wang2, Chemical Activation of Nitrogen and Sulfur Co-doped Graphene as Defect-Rich Carbocatalyst for Electrochemical Water Splitting, Carbon 2019, 148, 540-549.

5. Weiwei Han1‡, Lulu Chen2‡, Biao Ma1, Jun Wang1, Weiyu Song2*, Xiaobin Fan1, Yang Li1, Fengbao Zhang1, and Wenchao Peng1*, Ultra-small Mo2C nanodots encapsulated in nitrogen-doped porous carbon for pH-universal hydrogen evolution: insights into the synergistic enhancement of HER activity by nitrogen doping and structural defects. Journal of Materials Chemistry A 2019, 7, 4734-4743.

6. Weiwei Han, Lulu Chen, Weiyu Song*, Shaobin Wang, Xiaobin Fan, Yang Li, Fengbao Zhang, Guoliang Zhang, Wenchao Peng*, Synthesis of Nitrogen and Sulfur Co-doped Reduced Graphene Oxide as Efficient Metal-free Cocatalyst for the Photo-activity Enhancement of CdS. Applied Catalysis B: Environmental2018, 236: 212-221.

7. Xiaomeng Guo1, Yuanzhi Zhu1, Weiwei Han1, Xiaobin Fan1, Yang Li1, Fengbao Zhang1, Guoliang Zhang1, Wenchao Peng1*, Shaobin Wang2*, Nitrogen-doped Graphene Quantum Dots Decorated Graphite Foam as Ultra-high Active Free-standing Electrode for Electrochemical Hydrogen Evolution and Phenol Degradation. Chemical Engineering Science 2019, 194, 54-57.

8. Xiaomeng Guo‡, Junyi Ji‡, Quanguo Jiang, Lili Zhang, Zhimin Ao*, Xiaobin Fan, Shaobin Wang, Yang Li, Fengbao Zhang, Guoliang Zhang, Wenchao Peng* .,Few-layered Trigonal WS2 Nanosheets Coated Graphite Foam as an Efficient Free-standing Electrode for Hydrogen Evolution Reaction. ACS Applied Materials & Interfaces 2017, 9, 30591-30598.

9. Yizhe Liu, Yuanzhi Zhu, Xiaobin Fan, Shaobin Wang**, Yang Li, Fengbao Zhang, Guoliang Zhang, Wenchao Peng*, (0D/3D) MoS2 on Porous Graphene as Catalysts for Enhanced Electrochemical Hydrogen Evolution. Carbon2017(121):163-169.

10. Wenchao Peng, Xiaoyan Li*, Synthesis of a sulfur-graphene composite as an enhanced metal-free photocatalyst. Nano Research 2013, 6, (4), 286-292.

11. Wenchao Peng, Shaobin Wang, Xiaoyan Li, The synergetic effect of MoS2 and graphene on Ag3PO4 for its ultra-enhanced photocatalytic activity in phenol degradation under visible light. Nanoscale 2014, 6, (14), 8311-8317.

12. Wenchao Peng, Shizhen Liu, Hongqi Sun, Yunjin Yao, Linjie Zhi, Shaobin Wang*, Synthesis of porous reduced graphene oxide as metal-free carbon for adsorption and catalytic oxidation of organics in water. Journal of Materials Chemistry A 2013, 1, (19), 5854-5859. （封面）

13. Wenchao Peng, Ying Chen, Y.; Xiaoyan Li, MoS2/reduced graphene oxide hybrid with CdS nanoparticles as a visible light-driven photocatalyst for the reduction of 4-nitrophenol. Journal of Hazardous Materials 2016, 309, 173-179.

14. Wenchao Peng, Ying Chen, Shidong Fan, Fengbao Zhang, Guoliang Zhang, Xiaobin Fan*, Use of 4,4 '-Dinitrostilbene-2,2'-Disulfonic Acid Wastewater As a Raw Material for Paramycin Production. Environmental Science & Technology2010, 44, (23), 9157-9162. （年度十佳论文）

15. Shizhen Liu‡, Wenchao Peng‡, Hongqi sun, Shaobin Wang*,Physical and chemical activation of reduced graphene oxide for enhanced adsorption and catalytic oxidation. Nanoscale 2014, 6, 766-771. (封面)

专利：

1.一种氮硫共掺杂活性炭负载铜镍复合金属催化剂、其制备方法及用途。（CN 106861743 A）

2. 4-氨基-2-磺酸基苯甲酸的制备方法。(CN102417471A)

3. TiO2负载Ni-Au-Pt纳米复合金属催化剂及制备方法和应用。(CN102500395A)