Article
Chemistry, Multidisciplinary
Anmin Liu, Xingyou Liang, Qiyue Yang, Xuefeng Ren, Mengfan Gao, Yanan Yang, Tingli Ma
Summary: In this study, a Cu/Ti3C2 composite catalyst was prepared for efficient electrochemical conversion of N2 into NH3. This catalyst exhibited high Faradaic efficiency and NH3 production rate in 0.1 M KOH solution. Moreover, it showed superior electrochemical stability and durability, with Cu playing a vital role in enhancing the catalytic activity and conductivity of Ti3C2-based materials.
Article
Chemistry, Physical
Mengzhao Zhang, Hanqing Yin, Fuhao Jin, Jingquan Liu, Xuqiang Ji, Aijun Du, Wenrong Yang, Zhen Liu
Summary: Nb-based MXenes are developed to enhance the NRR activity and achieve efficient conversion of nitrogen into ammonia through the engineering of the stretched 3D structure and oxygen vacancies. The catalysts show high ammonia production rate and excellent Faradic efficiency, and the selectivity is attributed to the unique structure including layered graphitic structure, reactive oxygen vacancies, and expanded interlayer space.
GREEN ENERGY & ENVIRONMENT
(2023)
Article
Chemistry, Physical
Wenzhuo Wu, Chunyao Niu, Pengfei Yan, Feng Shi, Chunyan Ma, Xinan Yang, Yu Jia, Jun Chen, Muhammad Ibrar Ahmed, Chuan Zhao, Qun Xu
Summary: Efficient electroreduction of N-2 into NH3 remains challenging due to scaling relations and competing HER. However, a sub-monolayer MoS2-x structure can dissociate and dynamically hydrogenize N-2, stabilize nitrogen intermediates selectively, and bypass inherent scaling relations, achieving outstanding electrocatalytic performance at ultra-low overpotential.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Article
Chemistry, Multidisciplinary
Xianhong Wu, Junhui Wang, Zhiyu Wang, Fu Sun, Yuzhao Liu, Kaifeng Wu, Xiangyu Meng, Jieshan Qiu
Summary: An efficient strategy is proposed to enhance the electrochemical activity of MXenes for electrocatalysis by utilizing their plasmonic response to electromagnetic waves, resulting in a significant thermoplasmonic effect that lowers the energy requirements and activation energy of the hydrogen evolution reaction. This approach also facilitates interfacial charge transfer and boosts the HER activity of various types of MXenes with improved kinetics and Faradaic efficiency across a wide pH range.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Kai S. Exner
Summary: This article compares the methods of breaking scaling relation and catalytic resonance in the context of electrocatalysts for nitrogen reduction reaction (NRR) over transition-metal oxides. The findings suggest that fine-tuning the nitrogen-containing scaling relations can enhance the catalytic activity, while the success of catalytic resonance theory depends on the positive or negative scaling correlations.
Article
Chemistry, Physical
Benjamin D. Groff, James M. Mayer
Summary: This study demonstrates the generality of molecular scaling relationships in achieving faster catalysis at lower overpotentials. By independently controlling the characteristics of the catalyst and the buffer solution, both the maximum turnover frequency and the effective overpotential have been improved. The most optimal system is achieved with the most reducing catalyst and a weak buffered acid, which may seem counterintuitive.
Article
Chemistry, Multidisciplinary
Guilan Fan, Wence Xu, Jinhan Li, Jia-Liang Chen, Meng Yu, Youxuan Ni, Shengli Zhu, Xun-Cheng Su, Fangyi Cheng
Summary: The nanoporous NiSb alloy is reported as an efficient electrocatalyst for N-2 fixation, achieving high ammonia yield rate and Faradaic efficiency. Density functional theory calculations reveal the advantages of NiSb alloy in N-2 hydrogenation, providing a promising strategy for enhancing the reduction of inert molecules.
ADVANCED MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Qi Zhao, Chao Zhang, Riming Hu, Zhiguo Du, Jianan Gu, Yanglansen Cui, Xiao Chen, Wenjie Xu, Zongju Cheng, Songmei Li, Bin Li, Yuefeng Liu, Weihua Chen, Chuntai Liu, Jiaxiang Shang, Li Song, Shubin Yang
Summary: An efficient method for producing single atom copper immobilized MXene for catalyzing CO2 reduction to methanol through selective etching of hybrid A layers in quaternary MAX phases was demonstrated. The single atom Cu catalyst exhibited high Faradaic efficiency and good electrocatalytic stability, attributed to its unique electronic structure and surface functional groups.
Article
Chemistry, Physical
Shoushuang Huang, Jinmei Bao, Deyu Xiang, Chunyan Gao, Kaimei Peng, Qiaochuan Chen, Shuzhen Ma, Yong Jiang, Zhangjun Hu, Jiujun Zhang
Summary: In this study, uniform Ag@AgP2@Ni-CoP@C core-shell nanowires have been synthesized using a template-engaged strategy. The merging of conductive Ag core with active AgP2 and porous carbon-coated Ni-doped CoP shells favors the mass and electron transfers, effectively lowering the activation energy toward the reduction of N2 to NH3. The titled catalyst achieved a high NH3 yield of 16.84 μg h-1 mg-1 cat. at -0.4V (vs. RHE) and a high Faradaic efficiency of 21.7% at -0.3V vs. RHE, as well as high electrochemical and structure stability.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Physical
Jiabin Tan, Xiaobo He, Fengxiang Yin, Xin Liang, Guoru Li, Zhichun Li
Summary: Zr-doped alpha-FeOOH was developed as an electrocatalyst for electrochemical nitrogen reduction reaction, achieving high NH3 yield and increased Faradaic efficiency. Zr doping induces more O vacancies as active sites for NRR, while also suppressing competing side reactions effectively. Additionally, in situ spectroscopy revealed an associative reaction pathway on the Zr/alpha-FeOOH surface.
APPLIED SURFACE SCIENCE
(2021)
Review
Chemistry, Physical
Usman Bin Shahid, Kumar Siddharth, Minhua Shao
Summary: The Haber-Bosch (HB) process revolutionized the chemical industry by making various nitrogenous derivatives accessible, but depleting natural resources and environmental concerns are driving a shift towards energy-efficient and environmentally friendly alternatives. The electro-chemical reduction pathway is seen as one of the most promising prospects as a carbon-free, environment-friendly, energy-efficient alternative to the HB process.
CURRENT OPINION IN ELECTROCHEMISTRY
(2021)
Article
Materials Science, Multidisciplinary
Xuyan Zhou, Shufen Chu, Zeyu Jin, Kailong Hu, Pan Liu, Hua-Jun Qiu, Xi Lin
Summary: Modifying the structures of metal-N-C single-atom catalysts to enhance their catalytic activities is challenging but desirable. The introduction of Ru to create RuFe-N-C or RuCo-N-C double-atom catalysts (DACs) can significantly improve the bifunctional ORR/OER activities, surpassing the individual Fe(Co)-N-C and Ru-N-C. The synergistic effect in RuM-N-C DACs is attributed to the combined optimized metal atoms, which alter the charge density and d-band center, affecting the adsorption energies and catalytic activity of intermediates. The synthesis of RuFe-N-C using a bimetal MOF precursor demonstrates exceptional ORR/OER activities, outperforming Fe-N-C, Ru-N-C, and even commercial Pt/C-RuO2.
ACS MATERIALS LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Ruoqi Liu, Ting Guo, Hao Fei, Zhuangzhi Wu, Dezhi Wang, Fangyang Liu
Summary: In this study, different active sites of MoS2 were found to exhibit different catalytic selectivity for nitrogen reduction and hydrogen evolution reactions through DFT calculations. A new synergistic mechanism was proposed and a self-sacrificial strategy using g-C3N4 as templates was developed to synthesize 1T-MoS2 with an ultrahigh 1T content. This work provides a promising new direction for synchronizing selectivity and activity in multistep catalytic reactions.
Article
Chemistry, Physical
Qian Liu, Yiting Lin, Shuang Gu, Ziqiang Cheng, Lisi Xie, Shengjun Sun, Longcheng Zhang, Yongsong Luo, Abdulmohsen Ali Alshehri, Mohamed S. Hamdy, Qingquan Kong, Jiahong Wang, Xuping Sun
Summary: Cu3P nanoribbon is proposed as a highly efficient electrocatalyst for the conversion of nitrogen to ammonia. It shows excellent catalytic performance and stability under benign conditions and achieves high Faradaic efficiency and large yield.
Article
Chemistry, Multidisciplinary
Jun-Lin Shi, Shi-Qin Xiang, Dai-Jian Su, Xiaohong Liu, Wei Zhang, Liu-Bin Zhao
Summary: Theoretical simulations suggested that Au-Mo alloy materials act as high-performance electrocatalysts for nitrogen reduction reaction (NRR) by simultaneously promoting NRR and suppressing HER. Adjusting the atomic proportion in alloys could optimize catalytic activity for NRR and HER.
Article
Chemistry, Multidisciplinary
Qi Liu, Xianyang Lu, Yuxiang Liu, Zhihao Li, Pengfei Yan, Wang Chen, Qinghao Meng, Yongheng Zhang, ChiYung Yam, Liang He, Yu Yan, Yi Zhang, Jing Wu, Thomas Frauenheim, Rong Zhang, Yongbing Xu
Summary: By introducing different contents of Bi adatoms to the surface of monolayer graphene, the carrier concentration and their dynamics have been effectively modulated as probed directly by the time- and angle-resolved photoemission spectroscopy technique. The Bi adatoms are found to assist acoustic phonon scattering events mediated by supercollisions as the disorder effectively relaxes the momentum conservation constraint. A reduced carrier multiplication has been observed, which is related to the shrinking Fermi sea for scattering, as confirmed by time-dependent density functional theory simulation. This work gives insight into hot carrier dynamics in graphene, which is crucial for promoting the application of photoelectric devices.
Article
Physics, Applied
Jiayi Li, Yanming Lin, Minjie Zhang, Ying Peng, Xinru Wei, Zhengkun Wang, Zhenyi Jiang, Aijun Du
Summary: Designing an efficient heterostructure for photocatalytic hydrogen production is of great significance in addressing the energy shortage and environmental crisis. This study investigates the structure, electron of interface, optical properties, charge transfer, and photocatalytic mechanism of three ZnIn2S4/alpha-In2Se3 heterostructures using density functional calculation. The results show that the presence of an external electric field can not only change the bandgap but also modulate the band alignment type. Among the three heterostructures, A is a type II heterostructure, while B and C are Z-scheme heterostructures, with heterostructure C demonstrating the importance of electrons on the conduction band maximum of a ZnIn2S4 monolayer in the hydrogen production process. Additionally, the small bandgap of ZnIn2S4/alpha-In2Se3 Z-scheme heterostructures allows for a wide light absorption range. Overall, this study contributes to the design of a novel and potential Z-scheme heterostructure photocatalyst with broad application prospects in both electronic and optoelectronic fields.
JOURNAL OF APPLIED PHYSICS
(2023)
Article
Chemistry, Physical
Qingchao Fang, Hanqing Yin, Xin Mao, Yun Han, Cheng Yan, Anthony P. O'Mullane, Aijun Du
Summary: In this study, the potential of InBi as a catalyst for nitrate reduction to ammonia (NRA) was systematically studied using density functional theory calculations. The results show that InBi exhibits high activity for NRA through an O-end pathway, with the free energy evolution of all intermediates being downhill in the most favorable elementary steps. The activation of nitrate is attributed to the strong orbital hybridization between oxygen and indium atoms, resulting in enhanced charge transfer and NO3- adsorption. Moreover, the competitive hydrogen evolution reaction (HER) is effectively suppressed due to the weak adsorption of proton. This study not only confirms the great electrocatalytic potential of InBi as a novel catalyst for NRA but also suggests a new approach for the design of practical NRA electrocatalysts.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Xiaoming Zhang, Weizhen Meng, Ying Liu, Xuefang Dai, Guodong Liu, Liangzhi Kou
Summary: Electrides are a unique class of materials where excess electrons are localized in lattice sites, leading to unique properties. Magnetic electrides, which have received limited attention, were identified using high-throughput computational screening methods. These materials have potential applications in spintronics, topological electronics, electron emission, and catalysis. This work marks the beginning of a new era in the study and application of magnetic electrides.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Hao Wu, Lei Zhang, Songying Qu, Aijun Du, Junwang Tang, Yun Hau Ng
Summary: Hydrogen dopants and oxygen vacancies are important in BiVO4 photoanodes, but the impact of hydrogenation on charge transport, particularly electron small polaron formation, is not well understood. This study demonstrates that mild hydrogenation of nanoporous BiVO4 reduces the charge transport barrier, as shown by thermally activating photocurrent responses. The hydrogen atoms occupy oxygen vacancies, reducing the activation energy and facilitating electron small polaron transport. A BiVO4 photoanode with NiFeOx cocatalyst achieves an applied-bias photon-to-current efficiency of 1.91% at 0.58 V vs RHE. This study expands the understanding of hydrogen doping beyond conventional donor density/surface chemisorption mediations to include small polaron hopping.
ACS ENERGY LETTERS
(2023)
Article
Chemistry, Physical
Juan Bai, Jun Mei, Jing Shang, Xin Mao, Dongchen Qi, Ting Liao, Aijun Du, Ziqi Sun
Summary: It is well known that the activity of electrocatalytic oxygen evolution reaction (OER) depends on the active centers of electrocatalysts. In this study, molybdenum oxide catalysts were used as a representative model and it was found that the inactive molybdenum sites can be regenerated as synergistic active centers for promoting OER through phosphorus-modulated defective engineering. The optimal catalyst achieved an overpotential of 287 mV for a current density of 10 mA cm(-2) with only 2% performance decay after 50 hours of continuous operation. This work provides insights into activating inert metal sites on oxide catalysts to enhance their electrocatalytic properties.
Article
Chemistry, Physical
Fuhao Jin, Hanqing Yin, Ru Feng, Wei Niu, Wanting Zhang, Jingquan Liu, Aijun Du, Wenrong Yang, Zhen Liu
Summary: In this study, a core-shell nanostructure of polypyrrole (PPy) coated sulfur-doped iron oxide nanoparticles (S-Fe2O3@PPy) is prepared as highly selective and durable electrocatalysts for N-2 reduction reaction (NRR). Sulfur doping and PPy coating greatly enhance the charge transfer efficiency and produce abundant oxygen vacancies as active sites for NRR. The catalyst achieves a NH3 production rate of 22.1 μg/h(mg(cat)) and a very-high Faradic efficiency of 24.6%, surpassing other Fe2O3 based NRR catalysts. Density functional theory calculations demonstrate that the S-coordinated iron site can activate the N-2 molecule and optimize the energy barrier during the reduction process, leading to a small theoretical limiting potential.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Chemistry, Physical
Mengnan Qu, Aijun Du, Qiao Sun
Summary: This study systematically investigated a series of surface functional group decorated MXenes for their adsorption properties towards strontium (Sr) and cesium (Cs) through density functional theory calculations. It was found that the MXene with an O/OH ratio of 3/16 exhibited the best adsorption performance, with adsorption energies ranging from -2.07 to -4.34 eV for Sr and -1.42 to -2.58 eV for Cs. Among these MXenes, the Sc2C monolayer showed the strongest adsorption capacity for Sr and Cs, achieved by forming three Sr-O and Cs-O covalent bonds between the radioactive nuclides and the oxygen atoms of the Sc2C monolayer. (c) 2023 Elsevier B.V. All rights reserved.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Multidisciplinary
Muhammad Ahmed, Gurpreet Kour, Ziqi Sun, Aijun Du, Xin Mao
Summary: The hydrogen evolution reaction (HER) is a notable mechanism for hydrogen production through water electrolysis. However, the use of noble metal catalysts like platinum presents limitations in terms of availability and cost. In this study, we demonstrated the effectiveness of aryl-functionalised catalysts on single-walled carbon nanotubes (SWCNTs) for the HER using density functional theory (DFT) calculations. We found that the curvature of the nanotubes and the proposed aryl-functionalised catalysts have a significant impact on the HER performance.
Article
Chemistry, Multidisciplinary
Huijie Liu, Mengnan Qu, Aijun Du, Qiao Sun
Summary: Through DFT calculations, the study demonstrates that uranium-doped C2N/C3N4 monolayers can strongly embed uranium atoms and allow for strong adsorption of N-2 on the surfaces with adsorption energies ranging from -0.69 to -0.98 eV. The NH3 formation process on these catalysts has relatively low limiting potentials, especially for uranium-doped C2N (-0.44 V). Additionally, the study shows that nitrogen reduction reaction (NRR) is predominant over competing hydrogen evolution reaction (HER) on the uranium-doped substrates.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Tsz Lok Wan, Junxian Liu, Xin Tan, Minghao Liu, Sean Smith, Liangzhi Kou
Summary: Stable, high-efficiency, and highly active electrocatalysts are crucial for converting renewable energy through overall water splitting. Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) with dual metal sites, particularly PcCo-O-8-Rh, show promising potential as catalysts for this process, with Rh serving as the active site for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Tensile strain can optimize the HER/OER activity of PcTM-O-8-TM' by influencing the absorption strength of intermediates and the d-band center (epsilon(d)) of the TM atom. This study presents a new family of 2D c-MOFs as high-performance bifunctional electrocatalysts for overall water splitting, contributing to sustainable energy conversion.
Article
Chemistry, Multidisciplinary
Lei Zhang, Cheng Tang, Stefano Sanvito, Aijun Du
Summary: A new concept of highly degenerate ferroelectricity with multiple FE states coexisting in a single 2D material is proposed through the asymmetrical decoration of porous COFs/MOFs. First-principles calculations and MC simulations reveal that Li-decorated 2D Cr(pyz)(2) is a prototype of highly degenerate 2D FE materials, showing four-fold and eight-fold degenerate ferroelectricity. Three-fold and six-fold degenerate ferroelectricity is also demonstrated in P-decorated g-C3N4 and Ru-decorated C2N, respectively. This work presents a general route to obtain highly degenerate 2D ferroelectricity, expanding the applications of 2D FE compounds.
MATERIALS HORIZONS
(2023)
Review
Chemistry, Physical
Yun Han, Xuecheng Yan, Qilong Wu, Hongzhe Xu, Qin Li, Aijun Du, Xiangdong Yao
Summary: In the past decades, significant progress has been made in the exploration of electrocatalysts with high activity, long durability, and low cost. Among them, defective graphene (DG)-based catalysts are considered as potential replacements for precious metal-based electrocatalysts. This overview highlights recent advancements in four types of DG-based catalysts: 1) heteroatoms-doped graphene; 2) intrinsic DG (vacancy and topological defect); 3) nonmetal atoms or/and metal species-modified intrinsic DG (heterogeneous species and intrinsic defects co-tuned DG); and 4) DG-based van der Waals-type multilayered heterostructures. The synergistic effects between different defects and the catalytic mechanism derived from defects are discussed, providing insights for the rational design and fabrication of high-performance electrocatalysts for practical energy-related applications. The challenges and future research directions on defect engineering in noble metal-free materials for electrocatalysis are proposed.
Article
Chemistry, Physical
Shuang Wu, Huijie Liu, Mengnan Qu, Aijun Du, Jianfen Fan, Qiao Sun
Summary: The electrocatalytic nitrogen reduction reaction (NRR) is a green and sustainable approach for producing ammonia. Cu-N-4-graphene is a promising catalyst for the NRR, and its performance has been clarified in this work. DFT computations reveal that the activation of the N = N bond and the NRR proceed in an alternating hydrogenation pathway at a specific surface charge density on Cu-N-4-graphene. This work provides new insights into the mechanism of the NRR and highlights the importance of environmental charges in the electrocatalytic process.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Engineering, Electrical & Electronic
Minghao Liu, Lei Zhang, Junxian Liu, Tsz Lok Wan, Aijun Du, Yuantong Gu, Liangzhi Kou
Summary: Controlling magnetism via electric fields instead of magnetic fields has long been envisioned as a revolutionary technology, but it faces challenges of volatility, high energy cost, and low storage density. In this work, effective approaches to achieve magnetic control in bilayer NiI2 are developed through electrostatic doping and polarization field. The interlayer antiferromagnetic to ferromagnetic transition has been observed when the critical electron doping concentration reaches 0.625%. The critical concentration of magnetic transition can be reduced or increased depending on the polarization direction on the ferroelectric substrate of Sc2CO2.
ACS APPLIED ELECTRONIC MATERIALS
(2023)
