摘要：
<jats:title>Abstract</jats:title><jats:p>Light‐driven hydrogen production from biomass derivatives offers a path towards carbon neutrality. It is often however operated with the limitations of sluggish kinetics and severe coking. Herein, a disruptive air‐promoted strategy is explored for efficient and durable light‐driven hydrogen production from ethanol over a core/shell Cr<jats:sub>2</jats:sub>O<jats:sub>3</jats:sub>@GaN nanoarchitecture. The correlative computational and experimental investigations show ethanol is energetically favorable to be adsorbed on the Cr<jats:sub>2</jats:sub>O<jats:sub>3</jats:sub>@GaN interface, followed by dehydrogenation toward acetaldehyde and protons by photoexcited holes. The released protons are then consumed for H<jats:sub>2</jats:sub> evolution by photogenerated electrons. Afterward, O<jats:sub>2</jats:sub> can be evolved into active oxygen species and promote the deprotonation and C−C cleavage of the key C<jats:sub>2</jats:sub> intermediate, thus significantly lowering the reaction energy barrier of hydrogen evolution and removing the carbon residual with inhibited overoxidation. Consequently, hydrogen is produced at a high rate of 76.9 mole H<jats:sub>2</jats:sub> per gram Cr<jats:sub>2</jats:sub>O<jats:sub>3</jats:sub>@GaN per hour by only feeding ethanol, air, and light, leading to the achievement of a turnover number of 266,943,000 mole H<jats:sub>2</jats:sub> per mole Cr<jats:sub>2</jats:sub>O<jats:sub>3</jats:sub> over a long‐term operation of 180 hours. Notably, an unprecedented light‐to‐hydrogen efficiency of 17.6 % is achieved under concentrated light illumination. The simultaneous generation of aldehyde from ethanol dehydrogenation enables the process more economically promising.</jats:p>
摘要：
Seawater electrolysis for green hydrogen production is one of the key technologies for achieving carbon neutrality. However, in anode systems, the chloride ions (Cl−) in seawater will trigger an undesired chlorine evolution reaction (CER) that competes with an oxygen evolution reaction (OER), resulting in inferior OER activity and selectivity. Besides, the corrosive Cl− and its derivative products will corrode anodes during seawater electrolysis, leading to poor stability. Therefore, great efforts have been devoted to developing efficient strategies for chlorine inhibition to improve the activity, selectivity, and stability of anode materials. Herein, focusing on chlorine inhibition, we present a mini review to comprehensively and concisely summarize the recent progress in anode systems for boosting seawater electrolysis. In particular, two strategies of physical and chemical regulation to inhibit Cl− are summarized in some representative cases. Finally, some challenges and future opportunities in anode systems for seawater electrolysis are prospected. This mini review aims to shed light on designing highly efficient anode materials for seawater electrolysis.
摘要：
Zinc metal batteries (ZMBs) have received a lot of attention due to their high capacity, proper redox potential and low cost. However, zinc anodes suffer from serious dendritic problems and side reactions, resulting in poor cycling stability of zinc ion batteries. Herein, organic additive trimethyl phosphate (TMP) is introduced into inexpensive ZnSO4 electrolyte to stabilize Zn anode. TMP exhibits bifunctional properties in this cost-effective electrolyte system. It prefers adsorbing on (002) plane of zinc which leads to preferential crystal growth and uniform zinc deposition. Moreover, TMP can reshape the original hydrogen bond network, regulate the solvation structure and inhibit the parasitic reaction generated by water. As a result, the zinc anode with TMP addition could maintain 2000 h at a current density of 0.5 mA cm−2 which is superior to bare zinc anode. When paired with V2O5 cathode, the full cell also shows excellent cyclic performance. Such a low-cost bifunctional additive would offer a strategy for stabilizing Zn plating/stripping behaviors and suppressing side reactions in mild aqueous electrolyte.
摘要：
Using interface engineering, a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni, Mo, and P on Cu nanowires (NiMoP@CuNWs). This catalyst only requires an overpotential of 35 mV to reach a current density of 10 mA cm-2. The exceptional hydrogen evolution reaction (HER) activity is attributed to the unique amorphous rod-like nature of NiMoP@CuNWs, which possesses a special hydrophilic feature, enhances mass transfer, promotes effective contact between the electrode and electrolyte solution, and exposes more active sites during the catalytic process. Density functional theory revealed that the introduction of Mo weakens the binding strength of the Ni site on the catalyst surface with the H atom and promotes the desorption process of the H2 product significantly. Owing to its facile synthesis, low cost, and high catalytic performance, this electrocatalyst is a promising option for commercial applications as a water electrolysis catalyst. (c) 2024, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
摘要：
<jats:title>Abstract</jats:title><jats:p>In natural plants, Mn<jats:sub>4</jats:sub>CaO<jats:sub>5</jats:sub> cluster with metal‐oxo “distorted chair”‐like structure exhibits excellent oxygen evolution activity. However, the performance of biomimetic oxygen evolution catalysts based on the Mn<jats:sub>4</jats:sub>CaO<jats:sub>5</jats:sub>‐like structure is far inferior to expectations. Herein, Ca and Ni are first doped together into birnessite and constructed a “distorted chair”‐like structure unit Mn<jats:sub>4‐x</jats:sub>Ni<jats:sub>x</jats:sub>CaO<jats:sub>5</jats:sub> in a birnessite‐like Ca‐Mn(Ni)‐O catalyst, the biomimetic Mn<jats:sub>4‐x</jats:sub>Ni<jats:sub>x</jats:sub>CaO<jats:sub>5</jats:sub> unit efficiently activates lattice oxygen and boosts the O─O coupling in oxygen evolution reaction (OER), which allows the catalyst to perform superior OER activity with an outstanding overpotential of 184mV at 300 mA cm<jats:sup>−2</jats:sup>. Besides, the birnessite‐like Ca‐Mn(Ni)‐O catalyst is stabilized by coupling to NiMnO<jats:sub>3</jats:sub> nanoplate, thus forming a stable catalyst that can work for >500 h without attenuation. This work optimizes biomimetic structures by introducing new elements, which provides new insight into developing efficient biomimetic materials.</jats:p>
摘要：
Zincophilic property and high electrical conductivity are both very important parameters to design novel Zn anode for aqueous Zn-ion batteries (AZIBs). However, single material is difficult to exhibit zincophilic property and high electrical conductivity at the same time. Herein, originating from theoretical calculation, a zincophilic particle regulation strategy is proposed to address these limitations and carbon coated Na3V2(PO4)3 is taken as an example to be a protective layer on zinc metal (NVPC@Zn). Na3V2(PO4)3 (NVP) is a common cathode material for Zn-ion batteries, which is zincophilic. Carbon materials not only offer an electron pathway to help Zn deposition onto NVPC surface, but also enhance the zinc nucleophilicity of Na3V2(PO4)3. Hence, this hybrid coating layer can tune zinc deposition and resist side reactions such as hydrogen generation and Zn metal corrosion. Experimentally, a symmetrical battery with NVPC@Zn electrode displays highly reversible plating/stripping behavior with a long cycle lifespan over 1800 h at 2 mA cm-2, much better than carbon and Na3V2(PO4)3 solely modified Zn electrodes. When the Na3V2(PO4)3 is replaced with zincophobic Al2O3 or zincophilic V2O3, the stability of the modified zinc anodes is also prolonged. This strategy expands the option of zincophilic materials and provides a general and effective way to stabilize the Zn electrode. (c) 2023 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.
作者机构：
[Jianqing Zhou; Pengfei Li; Xinyi Xia; Yi Zhao; Zhihao Hu; Yunlong Xie; Lun Yang; Yisi Liu; Yue Du] Hubei Key Laboratory of Photoelectric Materials and Devices, School of Materials Science and Engineering, Hubei Normal University, Huangshi 435002, China;[Qiancheng Zhou; Ying Yu] College of Physical Science and Technology, Central China Normal University, Wuhan 430079, China;Department of Physics and Texas Center for Superconductivity at the University of Houston (TcSUH), University of Houston, Houston, TX 77204, USA;Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430078, China;[Luo Yu] Department of Physics and Texas Center for Superconductivity at the University of Houston (TcSUH), University of Houston, Houston, TX 77204, USA<&wdkj&>Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430078, China
通讯机构：
[Luo Yu] D;Department of Physics and Texas Center for Superconductivity at the University of Houston (TcSUH), University of Houston, Houston, TX 77204, USA<&wdkj&>Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430078, China
摘要：
d‐band center engineering is an effective approach to manipulate the electronic structure of an electrocatalyst for boosting water splitting performance. However, it is still challenging to precisely tailor the electronic structure with an optimized d‐band center for efficient hydrogen and oxygen evolution reactions (HER and OER) on one single catalyst simultaneously. Focusing on nickel sulfide (Ni3S2), herein we applied dual-atom modification to precisely regulate the d‐band center of Ni3S2, which dramatically enhances its bifunctional activity with outstanding HER and OER performance. Specifically, the V and Fe co-modified Ni3S2 achieves ultra-low overpotentials of 68 and 190 mV to output 10 mA cm−2 in 1 M KOH for HER and OER, respectively. Theoretical calculations reveal that the strong electronic interactions between Ni 3d and V 3d/Fe 3d orbitals effectively tailor the d‐band center of Ni3S2, resulting in optimized HER and OER intermediate adsorption, thus boosting the HER and OER simultaneously.
作者机构：
[Xie, Yunlong; Liu, Yisi; Yang, Lun; Zhou, Jianqing; Du, Yue] Hubei Normal Univ, Inst Adv Mat, Huangshi 435002, Peoples R China.;[Yu, Ying; Yu, Luo; Zhou, Jianqing] Cent China Normal Univ, Coll Phys Sci & Technol, Wuhan, Peoples R China.
通讯机构：
[Luo Yu; Ying Yu] C;College of Physical Science and Technology, Central China Normal University, Wuhan 430079, China
摘要：
Hydrogen is a green and efficient energy candidate for the sustainable development of society. The electrocatalytic hydrogen evolution reaction (HER) of water splitting is a facile and sustainable approach to produce high-purity green hydrogen with zero carbon emission. Compared with the strong corrosivity of acidic/alkali electrolytes, water splitting in neutral electrolytes is a more promising choice, since it provides a mild environment for large-scale hydrogen production. Multi-site engineering is one of the most effective strategies for improving the neutral HER activity, because the neutral HER involves water dissociation and hydrogen adsorption/desorption processes, which require appropriate adsorption energies for different intermediates. Obviously, single-site catalysts cannot satisfy these demands, but multi-site electrocatalysts can offer multiple catalytic sites to separately interact with different intermediates and optimize adsorption strengths. Herein, we focus on multi-site electrocatalysts for the neutral HER, with the aim of offering an overview of novel design principles, progress, and perspectives in this area. To clearly reveal the important functions of multiple sites for the neutral HER, we first introduce the theoretical fundamentals of multi-site electrocatalysts for the HER in neutral media, then summarize a series of representative multi-site electrocatalysts, and systematically discuss these electrocatalysts from the theoretical calculation and experimental aspects. Finally, some challenges and further perspectives for the future development of multi-site electrocatalysts are presented. It is hoped that the review will provide valuable guidance for the rational design of multi-site water splitting electrocatalysts.
通讯机构：
[Jun Song] D;[Ying Yu] I;[Xinqiang Wang] S;[Baowen Zhou] K;Department of Mining and Materials Engineering, McGill University, 3610 University Street, Montreal, Canada<&wdkj&>State Key Laboratory of Artificial Microstructure and Mesoscopic Physics, School of Physics, Nano-Optoelectronics Frontier Center of Ministry of Education (NFC-MOE), Peking University, Beijing 10087, China<&wdkj&>Peking University Yangtze Delta Institute of Optoelectronics, Nantong, Jiangsu 226010, China<&wdkj&>Collaborative Innovation Center of Quantum Matter, School of Physics, Peking University, Beijing 100871, China<&wdkj&>Institute of Nanoscience and Nanotechnology, College of Physical Science and Technology, Central China Normal University, Wuhan 430079, China<&wdkj&>Key Laboratory for Power Machinery and Engineering of Ministry of Education, School of Mechanical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
作者机构：
[Qiu, Dan; Huang, Xintang; Li, Xiaohui; Qiu, Huajun; Yang, Ze; Yu, Ying; Zhou, Qiancheng] Cent China Normal Univ, Coll Phys Sci & Technol, Inst Nanosci & Technol, Wuhan 430079, Peoples R China.;[Huang, Xintang; Yu, Ying; Zhou, Xing] Wuhan Univ Technol, State Key Lab Adv Technol Mat Synth & Proc, Wuhan 430070, Peoples R China.
通讯机构：
[Ze Yang; Xintang Huang; Ying Yu; Ze Yang Ze Yang Ze Yang; Xintang Huang Xintang Huang Xintang Huang; Ying Yu Ying Yu Ying Yu] I;Institute of Nanoscience and Technology, College of Physical Science and Technology, Central China Normal University, Wuhan, 430079 China
关键词：
core-shell nanostructure;MnO2 nanosheets;N-doped carbon;Zn ion batteries
期刊：
Advanced Energy Materials,2023年13(32):2301475- ISSN：1614-6832
通讯作者：
Luo Yu<&wdkj&>Ying Yu<&wdkj&>Luo Yu Luo Yu Luo Yu<&wdkj&>Ying Yu Ying Yu Ying Yu
作者机构：
[Luo Yu; Luo Yu Luo Yu Luo Yu] Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan, 430074 China;[Liping Li; Liping Li Liping Li Liping Li] State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012 China;[Chuqiang Huang; Qiancheng Zhou; Dingshuo Duan; Tianyu Cao; Shunhang Qiu; Zhouzhou Wang; Jin Guo; Yuxin Xie; Ying Yu; Chuqiang Huang Chuqiang Huang Chuqiang Huang; Qiancheng Zhou Qiancheng Zhou Qiancheng Zhou; Dingshuo Duan Dingshuo Duan Dingshuo Duan; Tianyu Cao Tianyu Cao Tianyu Cao; Shunhang Qiu Shunhang Qiu Shunhang Qiu; Zhouzhou Wang Zhouzhou Wang Zhouzhou Wang; Jin Guo Jin Guo Jin Guo; Yuxin Xie Yuxin Xie Yuxin Xie; Ying Yu Ying Yu Ying Yu] Institute of Nanoscience and Nanotechnology, College of Physical Science and Technology, Central China Normal University, Wuhan, 430079 China
通讯机构：
[Luo Yu; Luo Yu Luo Yu Luo Yu] L;[Ying Yu; Ying Yu Ying Yu Ying Yu] I;Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan, 430074 China<&wdkj&>Institute of Nanoscience and Nanotechnology, College of Physical Science and Technology, Central China Normal University, Wuhan, 430079 China
关键词：
bifunctional electrodes;functional bimetals;large current densities;nickel phosphide;seawater splitting
摘要：
A functional bimetal is incorporated into Ni2P, where Fe atoms improve the conductivity for improving electron transfer, and Co atoms accelerate the self‐reconstruction process to favorably generate a Co and Fe co‐incorporated NiOOH species on the electrode surface for inhibiting the adsorption of Cl− ions, thus ensuring excellent oxygen evolution reaction selectivity and stability for large‐current‐density seawater splitting. Abstract Designing efficient and durable electrocatalysts for seawater splitting to avoid undesired chlorine evolution reaction and resist the corrosive seawater is crucial for seawater electrolysis technology. Herein, a functional bimetal (Co and Fe) is designed specifically to modify nickel phosphide (denoted as CoFe‐Ni2P) for boosting seawater splitting, where the Fe atom improves the conductivity of Ni2P for improving electron transfer, and the Co atom accelerates the self‐reconstruction process to favorably generate bimetal co‐incorporated NiOOH (CoFe‐NiOOH) species on the electrode surface. Additionally, these in situ‐generated CoFe‐NiOOH species remarkably inhibit the adsorption of Cl− ions but selectively adsorb OH− ions, which contributes to excellent performance of the CoFe‐Ni2P electrode for large‐current‐density seawater splitting. Therefore, the CoFe‐Ni2P electrode only requires low overpotentials of 266 and 304 mV to afford current densities of 100 and 500 mA cm−2 in a harsh 6 m KOH + seawater electrolyte, and can work stably for 600 h. Impressively, a flow‐type anion exchange membrane electrolyzer assembled by the CoFe‐Ni2P/Ni‐felt bifunctional electrode is demonstrated to run stably at an industrially large current density of 1.0 A cm−2 in 6 m KOH + seawater electrolyte for 350 h, which shows promising application prospects.
作者机构：
[Chunchun Wang; Ying Yu; Ming Qiu] Institute of Nanoscience and Nanotechnology, College of Physical Science and Technology, Central China Normal University, Wuhan 430079, PR China
通讯机构：
[Ying Yu; Ming Qiu] I;Institute of Nanoscience and Nanotechnology, College of Physical Science and Technology, Central China Normal University, Wuhan 430079, PR China
摘要：
In the latest issue of Cell Reports Physical Science, Pérez-Ramírez and co-workers report the synthesis of chlorinated Cu2O via a gas-phase strategy that achieves superior performance in CO2 electroreduction. It’s a referential synthesis method to control the chlorination degree of copper electrocatalysts for promoting the formation of highly reduced products.
期刊：
Journal of Materials Chemistry A,2023年11(44):24359-24370 ISSN：2050-7488
通讯作者：
Qiu, Ming;Yu, Y
作者机构：
[Zhang, Hui; Dong, Hao; Masana, Jofrey J.; Yu, Ying; Xiao, Jiayong; Qiu, Ming; Yang, Haolan] Cent China Normal Univ, Coll Phys Sci & Technol, Wuhan 430079, Peoples R China.;[Masana, Jofrey J.] Mwalimu Nyerere Univ Agr & Technol, POB 976, Musoma, Tanzania.
通讯机构：
[Yu, Y ; Qiu, M] C;Cent China Normal Univ, Coll Phys Sci & Technol, Wuhan 430079, Peoples R China.
摘要：
Heterostructure molecular catalysts have attracted significant attention for their distinctive catalytic activity in the electrocatalytic CO2 reduction reaction. To investigate the intrinsic reaction mechanisms, 3d-transition metal-phthalocyanine-based catalysts were systematically investigated. The results demonstrate that the heterostructure catalysts, composed of 3d-transition metal phthalocyanine and two-dimensional nitrogen-doped graphene, successfully modulate the electron configuration of the central metal atom and push its d(z)(2) orbitals close to the Fermi level which can lower the energy barrier for the rate-limiting step in its electrocatalytic CO2 reduction reaction (CRR) and boost the overall reaction kinetics. In addition, the mechanism of dual-site synergistic hydrogenation was determined for the first time through molecular dynamics simulation. Meanwhile, the descriptors related to metal atoms' inherent characteristics and catalytic properties exhibit a volcano relationship with the overpotential. This study provides a theoretical comprehension of the CRR mechanisms over heterostructure molecular catalysts, as well as innovative concepts for new molecular catalyst design.
摘要：
The well‐constructed MoCoP sites are anchored on N, P codoped carbon substrate by one‐pot synthesis, in which phytic acid is in situ added. MoCoP–NPC catalysts with MoCoP binary species show excellent electrocatalytic performance for the ORR, OER, and HER, higher than that of Mo (Co)‐based unitary sites and Mo/Co‐based dual‐phase sites. Abstract Structural and compositional design of multifunctional materials is critical for electrocatalysis, but their rational modulation and effective synthesis remain a challenge. Herein, a controllable one‐pot synthesis for construction of trifunctional sites and preparation of porous structures is adopted for synthesizing dispersed MoCoP sites on N, P codoped carbonized substance. This tunable synthetic strategy also endorses the exploration of the electrochemical activities of Mo (Co)‐based unitary, Mo/Co‐based dual and MoCo‐based binary metallic sites. Eventually benefiting from the structural regulation, MoCoP–NPC shows excellent oxygen reduction abilities with a half‐wave potential of 0.880 V, and outstanding oxygen evolution and hydrogen evolution performance with an overpotential of 316 mV and 91 mV, respectively. MoCoP–NPC‐based Zn‐air battery achieves excellent cycle stability for 300 h and a high open‐circuit voltage of 1.50 V. When assembled in a water‐splitting device, MoCoP–NPC reaches 10 mA cm−2 at 1.65 V. Theoretical calculations demonstrate that the Co atom in the single‐phase MoCoP has a low energy barrier for oxygen evolution reaction (OER) owing to the migration of Co 3d orbital toward the Fermi level. This work shows a simplified method for controllable preparation of prominent trifunctional catalysts.
摘要：
For photocatalytic materials, the composites formed by metal oxides and heteroatom-doped carbon have outstanding activity. Among them, metal-organic framework (MOF) derived composites, usually composed of metal oxide and nitrogen-doped carbon, is not only simple to prepare, but also have far-exceeding catalytic performance than homogenous semiconductor. However, the relationship between the structure and performance in the photocatalytic system is still not clear. Here, we explored the tunable nitrogen configurations in sample N-ZnO@NC by controlling the thermal conversion of ZIF-8. Crucially, through ex situ and in-situ XPS characterization, it is found that the ZnO and nitrogen-doped carbon in N-ZnO@NC are connected by C-N-Zn bond, which enhances charge separation efficiency and becomes the origin of superior photocatalytic performance. DFT calculations further reveal the influence of different Zn-bonding nitrogen configurations on the adjusting of Fermi level and electron transfer. This study exhibits that the pyridine-N configuration in MOF-derived material is the main contributor for the improved performance and tunes Fermi level more appropriately than the pyrrolic-N, which can hold the key for future design of next-generation photocatalysts. (c) 2021 Published by Elsevier Ltd on behalf of Chinese Society for Metals.
