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当期目录

2024年  第39卷  第3期

2024-3-catalog
2024, 39(3): 1-1.
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202403YWML
2024, 39(3): 1-7.
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综合评述
A review of the synthesis, characterization, and mechanism of bimetallic catalysts for electrocatalytic CO2 reduction
LIAO Yin-li, HUANG Heng-bo, ZOU Ru-yu, SHEN Shu-ling, LIU Xin-juan, TANG Zhi-hong
2024, 39(3): 367-387. doi: 10.1016/S1872-5805(24)60860-7
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The electrocatalytic CO2 reduction reaction (CO2RR) is an environmentally friendly way to convert CO2 into valuable chemicals. However, CO2 conversion is a complex process, which contains 2, 4, 6, 8, and 12 electron transfer processes. It is very important to develop efficient catalysts to precisely control the number of electron transfers for the chemicals required. Single-metal catalysts have some deficiencies, including slow reaction kinetics, low product selectivity and inadequate stability. In response to these challenges, bimetallic catalysts have received significant attention owing to their unique structure and improved performance. The introduction of secondary metals alters the catalyst’s electronic structure, and creates novel active sites, as well as optimizing their interaction with the intermediates. This review provides a comprehensive account of atomically distributed bimetals based on carbon materials and non-atomic distributed bimetals such as alloys and heterostructures, including their synthesis methods, characterization, and the outcomes of different catalysts. Catalytic mechanisms of different bimetallic catalysts are proposed and challenges encountered in the CO2RR are considered.
石墨炔在水系离子电池中的研究进展
徐显敏, 封文聪, 任静柯, 罗雯
2024, 39(3): 388-406. doi: 10.1016/S1872-5805(24)60852-8
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石墨炔(Graphdiyne,GDY)是一种全新的炭材料,具有特殊的炭杂化排列方式、独特的化学性质和电子结构以及独特的孔隙结构等优点,在电化学储能领域具有良好的应用前景。新兴的水系离子电池具有低成本和高安全性等优点,然而,高性能电极材料的开发、新型隔膜体系的设计以及稳定界面的策略等仍是水系离子电池面临的主要挑战。石墨炔在负极保护、正极包覆、隔膜设计以及稳定界面pH值等方面,可以改善离子传输与界面沉积行为、电解液不稳定等问题。特别是石墨炔自下而上的分子结构设计策略使其具有易修饰、掺杂的特点,改性的石墨炔类似物具有更加优异的性能,拓宽了其在水系离子电池中的应用。本文系统综述了石墨炔的结构与性质以及合成方法,特别对石墨炔在水系离子电池中的研究进行了总结。此外,对石墨炔在水系离子电池中应用时仍存在的问题与挑战进行了探讨,对石墨炔在水系离子电池中的发展进行了展望。

A review of carbon-supported single-atom catalysts for electrochemical reactions
WANG Yi-cheng, MA Xiao-bo, Ayeza, WANG Chen-xu, LI Yang, YANG Cheng-long, WANG Zhe-fan, WANG Chao, HU Chao, ZHANG Ya-ting
2024, 39(3): 407-438. doi: 10.1016/S1872-5805(24)60863-2
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Recent advances in the use of carbon-supported single-atom catalysts (SACs) for electrochemical reactions are comprehensively reviewed. The development and advantages of carbon-supported SACs are briefly introduced, followed by a detailed summary of the synthesis strategies used, including vapor phase transport, high temperature pyrolysis and wet chemical methods. Advanced characterization techniques for carbon-supported SACs are also reviewed. The use of carbon-supported SACs in different fields, such as the oxygen reduction reaction, carbon dioxide reduction reaction, nitrogen reduction reaction, hydrogen evolution reaction, and oxygen evolution reaction are summarized. Special emphasis is given to the modification strategies used to enable carbon-supported SACs to have an excellent electrocatalytic performance. Finally, the prospects and challenges associated with using carbon-supported SACs for electrochemical reactions are discussed.
Advances in graphene/molybdenum dichalcogenide-based van der Waals heterostructure photodetectors
ZHANG Xin-hua, LIU Wei-di, GONG You-pin, LIU Qing-feng, CHEN Zhi-gang
2024, 39(3): 439-457. doi: 10.1016/S1872-5805(24)60853-X
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Graphene is widely used in photodetection because of its high carrier mobility and wide spectral absorption range. However, its high dark current caused by its low light absorption severely limits its performance. Molybdenum dihalide (MoX2, X= S, Se and Te) has a high absorption coefficient, which can compensate for the high dark current in graphene-based photodetectors and result in outstanding photoelectronic properties of those based on a graphene/MoX2 van der Waals heterostructure (vdWH). In this review, we firstly review working principles, performance indicators, and structures of photodetectors. After that, the significance of graphene/MoX2 vdWH photodetectors is highlighted from the fundamental perspective. Preparation methodologies and performance enhancement strategies of graphene/MoX2 vdWH photodetectors are correspondingly summarized. In the end, we highlight the current challenges and future directions of the graphene/MoX2 vdWH photodetectors. This review will guide the design of high-performance vdWH photodetectors.
A review of carbon material-based Z-scheme and S-scheme heterojunctions for photocatalytic clean energy generation
Sahil Rana, Amit Kumar, WANG Tong-tong, Gaurav Sharma, Pooja Dhiman, Alberto García-Penas
2024, 39(3): 458-482. doi: 10.1016/S1872-5805(24)60857-7
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Carbon materials, including carbon nanotubes/nanofibers, graphene, graphene oxide, reduced graphene oxide, graphyne, graphdiyne, carbon quantum dots and fullerenes, have received considerable attention in recent years because of their unique properties such as high conductivity, excellent stability and biocompatibility. The integration of these materials into Z-scheme and S-scheme heterojunctions has emerged as a transformative strategy to increase their photocatalytic efficiency for energy conversion applications. We first consider the fundamental principles of clean energy generation such as photocatalytic H2 generation and CO2 reduction, elucidating their respective mechanisms and advantages. Various types of carbon materials, their synthesis and construction of Z-scheme and S-scheme heterojunctions are then discussed, emphasizing their role in promoting charge separation, reducing recombination losses and extending the spectral response range. With a focus on solar energy production, recent advances in carbon-based Z-scheme and S-scheme heterojunctions are discussed and summarized for photocatalytic H2 generation and CO2 reduction. Lastly, the current problems in the field of carbon-based photocatalysts are discussed with insights for the future development of this field.
A review of the high-concentration processing, densification, and applications of graphene oxide and graphene
WANG Yue, LUO Jia-liang, LU Zhe-hong, DI Jun, WANG Su-wei, JIANG Wei
2024, 39(3): 483-505. doi: 10.1016/S1872-5805(24)60856-5
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Dense graphene assemblies, composed of tightly stacked graphene sheets, have outstanding chemical stability and excellent mechanical, thermal, and electrical properties. They also do not have the problems of low density, low mechanical strength, poor electrical conductivity, or poor thermal conductivity found in porous graphene aerogels, making them ideal materials for future portable electronic and smart devices. We summarize work on high-concentration graphene oxide (GO) and graphene dispersions prepared by mechanical dispersion, evaporation concentration, centrifugal concentration, and liquid phase exfoliation, as well as two-dimensional (2D) dense graphene-based films and three-dimensional (3D) dense graphene-based structures prepared by vacuum-assisted filtration, interfacial self-assembly, and press-forming, and evaluate the advantages and disadvantages of each method. The applications of dense graphene-based assemblies in energy storage, thermal management, and electromagnetic interference (EMI) shielding are summarized. Finally, their challenges and prospects in future research are outlined. This review provides a reference for exploring and developing their large-scale, cost-effective manufacture and use.
研究论文
Boron and nitrogen co-doped sodium alginate-based porous carbons for durable and fast Zn-ion hybrid capacitors
LU Ya-ping, WANG Hong-xing, LIU Lan-tao, PANG Wei-wei, CHEN Xiao-hong
2024, 39(3): 506-514. doi: 10.1016/S1872-5805(24)60847-4
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In recent years, zinc-ion hybrid capacitors (ZIHCs) have attracted increasing attention due to their environmental friendliness and excellent electrochemical properties. However, their performance is mainly limited by the electrochemical performance of the cathode, so it is necessary to develop an advanced cathode material. N, B co-doped sodium alginate-based porous carbon (NBSPC) was prepared by one-step co-carbonization using sodium alginate as the matrix and NH4B5O8 as the N and B source. This N, B co-doping strategy improves the pore structure of the carbon materials and increases the number of surface functional groups, greatly improving the capacitive behavior of the raw materials and thus improving their electrochemical performance. When used as the cathode in ZIHCs, the NBSPC had an excellent rate performance (85.4 mA h g1 even at ultra-high current density of 40 A g1) and good cycling stability (15 000 cycles at 20 A g1 with a capacity retention rate of 94.5%).
Controlled growth of a graphdiyne/cobalt hydroxide heterointerface for efficient chlorine production
LIU Hui-min, LUAN Xiao-yu, YAN Jia-yu, BU Fan-le, XUE Yu-rui, LI Yu-liang
2024, 39(3): 515-525. doi: 10.1016/S1872-5805(24)60861-9
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The chlor-alkali process plays a key and irreplaceable role in the chemical industry because of its use in various industrial processes. However, the low selectivity and efficiency of the reported chlorine evolution reaction (CER) electrocatalysts obviously hinder its practical use. We report a simple method for the controlled growth of high-performance CER electrocatalysts by first growing cobalt hydroxide on the surface of carbon cloth, followed by the in-situ growth of graphdiyne (GDY/Co(OH)2). As expected, the as-synthesized catalyst has a small overpotential of only 83 mV at 10 mA cm2, a maximum Faradaic Efficiency (FE) of 91.54%, and a high chlorine yield of 157.11 mg h1 cm2 in acidic simulated seawater. Experimental results demonstrate that the in-situ growth of GDY on the Co(OH)2 surface leads to the formation of heterointerfaces with strong electron transfer between GDY and Co atoms, resulting in a higher conductivity, larger active specific surface area and more active sites, thereby improving the overall electrocatalytic selectivity and efficiency.
Controllable construction of CoP nanoparticles anchored on a nitrogen-doped porous carbon as an electrocatalyst for highly efficient oxygen reduction in Zn-air batteries
YAN Xiao-li, WANG Kui, HAO Shu-wei, ZHOU Guang-da, YANG Hao-wei, ZHANG Hua, GUO Jun-jie
2024, 39(3): 526-537. doi: 10.1016/S1872-5805(24)60848-6
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Exploring cost-efficient and highly-efficient noble metal-free catalysts for the oxygen reduction reactions (ORRs) involved in sustainable energy devices remains a great challenge. Transition-metal phosphides supported on heteroatom-doped carbons have shown potential as alternative candidates for precious metals because of their tunable electronic structures and higher catalytic performance. Phosphating was used to construct CoP nanoparticles (NPs) anchored on a nitrogen-doped porous carbon framework (CoP@NC) from Co NPs loaded on NC, using PH3 gas released from NaH2PO2 during heat treatment. The dodecahedral structure of Co NPs was retained in their transformation to CoP NPs. The CoP@NC electrocatalyst shows a remarkable ORR activity with a half-wave potential up to 0.92 V under alkaline conditions, which is attributed to the combined coupling between the well dispersed CoP nanoparticles on the nitrogen-doped carbon and the efficient mass transport in the porous structure. Zinc-air batteries assembled with the CoP@NC electrocatalyst as a cathode have a high open-circuit voltage of 1.51 V and power density of 210.1 mW cm2. This work provides a novel strategy to develop low-cost catalysts with an excellent ORR performance to promote their practical use in metal-air batteries.
Sulfonyl chloride-intensified metal chloride intercalation of graphite for efficient sodium storage
LAN Shu-qin, REN Wei-cheng, WANG Zhao, YU Chang, YU Jin-he, LIU Ying-bin, XIE Yuan-yang, ZHANG Xiu-bo, WANG Jian-jian, QIU Jie-shan
2024, 39(3): 538-548. doi: 10.1016/S1872-5805(24)60851-6
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Metal chloride-intercalated graphite with excellent conductivity and a large interlayer spacing is highly desired for use in sodium ion batteries. However, halogen vapor is usually indispensable in initiating the intercalation process, which makes equipment design and experiments challenging. In this work, SO2Cl2 was used as a chlorine generator to intensify the intercalation of BiCl3 into graphite (BiCl3-GICs), which avoided the potential risks, such as Cl2 leakage, in traditional methods. The operational efficiency in the experiment was also improved. After the reaction of SO2Cl2, BiCl3, and graphite at 200 °C for 20 h, the synthesized BiCl3-GICs had a large interlayer spacing (1.26 nm) and a high amount of BiCl3 intercalation (42%), which gave SIBs a high specific capacity of 213 mAh g1 at 1 A g1 and an excellent rate performance (170 mAh g1 at 5 A g1). In-situ Raman spectra revealed that the electronic interaction between graphite and intercalated BiCl3 is weakened during the first discharge, which is favorable for sodium storage. This work broadly enables the increased intercalation of other metal chloride-intercalated graphites, offering possibilities for developing advanced energy storage devices.
Increasing the interlayer spacing and generating closed pores to produce petroleum coke-based carbon materials for sodium ion storage
ZHUANG Hong-kun, LI Wen-cui, HE Bin, LV Jia-he, WANG Jing-song, SHEN Ming-yuan, LU An-hui
2024, 39(3): 549-560. doi: 10.1016/S1872-5805(24)60858-9
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Petroleum coke (PC) is a valuable precursor for sodium-ion battery (SIB) anodes due to its high carbon content and low cost. The regulation of the microcrystalline state and pore structure of the easily-graphitized PC-based carbon is crucial for creating abundant Na+ storage sites. Here we used a precursor transformation strategy to increase the carbon interlayer spacing and generate abundant closed pores in PC-based carbon, significantly increasing its Na+ storage capacity in the plateau region. This was achieved by introducing a large number of oxygen functional groups through mixed acid treatment and then using high-temperature carbonization to decompose the oxygen functional groups and rearrange the carbon microcrystallites, resulting in a transition from open to closed pores. The optimized samples provide a large reversible capacity of 356.0 mAh g1 at 0.02 A g1, of which approximately 93% is below 1.0 V. Galvanostatic intermittent titration (GITT) and in-situ X-ray diffraction (XRD) analysis indicate that the sodium storage capacity in the low voltage plateau region involves a joint contribution of interlayer insertion and closed pore filling processes. This study presents a comprehensive method for the development of high-performance carbon anodes using low-cost and highly aromatic precursors.
等离子体辅助制备炭布负载大层间距NiCoAl-LDHs及其电化学去离子性能
姜秋彤, 王国庆, 李益, 黄宏伟, 李倩, 杨建
2024, 39(3): 561-572. doi: 10.1016/S1872-5805(24)60854-1
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电容去离子技术近年来被认为是一种新兴的海水淡化技术,尤其在苦咸水范围内具有经济节能的特点。然而,目前关于除氯电极的研究较少,同时缓慢的除盐动力学也制约了除氯电极的发展。本工作通过在表面酸处理后的柔性炭布(ACC)上原位生长层状氢氧化物NiCoAl-LDHs纳米片阵列并进行Ar等离子体处理,制备了具有扩大层间距的Ar-NiCoAl-LDHs@ACC材料。炭布基底抑制了NiCoAl-LDHs纳米片的团聚并提高了电导率,Ar等离子体处理则进一步扩大了NiCoAl-LDHs层间距并改善了亲水性,提供了快速的氯离子扩散通道,并释放了更多的层间活性位点,实现了高除盐动力学。将Ar-NiCoAl-LDHs@ACC作为除氯电极与活性炭组装了混合式电容去离子器件。在1000 mg L−1 NaCl溶液及1.2 V工作电压下,除盐容量可达到93.26 mg g−1,除盐速率可达到0.27 mg g−1 s−1,电荷效率高达0.97。在300 mg L−1 NaCl溶液及0.8 V工作电压下,经100次循环后容量保持率仍在85%以上。本工作的制备策略为大层间距二维金属氢氧化物材料的可控制备和高性能电化学除氯电极的设计构建提供了新思路。

废旧三元锂电池石墨负极电化学除杂及其性能研究
张锐, 田勇, 张维丽, 宋佳音, 闵杰, 庞博, 陈建军
2024, 39(3): 573-582. doi: 10.1016/S1872-5805(24)60843-7
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随着新能源汽车迅速发展,动力锂离子电池应用越来越广泛,大量锂电池也迎来退役高峰期,废旧锂电池的回收综合利用引起各国高度关注。废旧锂电池石墨负极层状结构基本未变化,因此回收时不需高温石墨化,只需关注其内部杂质的去除。本文将废旧石墨负极进行热处理、超声分离和酸浸处理后,创新性地采用电化学处理将内部金属杂质深度去除。对比不同回收阶段的石墨,发现石墨中有机杂质的存在会严重影响各项电化学性能,微量Cu、Fe等无机杂质的存在对初始放电比容量影响不大,但会降低石墨的循环稳定性。最终回收的石墨内部主要金属杂质含量低于20 mg/kg,在0.1 C倍率下放电比容量达到358.7 mAh/g,循环150圈后容量保持率为95.85%。对比已报道的废旧石墨回收方法,此方法可深度去除石墨负极内部杂质,解决了目前酸碱用量大、除杂不彻底、能耗高等问题,回收再生石墨负极电化学性能较好,为废旧锂电池石墨负极提供了一条新的回收再生路径。