ZIF-8@ZIF-67/LDH高效核壳纳米复合物的制备及其电催化性能研究

采用共沉淀法制备出ZIF-8@ZIF-67/LDH纳米复合物。使用扫描电子显微镜（scanning electron microscope,SEM）、X射线衍射仪（X-ray diffractometer,XRD）、拉曼光谱仪（Raman spectrometer,Raman）和X射线光电子能谱仪（X-ray photoelectron spectrometer,XPS）对复合物的表面形貌、晶体结构和组成进行了表征。采用电化学工作站进行析氧反应（oxygen evolution reaction, OER）、析氢反应（hydrogen evolution reaction, HER）以及水分解性能测试。结果表明,该复合物在1 mol/L的KOH水溶液中,所需的OER过电势为329 mV (η₁₀);HER过电势为175 mV (η₁₀);在双电极体系中,电流密度达到10 mA/cm²,完全水分解所需的电压为1.761 V。经过12 h的HER(-20 mA/cm²)计时电位稳定性测试,末电势较初始电势只下降了6 mV左右。结合相关表征分析,催化剂的高活性得益于大的电化学活性面积的核壳结构,为反应提供丰富的活性位点,通过ZIF-8@ZIF-67和LDH的共同效应,ZIF-8@ZIF-67/LDH表现出良好的OER和HER活性以及优异的稳定性。     

铁镍磷化物电极材料的制备及电催化析氢性能

为了解决电解水析氢过程中所用贵金属材料的高昂成本问题,采用水热-低温磷化法制备了一种低廉、环保、高效的析氢催化剂Fe_xNi_1-x-P。与传统制备方法比较,该方法在水热合成前驱体过程中,利用镍盐和铁盐与无水乙醇发生氧化还原反应,生成的OH^-可以沉淀金属离子,随后前驱体与NaH₂PO₂低温磷化制得Fe_xNi_1-x-P。通过研究发现,Fe_0.5Ni_0.5-P电极材料表现出优异的催化活性。在1.0 mol·L^-1 KOH溶液中,电流密度为10 mA·cm^-2时,电极Fe_0.5Ni_0.5-P需要的过电位仅为113 mV,1 000圈循环伏安测试后,极化曲线无明显衰减。提供了一种制备Fe_xNi_1-x-P的简便方法,为开发清洁能源系统的环境友好型催化剂提供了新思路。     

Al/Pb-WC-ZrO2复合电极材料的电化学性能研究

 研究了电镀液中固体微粒质量浓度及工艺条件对Al/Pb-WC-ZrO₂复合电极材料的表面化学组成及稳态析氧极化曲线的影响规律,对上述工艺条件进行了优化,优化后的工艺条件如下:WC:50 g/L,ZrO₂:40g/L,温度:20℃,电流密度:1.5 A/dm²,电沉积时间:2 h.所获得Al/Pb-WC-ZrO₂复合电极材料的析氧动力学参数为:a=771 mV,b=140 mV,i⁰=3.11×10^-6A·cm^-2,并且电极的析氧过电位为η=1 009 mV,复合镀层中WC和ZrO₂质量分数分别为10.02%和3.55%.     

氨化改性Sr2Ta2O7/SrTa4O11光催化剂用于光电催化性能研究

以钽酸锶同素异质结Sr₂Ta₂O₇/SrTa₄O₁₁（STO）为原始材料,采用高温氨化法对原始材料做氮掺杂改性处理,得到了新型氮掺杂钽酸锶同素异质结材料Sr₂Ta₂O_7-xN_x/SrTa₄O_11-xN_x(STO-N),并对其光电催化性能进行研究。结果显示,对比改性前的STO,STO-N具有更强的可见光吸收能力。紫外可见漫反射光谱证明,氮掺杂使得STO的吸收阈值从319 nm红移到485 nm,相应的带隙由3.97 eV减小到2.51 eV,这主要是由于N 2p和O 2p轨道的混合作用导致价带顶部上移。性能测试结果表明：STO-N₂₀的光电催化性能提升最为显著,在施加0.7 V偏压下,STO-N₂₀电极测得的光电流密度达到了570 nA/cm²,是STO电极的光电流密度（8.6 nA/cm²）的66倍。根据推算出的STO及STO-N₂₀的能带结构可知,STO-N₂₀性能提升的原因是禁带宽度变窄。     

Rh/Ti3C2Tx MXene催化剂用于氨硼烷催化产氢

二维过渡金属碳/氮化合物基（MXene）催化剂对于水解产氢反应具有优异的催化活性.以二维过渡金属碳化钛（Ti₃C₂T_x MXene）材料为载体,采用原位还原法,制备了超高分散度的二维Ti₃C₂T_x MXene材料担载的金属铑（Rh）催化剂（Rh/Ti₃C₂T_x MXene）.利用单层二维Ti₃C₂T_x MXene材料高度暴露的表面,实现了Rh亚纳米团簇的高度分散.在常压的温和条件下,将制得的Rh/Ti₃C₂T_x MXene催化剂用于氨硼烷的常温分解.在35℃,0.1 MPa的条件下,氨硼烷可以在3 min内完全实现氢气（H₂）的释放.催化剂的结构表征证明：Rh亚纳米团簇的平均尺寸约为0.66 nm.构效关系研究表明：二维Ti₃C₂T_x MXene载体表面高度暴露的碳钛键（C-Ti）结构可以起到锚定和高度分散Rh亚纳米团簇的作用.     

高载量钴离子掺杂MnO2用于高性能锌离子混合电容器

通过恒流电沉积的方法在柔性碳布上制备了钴离子掺杂的MnO₂，其负载量达到13.8 mg/cm²。利用X射线衍射仪（X-ray diffractometer, XRD）、扫描电子显微镜（scanning electron microscope, SEM）、X射线光电子能谱（X-ray photoelectron spectrometer, XPS）和电化学工作站等对材料的结构和性能进行表征，探究了钴离子掺杂对MnO₂电化学性能的影响。结果表明，当该电极与活性炭组装成液态锌离子混合电容器（zinc ion hybrid capacitors, Zn-HCs）时，Zn-HCs在2 mA/cm²的电流密度下，面积比电容高达5 883.0 mF/cm²，面积能量密度为3 154.9 μWh/cm²，与锌离子电池的能量水平相当。当该电极与活性炭组装成准固态柔性Zn-HCs时，Zn-HCs具有较好能量密度（在1 mW/cm²的功率密度下达1 351.1 μWh/cm² ）的同时具有优异的机械柔韧性，使Zn-HCs有望应用于新一代的柔性可穿戴设备。     

BaCoO3基透氧材料的B位掺杂优化

采用传统的固相合成法制备BaCo_0.9-xFe_xNb_0.1O3-δ(BC0.9-xFxN0.1O, x=0.1,0.2,0.3,0.4)和BaCo_1-yNb_yO_3-δ(BC_1-yN_yO,y=0.10,0.12,0.14,0.16)混合导体透氧膜材料,较系统地研究Fe和Nb掺杂量对BC_0.9-xF_xN_0.1O和BC_1-yN_yO的晶体结构、晶粒大小、结构稳定性以及透氧率的影响.结果表明：Fe和Nb掺杂有助于提高BaCoO₃基钙钛矿材料的结构稳定性,但会降低材料的透氧能力;与Fe相比,Nb掺杂能够更有效地提高材料的高温化学稳定性,并细化晶粒;厚度为1 mm的BaCo_0.88Nb_0.12O_3-δ膜片在850 ℃和Air/He（110 mL·min^-1/80 mL·min^-1）的吹扫条件下,透氧率为2.02 mL·cm-²·min^-1.     

原位合成NiCo-MOF/MXene材料的电容性能研究

在不使用任何黏合剂的情况下,将镍钴双金属有机框架材料(NiCo-metal organic framework,NiCo-MOF)和MXene材料附着在泡沫镍(nickel foam,NF)表面,合成了高性能电极材料,这两种材料结合生长出的层状结构有利于离子的快速传导,减少了活性材料的无效堆砌,同时表现出理想的电化学性能。当投入原料的镍钴物质的量之比为1∶2时,制得的电极材料在5 mA/cm²的电流密度下表现出4.96 C/cm²的优良比电容。得到的电极与活性炭(activated carbon,AC)负极组装成不对称超级电容器后,在10.09 W/cm²的功率密度下,得到的超级电容器的能量密度可达到1 530 mWh/cm²,并且当功率密度升高到102.29 W/cm²时,能量密度仍可以保持在770 mWh/cm²。在15 mA/cm²的电流密度下,经过5 000次充放电循环后,不对称超级电容器的电容保持率为98.52%。     

模板法制备CexZr1-xO2及催化餐饮废油合成生物柴油

以松木为模板,使用模板法制备了不同铈锆含量的Ce_xZr_1-xO₂复合氧化物的催化剂,用于餐饮废油与甲醇进行酯交换反应合成生物柴油.采用BET、SEM对Ce_xZr_1-xO₂进行表征分析.研究不同制备方法、CeO₂的负载量和煅烧温度对催化剂活性的影响,以及不同的酯交换反应条件对生物柴油产率的影响.制备的Ce_xZr_1-xO₂具有松木的生物形态,并有助于催化剂形成多孔道结构.以Ce_xZr_1-xO₂为催化剂,考察甲醇和餐饮废油的酯交换反应.结果表明：当x=0.5,煅烧温度为600℃时,甲醇与餐饮废油物质的量比为60：1,催化剂用量（基于餐饮废油的质量）的质量分数为5%,反应温度为190℃,反应时间为6 h的反应条件下,酯交换反应的甲酯收率达到91.1%.     

泡沫镍上原位生长CoMn2O4多级空心纳米球作为超级电容器电极材料的电化学性能研究

采用水热法结合空气气氛中的热处理过程,在泡沫镍（NF）表面生长了锰酸钴（CoMn₂O₄）多级空心纳米球,通过X射线衍射仪（XRD）、场发射扫描电镜（FE-SEM）和X射线光电子能谱（XPS）等测试手段对纳米球进行了表征.在三电极电化学测量系统中,0.1Co²⁺-250电极材料在5 mA·cm^-2时的面积比电容高达6 184 mF·cm^-2.以0.1Co²⁺-250为正极,商用活性炭（AC）为负极组装而成的混合超级电容器,在1.6 mW·cm^-2时的最大能量密度为0.112 mWh·cm^-2.即使在功率密度为16 mW·cm^-2时,能量密度仍达到0.064 mWh·cm^-2.在2 mA·cm^-2的电流密度下,经过10 000次充放电循环后,电容保持了初始值的93%.因其优越的电化学性能和低成本的便捷合成方法,CoMn₂O₄多级空心纳米球作为电极材料具有重要的应用前景.     

Unveiling the role of Zn dopants in NiFe phosphide nanosheet for oxygen evolution reaction

Transition metal phosphides have been recognized as promising electrocatalysts for oxygen evolution reaction(OER) due to their low cost and high activity. However, the insufficient exposed active region limited the OER performance. Recently, the introduction of sacrificial dopants has been considered an effective strategy to enlarge the surface area. Herein, the Zn dopants are introduced in NiFe phosphide(NiFeZnP) nanosheet, which work as the sacrificial dopants to generate more exposed active N...     

Multiple metallic dopants in nickel nanoparticles for electrocatalytic oxygen evolution

Developing efficient oxygen evolution reaction(OER) electrocatalysts is of great importance for sustainable energy conversion and storage. Ni-based catalysts have shown great potential as OER electrocatalysts, but their performance still needs to be improved. Herein, we report the multiple metal doped nickel nanoparticles synthesized via a simple oil phase strategy as efficient OER catalysts. The FeMnMoV–Ni exhibits superior OER performance with an overpotential of 220 mV at 10 mA cm^-2     

Cu2O-templated fabrication of Ni(OH)2·0.75H2O hollow tubes for electrocatalytic oxygen evolution reaction

Cu₂O is an ideal template material for the preparation of transition metal hydroxide/oxyhydroxides with oxygen evolution reaction (OER) enhanced catalytic performance. Here, inspired by Pearson's principle, Cu₂O wires were prepared and used as a sacrificial template to prepare Ni(OH)₂·0.75H₂O hollow tubes (Ni(OH)₂ HTs) with highly improved surface roughness. Benefiting from unique structural advantages, the Ni(OH)₂ HTs showed excellent catalytic activity, rapid kinetics and a long-term stability as the OER catalyst, where an overpotential of only 207 ?mV was required to drive a current density of 10 ?mA ?cm^?2, an ideal kinetics with a Tafel slope as 79.8 ?mV dec^?1 was calculated, and no obvious attenuation in chronoamperometry was discovered after operation for 24 ?h. This paper provides a novel template-assisted strategy to prepare high-performance transition metal-based OER catalysts possessing hollow and tubular structures.     

Dual elemental modulation in cationic and anionic sites of the multi-metal Prussian blue analogue pre-catalysts for promoted oxygen evolution reaction

Designing advanced electrocatalysts for the oxygen evolution reaction (OER) is of great significance owing to its crucial role in facilitating the production of clean hydrogen energy via water splitting. To date, it has been widely accepted that a pre-oxidation process with the in-situ generation of the catalytically active high-valence metal sites is essential for promoting the OER behavior of most transition-metal-based OER catalysts, or more felicitously speaking, pre-catalysts. Hence, exploring such pre-catalysts with high pre-oxidation reactivity is of high promise. Herein, we proposed the dual elemental modulation in the cationic and anionic sites of the multi-metal Prussian blue analogue (PBA) pre-catalysts, resulting in promoted OER behavior benefitted from the efficient pre-oxidation ability as well as the multi-metal synergy. Detailed investigations indicate that the Co-containing multi-metallic cations and mixed Fe^IIICo^III cyanide anions in NiCuCo^II–Fe^IIICo^III PBA (denoted as NiCuCo^II–Fe^IIICo^III) are beneficial to OER catalysis owing to the high intrinsic activity guaranteed by the local Co³⁺ active sites as well as the optimal multi-metal synergy. After the facile pre-oxidation process, additional high-valence Ni, Cu and Fe ions can be in-situ formed and serve as the active sites, thereby resulting in significantly improved OER behavior. For example, the OER current density of NiCuCo^II–Fe^IIICo^III exhibits 1.81 times enhancement even after 72 ?h continuous OER catalysis, and the required overpotential for 10 ?mA ?cm^?2 reduces from 288 ?mV for the fresh pre-catalyst to a remarkable record of 251 ?mV after the pre-oxidation-induced activation, making the optimal PBA-based catalyst a promising candidate for efficient and durable water electrolysis.     

Gas-Liquid Interfacial Plasma engineering under dilute nitric acid to improve hydrophilicity and OER performance of nickel foam

The world has been moving rapidly to find new eco-friendly energy sources. Water electrolysis consists of two reactions of Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER), whereas the OER is considered the rate-limiting step. The most commercialized electrode for OER in the alkaline electrolyte is Ni foam, but its original surface is hydrophobic. It is possible to accelerate the adsorption and desorption process of reactants and products during OER by adding hydrophilic functional groups such as –OH on the surface of Ni foam. In this study, a novel Gas-Liquid Interfacial Plasma (GLIP) engineering at room temperature was successfully applied to modify the Ni foam surface dilute (1 ?M) HNO₃ solution. At a current density of 400 ?mA ?cm^?2, GLIP-treated Ni foam electrodes at 1 ?M HNO₃ concentrations showed OER overpotentials of 458 ?mV. Among all, GLIP with 1 ?M HNO₃ treatment of 30 ?min showed 129 ?mV less overpotential than the nickel foam before treatment. In summary, GLIP can be justified as an environmentally friendly and efficient surface treatment to improve the wettability and OER performance of Ni-based electrodes in water electrolysis.     

镍铁钴磷化物纳米片阵列的制备及其电催化析氧性能

采用溶剂热法将镍、铁和钴的硝酸盐溶液在180 ℃条件下反应24 h，经过后续磷化反应，在泡沫镍基底上生长镍铁钴磷化物纳米片阵列(NiFeCoP@NF).采用X射线衍射、扫描电子显微镜、透射电子显微镜、X射线光电子能谱等测试手段对材料进行了表征，并用电化学工作站研究了镍铁钴磷化物纳米片阵列的析氧性能.结果表明:当电流密度达到10 mA/cm2时，需要的过电势仅为160 mV，并且在恒定电流密度下，过电势可保持24 h.研究结果对于研究纳米结构的过渡金属磷化物电催化剂具有借鉴意义.     

Effect of B sites on the catalytic activities for perovskite oxides La_(.6)Sr_(.4)Co_xFe_(1-x)O_(3-δ) as metal-air batteries catalysts

The effect of B sites on the catalytic activities of oxygen evolution reaction(OER)for perovskite oxides La_(0.6)Sr_(0.4)Co_xFe_(1-x)O_(3-δ)(x=0,0.2,0.4,0.6,0.8,1,denoted as LSF,LSCF-28,LSCF-46,LSCF-64,LSCF-82 and LSC,respectively)prepared by a convenient and simple method of electrospinning technique is reported.The prepared La_(0.6)Sr_(0.4)Co_xFe_(1-x)O_(3-δ)catalysts possess almost same crystal structures,similar morphologies(except for the LSC catalyst)and slightly different BET surface areas.Upon the optimization of the Co/Fe atomic ratio,the optimal LSCF-82 catalyst exhibits the OER performance with a low onset potential of 1.541 V,a small Tafel slope of 80.56 mV dec~(-1),a high charge-transfer rate and a large electrochemical surface area in 0.1 M KOH solution.LSCF-82 catalyst exhibits the long-term stability under the catalytic operation condition for 12 h.Such catalytic activity may mainly cause by the synergy of higher catalytic activity Co and lower catalytic activity Fe.Thus,the reasonable optimization of the transition metal composition in B sites for the perovskite oxides is in favor of the improvement of OER performance.     

Bimetal nickel–cobalt phosphide directly grown on commercial graphite substrate by the one-step electrodeposition as efficient electrocatalytic electrode

It is challenging to find a method to obtain a catalyst with low cost and efficient multifunctional performances. Herein, in order to obtain the electrode with high-performance water splitting and non-enzymatic glucose detection, the commercial graphite sheet (GS) with excellent durability and electroconductivity was used as substrate material, and the non-noble ternary component Ni–Co–P catalyst with hierarchical architecture was fabricated on GS via a co-electrodeposition. The catalyst only required low overpotentials of 44.6, 76.5 and 49 mV to drive the current density of 10 mA cm⁻² alongside with the smaller Tafel slopes of 39.2, 44.8 and 112 mV dec⁻¹ for hydrogen evolution reaction (HER) in 1.0 M KOH, 0.5 M H₂SO₄ and 1.0 M PBS solution, respectively. For oxygen evolution reaction (OER), the catalyst demonstrated a low overpotential of 304 mV to achieve the current density of 20 mA cm⁻² with excellent Tafel slope of 89.8 mV dec⁻¹ in alkaline solution. Furthermore, the Ni–Co–P/GS electrode serving as non-enzymatic glucose sensor exhibited the superior electrocatalytic activity with an ultrahigh sensitivity of 7400 μA mM⁻¹ cm⁻², low detection limit of 0.425 μM (S/N = 3), and wide linear range (1–1200 μM).     

Co4S3纳米片的制备以及Fe3+掺杂对其电催化析氧性能的影响

采用溶剂热和超声剥离相结合的方法制备了超薄Co₄S₃纳米片,通过透射电子显微镜（TEM）、扫描电子显微镜（SEM）、原子力显微镜（AFM）、X-射线衍射分析（XRD）、拉曼光谱（Raman）等手段对其进行了结构和形貌的表征,并研究了其电催化产氧性能。结果表明,Co₄S₃纳米片在电流密度为10 mA/cm²下的过电势为377 mV,塔菲尔（Tafel）斜率为64.47 mV/dec;溶剂热过程中反应温度和溶剂比对产物的析氧反应（OER）催化活性影响不大,但是Fe³⁺的掺杂可以显著降低Co₄S₃纳米片的析氧过电势和Tafel斜率,提高材料的电催化稳定性。最后通过X-射线光电子能谱（XPS）分析了Fe³⁺的掺杂对Co₄S₃纳米片OER性能影响的机理。