ZIF-derived Co–N–C ORR catalyst with high performance in proton exchange membrane fuel cells

Metal and nitrogen-doped carbon (M-N-C) materials have been considered as the most promising non-precious metal oxygen reduction (ORR) catalysts to replace expensive Pt catalysts. Due to high Fenton catalytic activity of Fe element and the resulting instability, Co-based N–C (Co–N–C) catalysts without Fenton catalytic activity should be a worthier ORR catalyst being explored. Although the high ORR activity of Co–N–C catalyst has been demonstrated in aqueous half-cell tests, their performance under PEMFC working condition is still far away from that of state-of-the-art Fe–N–C catalysts. In this study, a high-performance Co–N–C catalyst was synthesized by one-step pyrolyzing Co-doped ZIF-8 (zeolitic imidazolate framework-8) particles in-situ grown on the high-surface-area KJ600 carbon black with high electronic conductivity. The resulting Co–N–C catalyst exhibited high intrinsic ORR activity, fast mass transfer rate and high electronic conductivity, and thus yielded a remarkable peak power density of 0.92 W cm^-2 in H₂–O₂ PEMFC, which is comparable to state-of-the-art Fe–N–C catalyst. This strategy is helpful to synthesize highly active M-N-C ORR catalysts with improved mass transfer and electric conductivity.     

Nitrogen-doped graphene nanosheets as high efficient catalysts for oxygen reduction reaction

It is of great significance in exploring alternative catalysts to platinum (Pt)-based materials for oxygen reduction reaction (ORR),because this reaction is invariably involved in various fuel cells and metal-air batteries.We herein reported the nitrogen doped graphene nanosheets (NGNSs) with pore volume of as high as 3.42 m 3 /g and investigated their potential application as ORR catalysts,it was demonstrated the NGNSs featured high activity,improved kinetics and excellent long-term stability for ORR.The NGNSs were successfully used as cathode catalysts of microbial fuel cells (MFCs) and performed even better than the commercial Pt/C (Pt 10%) catalysts at the maximum power output.     

氮掺杂还原氧化石墨包覆金属钴复合材料的制备及其氧还原性能的研究

采用搅拌反应法制备了ZnCo（ZIF）与氧化石墨（graphite oxide,GO）的复合材料,热处理得到Co@N-doped rGO催化剂。通过X射线衍射（X-ray diffraction,XRD）和扫描电子显微镜（scanning electron microscopy,SEM）对催化剂进行结构表征,通过X射线光电子能谱（X-ray photoelectron spectroscopy,XPS）对催化剂进行表面元素分析,分别考察了金属（Zn和Co）加入量和热处理温度对催化剂氧气还原反应（oxygen reduction reaction,ORR）催化性能的影响,结果表明：所制备的催化剂整体呈层状分布,表面附着金属小颗粒团簇;随着金属加入量的增加,催化剂的ORR催化性能先增强后减弱;随着热处理温度的升高,催化剂的ORR催化性能先增强后减弱。所制备的S-2-850催化剂具有最好的ORR催化性能,在0.1 mol/L KOH电解液中,其起始电位和半波电位分别为0.871 V和0.804 V,在相同测试条件下活性稳定性优于20% Pt/C。     

Nickel-introduced structurally ordered PtCuNi/C as high performance electrocatalyst for oxygen reduction reaction

Designing highly active and durable oxygen reduction reaction (ORR) electrocatalysts is essential for developing efficient proton-exchange membrane fuel cells (PEMFCs). In this work, ordered PtCuNi/C nanoparticles (NPs) were synthesized using an impregnation reduction method. This study shows that the incorporation of Ni in ordered PtCu/C can effectively adjust the electronic structure of Pt, thereby optimizing oxygen binding energy for the ORR. The obtained intermetallic ordered PtCuNi/C NPs significantly improved ORR activity and durability compared to ordered PtCu/C. Specifically, PtCu_0·5Ni_0·5/C-700 shows a mass activity of 1.29 ​A ​mg _Pt⁻¹ ​at 0.9 ​V vs. reversible hydrogen electrode (RHE), which is about 9.2 times higher than that of commercial Pt/C. PtCu_0.5Ni_0.5/C-700 is also shown to be competent cathode catalyst for a single-cell system exhibiting high power density (461 ​mW ​cm⁻²). This work demonstrates that ordered PtCu_0·5Ni_0·5/C-700 can be used as a highly active and durable ORR catalyst in PEMFCs.     

CO2加氢逆水煤气变换（RWGS）催化剂研究进展

化石能源的广泛使用，导致CO2肆意排放至大气环境，引发一系列严重的环境问题。CO2逆水煤气变换（RWGS）反应，是实现CO2资源化利用的有效途径。对RWGS反应催化剂研究情况进行了系统的总结和综述，详细地分析了Pd、Au、Pt、Cu、Fe和Mo基等催化剂的RWGS反应性能，对金属与载体间相互作用和掺杂元素的电子效应对催化RWGS反应性能的影响进行了系统的分析。Pd、Au和Pt等贵金属对CO2弱的结合能力和定向转化能力，需进一步提高贵金属催化剂对CO2分子的吸附和活化能力来提升其催化性能。非贵金属Cu、Fe和Mo基催化剂的低温活性较差，借助新的催化剂制备方法和策略，将进一步提升CO2分子的低温催化转化活性。研究结果证实，通过优化催化剂中活性组分与载体或助剂的相互作用，能实现对相应催化剂的RWGS反应性能进行调控。总结了非贵金属和贵金属催化剂上CO2 加氢机理，分析了非贵金属和贵金属催化剂RWGS反应性能间的差异，为开发制备新型的RWGS反应催化剂材料提供了可行思路和理论依据。     

Co(S1-xSex)2.0化合物的制备及对阴极氧还原的催化性能

采用Co4(CO)12、S粉和Se粉为原料,在1,6-己二醇介质中利用低温回流法合成Co(S1-xSex)2.0(x=0.1～0.9)化合物。利用扫描电镜(SEM)、X-射线衍射仪(XRD)和旋转圆盘电极(RDE)表征了化合物的物理特征和电催化性能。这类化合物呈现出聚集的纳米粒子表面形貌,化合物中含有正交结构的CoSe2晶粒和立方结构的Co9S8晶粒。在氧气饱和的0.5 mol/LH2SO4电解液中,Co(S1-xSex)2.0化合物对氧还原反应(ORR)的催化活性、开路电位和交换电流密度随Se含量的增加而增大。     

Platinum-supported mesoporous carbon (Pt/CMK-3) as anodic catalyst for direct methanol fuel cell applications: The effect of preparation and deposition methods

Platinum-supported ordered mesoporous carbon catalysts were prepared employing colloidal platinum reduced by four different reducing agents, viz., paraformaldehyde, sodium borohydride, ethylene glycol and hydrogen, and deposited over ordered mesoporous carbon (CMK-3) synthesized by silica hard template (SBA-15). The resulting platinum nanoparticles supported mesoporous carbon, designated as Pt/CMK-3, catalysts were tested for the electocatalytic oxidation of methanol. The effect of the various reduction methods on the influence of particle size vis- a-vis on the electrocatalytic effect is investigated. All the catalysts were systematically characterized by XRD, BET and TEM. The results of the synthetic methods, characterization techniques and the electrocatalytic performance indicate that the Pt/CMK-3 catalysts are superior to that prepared with activated carbon (Pt/AC) as well as with that of the commercial platinumsupported carbon catalyst (Pt/E-TEK). In particular, the catalyst, Pt/CMK-3, prepared using paraformaldehyde reduced platinum showed much higher activity and long-term stability as compared to the other reducing methods.     

A novel bimetallic RuFe nanocluster to enable highly efficient oxygen reduction in zinc-air batteries

Zinc-air batteries (ZABs) have the advantages of high energy density and safety but their large-scale application is hindered by sluggish kinetics of four-electron aqueous O₂ redox reactions. Widely used Ruthenium (Ru)-based catalysts possess intrinsic oxygen evolution catalytic activity but suffer from insufficient oxygen reduction reaction (ORR) performance. Herein, to optimize the ORR activity of Ru-based catalyst, an iron (Fe)-coordinated, bimetallic RuFe cluster is constructed and homogeneously dispersed within nitrogen (N)-doped carbon layers (denoted as RuFe@NC). Benefitting from the optimized ORR activity and more active site exposure, the RuFe@NC exhibits superior ORR activity with a half wave potential (E_1/2) of 0.88 ?V higher than that of Pt/C (0.82 ?V). Accordingly, the RuFe@NC-based ZAB outperforms the Pt/C ?+ ?IrO₂-based device, presenting a reduced polarization of 0.7 ?V and an enhanced cycling lifetime of 50 ?h at 10 ?mA ?cm^?2. Moreover, the optimized structural design ultralow Ru loading (0.013 mg_Ru cm^?2) overcomes the cost barriers and demonstrates its high practicality. This bimetallic RuFe nanocluster opens a new way for future design of more efficient and stable catalytic systems.     

提升Pd基电催化剂氧还原活性的策略

氧还原反应(ORR)是许多电化学相关技术的核心反应,许多研究致力于制备同时具备高活性、高稳定性和低成本的催化剂。Pd基纳米材料由于其相对较优的催化性能和相对丰富的储量,有望成为Pt的替代品,受到了广泛关注,但要达到商品化程度,其性能需进一步提高。本文以Pd基催化剂应用于ORR电催化为背景,综述了近年来Pd基催化剂ORR的性能提升策略。围绕载体调控、形貌结构调控以及组分调控共3个部分进行总结,这些调控会利用配体效应、应变效应、系综效应(ensemble effect)和载体效应等从本质上改变Pd的分布状态、空间排列和电子结构,从而影响ORR中间产物在Pd表面的吸附状态。最后,简要介绍了Pd基催化剂面临的挑战和未来的发展方向,对高性能ORR催化剂的设计制备具有重要意义。     

活性炭负载Ptm^Au催化剂的制备与甲醇电催化氧化反应活性

采用溶胶负载法制备了Ptm^Au/C催化剂（m代表Pt/Au原子比）,通过X射线衍射、紫外-可见吸收光谱及透射电镜对催化剂进行了表征.利用循环伏安法测定了催化剂对甲醇电催化氧化反应的活性.考查了Pt/Au原子比和活性炭载体的预处理方式对甲醇电催化氧化反应活性的影响.结果表明,Pt0.05^Au/C对甲醇氧化的催化性能明显强于Pt/C催化剂;Pt/Au原子比越小,其催化活性相对越高;与未处理的活性炭相比,经过HNO3和HCl处理的活性炭负载Pt0.05^Au后,其电催化活性有所降低.     

Surface-confined Pt-based catalysts for strengthening oxygen reduction performance

Developing highly efficient catalysts for the oxygen reduction reaction (ORR) is a key to the fabrication of commercially viable fuel cell devices for future energy applications. Considerable progress has been made to reduce Pt usage and improve performance of the Pt catalysts by modulating exposed facets of Pt nanocrystals and combining Pt with other metals to generate bimetallic nanocrystals with structures in the form of alloys, core-shells, branches or anisotropies. Apart from the above methods, confining Pt-based nanoparticles (NPs) surfaces with elaborately selected layers such as polymers, silicon or carbons can also lead to an optimized Pt electronic structure, which is beneficial to ORR process. In this minireview, we summarize the recent advancements in the area of surface-confined Pt-based electrocatalysts for ORR with emphasis on introducing the design strategies and synthesis methodologies. The integration of these catalysts into ORR operations and the resulting performance as well as the strengthening mechanisms is also discussed. Meanwhile, the insights into the research directions are proposed in order to shed light on the future development of surface-confined Pt-based ORR catalysts.     

Large specific surface area S-doped Fe–N–C electrocatalysts derived from Metal–Organic frameworks for oxygen reduction reaction

It is highly desired but challenging to develop platinum group metal-free electrocatalysts for oxygen reduction reaction (ORR), which can promote the commercialization of fuel cell technology. To achieve this target, we report a one-step doping method to prepare S-doped Fe–N–C catalysts using zeolite imidazole framework (ZIF-8) and iron (III) thiocyanate (Fe(SCN)₃) as precursor. Different from conventional doping approach, i.e. physical mixing, Fe(SCN)₃ is in-situ added during ZIF-8 formation which would encapsulate Fe(SCN)₃ molecules inside ZIF-8 to avoid structure destruction and create potential replacement of Zn ions by Fe ions to form uniform Fe–N₄ complexes. As a result, the prepared S-doped Fe–N–C catalysts own large specific surface areas with a maximum value of 1326 ​m² ​g⁻¹ and a dual-scale porous structure that benefits mass transport. Significantly, the composition-optimized catalyst exhibits superior ORR activity in both 0.1 ​M HClO₄ electrolyte and 0.1 ​M KOH electrolyte, in which the half-wave potential reaches 0.81 ​V and 0.92 ​V (vs. RHE), respectively. Remarkable stability is also attained, which loses 2 ​mV only after 10000 potential cycles in O₂-saturated 0.1 ​M HClO₄ and remains almost constant in O₂-saturated 0.1 ​M KOH, surpassing commercial Pt/C catalyst in both acidic and alkaline medium.     

氧化锌负载金和铂选择催化氧化燃料电池氢源中微量CO的研究

采用共沉淀法制备了负载型Au/ZnO催化剂，采用催化氧化方法脱除富氢中微量的CO研究结果表明，催化剂中Au的合适含量 (质量分数 )为1.5%，适宜的焙烧温度为300℃，即Au(1.5)/ZnO-300。在Au(1.5) /ZnO-300体系中加入少量的PtO组分有利于提高催化剂的稳定性。进一步研究表明，当Pt含量超过1.0%时，会降低催化剂的催化氧化选择性。因此在实验条件下，催化剂比较理想的组成为1.5%Au，10%Pt，焙烧温度为300℃，即Au(1.5)-Pt(1.0)/ZnO-300。对制备的催化剂采用XRD，BET进行了基本表征，并应用ICP对催化剂的组成进行了分析。     

PdCo/C氧还原催化剂及其抗甲醇性能(英文)

以柠檬酸钠为络合剂,在乙二醇体系中采用有机溶胶法制备出了PdCo/C催化剂,XRD研究结果表明催化剂具有面心立方结构,粒度小,分散性好,同时元素钴的加入使催化剂的Pd-Pd间距缩小。采用电化学方法评价了催化剂对于氧气还原反应的活性,结果表明:PdCo/C催化剂具有比Pd/C要好的氧还原活性,同时具有Pt/C催化剂无法比拟的抗甲醇中毒能力。     

金原子簇催化应用的研究进展

在最近的10年里,原子精确的金原子簇(AunLm,L为有机配体)已经被证明是一种新型的纳米金催化剂.不同尺寸的AunLm催化剂表现出独特的电子和晶体结构,为关联催化性能和催化剂结构的内在关系及研究纳米金催化的化学反应机制提供了新的研究平台.在这篇综述中,主要介绍金原子簇催化剂在催化反应中的应用,如选择性氧化和加氢,及C—C偶联反应等,同时,也讨论金原子簇催化剂的尺寸效应、配体效应(例如,芳香族vs脂肪族)、杂金属掺杂(如铜、银、钯、铂)等.最后,在原子尺度上研究了金原子簇催化的反应机制以及结构-活性的构建关系.     

Pyrolysis of Iron(III) porphyrin coated Pt/C toward oxygen reduction reaction in acidic medium

Design and synthesis of highly active and durable electrocatalysts toward oxygen reduction reaction (ORR) is of particular importance for proton exchange membrane fuel cells (PEMFCs), yet remains a grand challenge. Herein, we report the deposition of iron (III) porphyrin (FeP) on house-made Pt/C by rotary evaporation of the mixture of FeP and house-made Pt/C dispersed in chloroform, followed by pyrolysis at 650 °C in argon atmosphere. This approach led to the synthesis of new non-precious metal electrocatalyst (NPME)-Pt/C composites (Pt/C–FeP) with an average nanoparticle diameter of 3.1 ± 1.5 nm without aggregation. According to X-ray photoelectron spectroscopy (XPS), the binding energy of Pt 4f_7/2 became larger due to the presence of pyrolyzed FeP. In addition, the electrochemically active surface area (ECSA) of Pt/C–FeP-650 is 65 m²/g less than that of house-made Pt/C (80.2 m²/g). This implies that the pyrolyzed FeP may have partially covered the surface of Pt nanoparticles and thus lowering the ECSA. Interestingly, the mass activity (MA) of Pt/C–FeP turns out to be 349.0 mA/mg_Pt @0.9 V vs. RHE, which is 2.6 times and 1.5 times of house-made Pt/C and commercial Pt/C, respectively. It is speculated that the electronic interaction and possible synergy between Pt and pyrolyzed FeP as NPME might have contributed to the ORR activity improvement despite of partial loss of ECSA. During accelerated durability tests (ADTs), the MA of Pt/C–FeP-650 degrades 64.3% inferior to commercial Pt/C (52.2%). The main reason likely arises from the degradation of pyrolyzed FeP, which is a bottleneck problem confronting NPMEs.     

超支化聚酰胺负载铂纳米簇杂化膜催化剂在苯加氢反应中的活性寿命

采用溶液缩聚合成了超支化聚酰胺,制备了超支化聚酰胺负载铂纳米簇杂化膜催化剂,对比新鲜和使用11次后的杂化膜催化剂,考察了催化剂在苯加氢反应中的活性寿命问题,并结合了透射电流(TEM)、X-射线衍射(XRD)、X-射线能谱(XPS)等手段对催化剂表征.结果表明:杂化膜型催化剂比传统粉末型催化剂寿命更长、活性更好;在杂化膜型催化剂中,使用超支化聚合物作为贵金属的载体,比线性聚合物作载体时苯的转化率高.起主要催化作用的可能是杂化膜表面的铂纳米颗粒.     

FeCo-based mesoporous carbon shells modified N-doped porous carbon spheres for oxygen reduction reaction

FeCo-based non-noble metal electrocatalysts (NNMEs) of FeCo/MCS-NPCS was fabricated by immobilization of hemin on mesoporous carbon shells modified N-doped porous carbon spheres (MCS-NPCS). The obtained FeCo/MCS-NPCS exhibits a half-wave potential (E_1/2) of 0.851 ​V versus the reversible hydrogen electrode (vs. RHE) and a limited-diffusion current density (J_L) of 5.45 ​mA ​cm⁻². In addition, FeCo/MCS-NPCS shows comparable oxygen reduction reaction (ORR) performances to 20 ​wt% Pt/C in terms of E_1/2 and J_L and better electrochemical properties, including the methanol tolerance and durability in alkaline solution. Such outstanding electrochemical activities of FeCo/MCS-NPCS can be ascribed to Fe and/or Co-based nitrides and carbides as well as N-doped carbon matrixes modified with mesoporous carbon shells. This research introduces a promising path to design and synthesize highly efficient FeCo–N–C electrocatalysts towards ORR.     

PtCo alloy nanoparticles supported on graphene nanosheets with high performance for methanol oxidation

PtCo alloy nanoparticles are deposited onto graphene sheets through a facile and reproducible hydrothermal method.During the hydrothermal reaction,the reduction of graphene oxide and PtCo alloy nanoparticles loading can be achieved.X-ray diffraction (XRD) analyses reveal a good crystallinity of the supported Pt nanoparticles in the composites and the formation of PtCo alloy.X-ray photoelectron spectra (XPS) results depict that Pt mainly exists in the metallic form,while much of the cobalt is oxidized.Transmission electron microscope (TEM) observations show that the PtCo alloy nanoparticles are uniformly dispersed on graphene nanosheets compared with multiwalled carbon nanotubes (MWNTs).This PtCo-graphene composite exhibits excellent electrocatalytic activity and high poison tolerance toward poisoning species for methanol oxidation reaction,far outperforming the Pt-graphene or PtCo-MWNTs composites with the same feeding ratio of Pt/carbon.     

ZrO_2-supported α-MnO_2:Improving low-temperature activity and stability for catalytic oxidation of methane

The single phaseα-Mn O_2and in-situ supportedα-Mn O_2/Zr O_2with different ratios of Mn/Zr were synthesized by one-pot hydrothermal method.They showed superior activity for catalytic oxidation of methane and even better than that of 1%Pt/Al_2O_3.The T_(50)of Mn O_2/Zr O_2catalysts with different ratios of Mn/Zr were located in the range of 315–335°C at a WHSV of 90 L g~(-1)h~(-1),whereas that of Pt/Al_2O_3was 380°C.After sulfur ageing,the Mn O_2/Zr O_2catalysts with Mn/Zr ratio of 2:1(2Mn O_2/1Zr O_2)and 1:1(1Mn O_2/1Zr O_2)exhibited satisfying sulfur resistance in comparison to the pure Mn O_2.The 2Mn O_2/1Zr O_2catalyst also showed acceptable catalytic stability,and the addition of 10 vol%CO_2had no obvious negative effect on its stability,whereas the addition of2.6 vol%H_2O caused slight but reversible decreasing methane oxidative activity.