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1.
Inefficient electrocatalysts and high-power consumption are two thorny problems for electrochemical hydrogen(H2)production from acidic water electrolysis.Herein we report the one-pot precise synthesis of ultrafine Au core-Pt Au alloy shell nanowires(Au@PtxAu UFNWs).Among them,Au@Pt0.077 Au UFNWs exhibit the best performance for formic acid oxidation reaction(FAOR)and hydrogen evolution reaction(HER),which only require applied potentials of 0.29 V and-22.6 m V to achieve a current density of 10 m A cm-2,respectively.The corresponding formic acid electrolyzer realizes the electrochemical H2 production at a voltage of only 0.51 V with 10 m A cm-2 current density.Density functional theory(DFT)calculations reveal that the Au-riched Pt Au alloy structure can facilitates the direct oxidation pathway of FAOR and consequently elevates the FAOR activity of Au@Pt0.077 Au UFNWs.This work provides meaningful insights into the electrochemical H2 production from both the construction of advanced bifunctional electrocatalysts and the replacement of OER.  相似文献   

2.
Lithium metal batteries are considered as high energy density battery systems with very promising prospects and have bee n widely studied.However,The uncon trollable plating/strippi ng behavior,infinite volume change and den drites formation of lithium metal anode restrict the applicati on.The unc on trolled n ucleati on of lithium caused by the non uniform multi-physical field distributions,can lead to the undesirable lithium deposition.Herein,a graphene composite uniformly loaded with Ag nano-particles(Ag NPs)is prepared through a facile Gamma ray irradiation method and assembled into self-supported film with layered structure(Ag-rGO film).Whe n such film is used as a lithium metal an ode host,the uncontrolled deposition is converted into a highly nucleation-induced process.On one hand,the Ag NPs distributed between the in terlayers of graphe ne can preferentially induce lithium nu cleati on and en able uniform deposition morphology of lithium between interlayers.On the other hand,the stable layered graphene structure can accommodate volume change,stabilize the interface between anode and electrolyte and inhibit dendrites formation.Therefore,the layered Ag-rGO film as anode host can reach a high Coulombic efficiency over 93.3% for 200 cycle(786 h)at a current density of 1 mA cm-2 for 2 mAh cm-2 in carbonate-based electrolyte.This work proposes a facile Gamma ray irradiation method to prepare metal/3D-skeleton structure as lithium anode host and demonstrates the potential to regulate the lithium metal deposition behaviors via manipulating the distribution of lithiophilic metal(e.g.Ag)in 3D frameworks.This may offer a practicable thinking for the subsequent design of the lithium metal anode.  相似文献   

3.
中国纤维素乙醇技术的研究进展   总被引:1,自引:0,他引:1  
杨斌  Charles E.Wyman 《化学进展》2007,19(7):1072-1075
中国面临着严重的能源短缺和环境污染问题,中国政府正在局部几个省份内政策性鼓励燃料乙醇生产和使用.尽管当前主要是用玉米和谷物作为生产乙醇的原料,然而中国具有大量潜在的低成本的纤维素生物质原料,可以极大地扩大乙醇的产量,降低原料成本.近20年来,由于技术的革命性进步,已使得纤维素乙醇的生产成本从4美元/加仑以上,降低至约1.2-1.5美元/加仑.其中,每吨生物质约44美元.因此,目前乙醇掺汽油具有十分强的市场竞争力.已有几个公司正在建造首批商业纤维素乙醇工厂,虽然这些刚起步的小型设施在合理利用和管理上风险较小,但规模经济需要较大型工厂.尽管配送生物质原料的成本会随需求的增加而增加,但在乙醇生产基础上的生物精炼技术的发展,尤其是化工产品和动力的协同生产,将会使全过程的经济可行性大大提高.进一步深入的基础研究,将解决低成本下实现纤维素的完全利用,以确保在无政策性补贴的前提下,真正使纤维素乙醇成为具有市场竞争力的低成本纯液体燃料.  相似文献   

4.
Hierarchically porous architecture of ir on-nitroge n-carb on(Fe-N-C)for oxyge n reducti on reaction(ORR)is highly desired towards efficient mass transfer in the fuel cell device manner.Herein,we reported a binary ligand strategy to prepare zeolitic imidazolate frameworks(ZIFs)-derived precursors,wherein the addition of secondary ligand endows precursors with the capabilities to transform into porously interweaved encapsulation-nanotubes structured composites after calcination.The optimal catalyst,i.e.,termed as Fe6-M/C-3,exhibits excellent durability with 88.8%current retention after 50,000 seconds in 0.1 M HClO4solution by virtue of nanoparticles-encapsulation features,which is more positive than the benchmark commercial 20 wt%Pt/C catalyst.Moreover,a promising maximum power density of Fe6-M/C-3 as cathode catalyst was also dem on strated in proton exchange membrane fuel cells(PEMFCs)measurements.Therefore,this binary ligand approach to the fabrication of hierarchically porous structures would also have significant implications for various other electrochemical reactions.  相似文献   

5.
Currently,pyrolysis as the most widely used method still has some key issues not well resolved for synthesis of carbon-supported single-atom catalysts(C-SACs),e.g.,the sintering of metal atoms at high temperature as well as the high cost and complicated preparations of precursors.In this report,molten salts are demonstrated to be marvellous medium for preparation of C-SACs by pyrolysis of small molecular precursors(ionic liquid).The ultrastrong polarity on one hand establishes robust interaction with precursor and enables better carbonization,resulting in largely enhanced yield.On the other hand,the aggregation of metal atoms is effectively refrained while no nanoparticle or cluster is formed.By this strategy,a C-SAC with atomically dispersed Fe-N4 sites and a high specific area over 2000 m2 g-1 is obtained,which illustrates high ORR activity in both acid and alkaline media.Moreover,this SAC exhibits superior methanol tolerance and stability after acid soaking at 85℃ for 48 h.It is believed that the molten-salts-assisted pyrolysis can be developed into a routine strategy as it not only can largely simply the synthesis of C-SACs,but also can be extended to prepare other types of SACs.  相似文献   

6.
镧对Mg-Si合金中Mg2Si相变质的影响   总被引:1,自引:0,他引:1  
研究了Mg-5Si合金中La的添加对初生Mg2Si相变质的影响。结果表明,适量的La能够有效地变质初生Mg2Si相。基于本文的研究,在添加约0.5%La时,获得了最佳的变质效果,此时,初生Mg2Si相的尺寸减小到25μm以下,其形态从粗大的树枝形状变为多面体形状。然而,当La增加到0.8%或者更高时,初生Mg2Si相又生长为粗大的树枝形态。而且,在凝固过程中发现形成了一些LaSi2化合物,这些化合物的数量随着La的增加而呈现逐渐增加的趋势。  相似文献   

7.
建立STD/KED模式-电感耦合等离子体质谱(ICP-MS)法同时测定天然水体中铍、硼、钛、钒、铬、锰、钴、镍、铜、锌、钼、镉、锑、钡、铊、铅、铁、砷和硒19种元素的分析方法。仪器调谐校准后,样品在线加入锂、钪、铑、铋校准溶液校正,以标准曲线内标法定量分析。标准曲线相关系数均大于0.999,样品加标回收率为92.6%~103.6%,质控样品测定值相对标准偏差为0.20%~2.6%(n=6),方法检出限为0.01~0.70μg/L。该方法灵敏度高,操作简便,节省人力,能满足天然水体中19种元素的同时检测需要。  相似文献   

8.
吕秉玲 《化学学报》1988,46(9):854-861
由于在研究的体系中, Na2SO4是非对称电解质, 且能生成水合盐, 故推导了由非对称型电解质与非电解质所构成的混合溶液的各组分的活度系数关联通式, 并在此基础上讨论了水合盐液固平衡的计算方法.  相似文献   

9.
从黄花棘豆的总皂苷中分离出两个新皂苷1和2.经光谱分析及化学方法确证,1为3-O-[α-L-鼠李吡喃糖基(1→2)-β-D-葡萄吡喃糖基(1→4)-β-D-葡萄吡喃糖醛酸基]-黄豆醇B;2为3-O-[α-L-鼠李吡喃糖基(1→2)-α-L-阿拉伯吡喃糖基(1→4)-β-D-葡萄吡喃糖醛酸基]-黄豆醇B.  相似文献   

10.
二氧化钛纳米管由于其新奇的光电、催化、气敏等性能引起了广泛的关注,在太阳能电池、光催化、环境净化、气体传感器等领域有潜在的应用价值.本文概述了近年来在制备方法、反应机理和组成、晶型和形貌及掺杂和应用方面的进展,并讨论了今后可能的研究发展方向.  相似文献   

11.
以1-丁基-3-甲基咪唑溴离子液体([Bmim]Br)、磷钨酸(H_3PW_(12)O_(40))和g-C_3N_4为原料,采用原位沉淀法合成了负载型[Bmim]_3PW_(12)O_(40)/g-C_3N_4催化剂(BPWO/g-C_3N_4)。通过XRD、FT-IR、UV-vis、氮气吸附、TEM和XPS等手段对催化剂的形貌和结构进行了表征,并以二苯并噻吩(DBT)的正庚烷溶液为模拟油、过氧化氢为氧化剂,考察了各组分负载量、催化剂用量、氧/硫物质的量比(O/S)和反应温度变量等对其氧化脱硫效果的影响。结果表明,BPWO/g-C_3N_4具有Keggin型杂多阴离子结构特征,BPWO (20%)/g-C_3N_4催化剂具有最优的对DBT的氧化脱硫性能,在50℃、O/S物质的量比为6.0的条件下反应180 min,可以完全氧化浓度为800μg/g的含DBT模拟油。同时,该BPWO/g-C_3N_4催化剂具有良好的重复使用性能,循环使用八次后其对DBT的氧化活性没有明显降低。  相似文献   

12.
As a unique two-dimensional material, graphitic carbon nitride (g-C3N4) has received significant attention for its particular electronic structure and chemical performance. Its instinctive defect can provide a stable anchoring site for metals, potentially improving the surface reactivity. Ni-based catalysts are economical but their activity for CO2 methanation is lower than that of noble metal catalysts. Ni nanoparticles (NPs) supported on a substrate can further enhance the stability and activity of catalysts. Based on the principles of strong metal-support interaction (SMSI) and the synergistic effect on an alloy, MNi12/g-C3N4 composites as novel catalysts are expected to improve stability and catalytic performance of Ni-based catalysts. The configurations are established with core-shell structures of MNi12 (M = Fe, Co, Cu, Zn) nanoparticles (NPs) supported on g-C3N4 in this work. In the CO2 methanation reaction, the reactivity of CO on slab (ECO) is a critical factor, which is relative to the catalytic activity. Thus, the catalytic reactivity of these complexes via CO adsorption were explored using density functional theory (DFT). The values of cohesive energy (Ecoh) for MNi12 NPs range from -39.90 eV to -34.82 eV, suggesting that the formation of these NPs is favored as per thermodynamics, and Ecoh and partial density of state (PDOS) reveal that the central M atom with the less filled d-shell interacts more strongly with surface Ni atoms. Therefore, ZnNi12 is the most unstable structure among all the studied alloy, and the synergistic effect is also the weakest among them. When MNi12 NPs are supported on the g-C3N4 substrate, the binding energies (Eb) vary from -9.40 eV to -8.39 eV, indicating that g-C3N4 is indeed a good material for stabilizing these NPs. The PDOS analysis of pure g-C3N4 suggests the sp2 dangling bonds of N atoms in g-C3N4 can stabilize these transition metal NPs. Furthermore, the results of CO adsorbed on MNi12 NPs and MNi12/g-C3N4 composites show that ECO and dCO reduced with the introduction of g-C3N4. According to the results of the analysis of the Hirshfeld charges and electrostatic potential (ESP), the reason is that CO obtains less electrons from MNi12 NPs after deposition on the g-C3N4 substrate, which lowers the reactivity of CO on catalysts. Additionally, the deformation charge density is analyzed to investigate the interaction between the NPs and g-C3N4. With the introduction of g-C3N4, charge redistribution indicates the strong metal-support interaction, which further reduces the CO adsorption energy. In summary, MNi12 supported on g-C3N4 exhibit not only high stability but also tunable reactivity in CO2 methanation. These changes are beneficial for CO2 methanation reaction.  相似文献   

13.
Photocatalytic reduction of carbon dioxide into chemical fuels is a promising route to generate renewable energy and curtail the greenhouse effect. Therefore, various photocatalysts have been intensively studied for this purpose. Among them, g-C3N4, a 2D metal-free semiconductor, has been a promising photocatalyst because of its unique properties, such as high chemical stability, suitable electronic structure, and facile preparation. However, pristine g-C3N4 suffers from low solar energy conversion efficiency, owing to its small specific surface area and extensive charge recombination. Therefore, designing g-C3N4 (CN) nanosheets with a large specific surface area is an effective strategy for enhancing the CO2 reduction performance. Unfortunately, the performance of CN nanosheets remains moderate due to the aforementioned charge recombination. To counter this issue, loading a cocatalyst (especially a two-dimensional (2D) one) can enable effective electron migration and suppress electron-hole recombination during photo-irradiation. Herein, CN nanosheets with a large specific surface area (97 m2·g-1) were synthesized by a two-step calcination method, using urea as the precursor. Following this, a 2D/2D FeNi-LDH/g-C3N4 hybrid photocatalyst was obtained by loading a FeNi layered double hydroxide (FeNi-LDH) cocatalyst onto CN nanosheets by a simple hydrothermal method. It was found that the production rate of methanol from photocatalytic CO2 reduction over the FeNi-LDH/g-C3N4 composite is significantly higher than that of pristine CN. Following a series of characterization and analysis, it was demonstrated that the FeNi-LDH/g-C3N4 composite photocatalyst exhibited enhanced photo-absorption, which was ascribed to the excellent light absorption ability of FeNi-LDH. The CO2 adsorption capacity of the FeNi-LDH/g-C3N4 hybrid photocatalyst improved, owing to the large specific surface area and alkaline nature of FeNi-LDH. More importantly, the introduction of FeNi-LDH on the CN nanosheet surface led to the formation of a 2D/2D heterojunction with a large contact area at the interface, which could promote the interfacial separation of charge carriers and effectively inhibit the recombination of the photogenerated electrons and holes. This subsequently resulted in the enhancement of the CO2 photo-reduction activity. In addition, by altering the loading amount of FeNi-LDH for photocatalytic performance evaluation, it was found that the optimal loading amount was 4% (w, mass fraction), with a methanol production rate of 1.64 μmol·h-1·g-1 (approximately 6 times that of pure CN). This study provides an effective strategy to improve the photocatalytic CO2 reduction activity of g-C3N4 by employing 2D layered double hydroxide as the cocatalyst. It also proposes a protocol for the successful design of 2D/2D photocatalysts for solar energy conversion.   相似文献   

14.
Carbon materials have become one of the research hotspots in the field of catalysis as a typical representative of non-metallic catalytic materials. Herein, a facile synthetic strategy is developed to fabricate a series of hollow carbon nanoworms (h-NCNWs) that contain nitrogen up to 9.83 wt% by employing graphitic carbon nitride (g-C3N4) as the sacrificing template and solid nitrogen source. The h-NCNWs catalysts were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), N2 adsorption-desorption, Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric (TG), Raman spectra, and X-ray photoelectron spectroscopies (XPS). The catalytic activities of the h-NCNWs catalysts for selective oxidation of benzyl alcohol with O2 were also evaluated. The characterization results revealed that the h-NCNWs catalysts displayed a unique hollow worm-like nanostructure with turbostratic carbon shells. The nitrogen content and shell thickness can be tuned by varying the relative ratio of resorcinol to g-C3N4 during the preparation process. Furthermore, nitrogen is incorporated to the carbon network in the form of graphite (predominantly) and pyridine, which is critical for the enhancement of the catalytic activity of carbon catalysts for the selective oxidation of benzyl alcohol. At a reaction temperature of 120 ℃, a 24.9% conversion of benzyl alcohol with > 99% selectivity to benzaldehyde can be achieved on the h-NCNWs catalyst prepared with a mass ratio of resorcinol to g-C3N4 of 0.5. However, the catalytic activities of the h-NCNWs catalysts were dependent on the amount of N dopants, in particular graphitic nitrogen species. The conversion of benzyl alcohol markedly decreased to 13.1% on the h-NCNWs catalyst prepared with a mass ratio of resorcinol to g-C3N4 of 1.5. Moreover, the h-NCNWs catalyst showed excellent stability during the reaction process. The conversion of benzyl alcohol and the high selectivity to aldehyde can be kept within five catalytic runs over the h-NCNWs0.5 catalyst. These results indicate that rationally designed carbon materials have great potential as highly efficient heterogeneous catalysts for oxidation reactions.  相似文献   

15.
黄艳  傅敏  贺涛 《物理化学学报》2015,31(6):1145-1152
用简单的超声分散法合成了具有可见光响应的类石墨氮化碳(g-C3N4)/BiVO4复合光催化剂. 采用X射线衍射(XRD), X射线光电子能谱(XPS), 扫描电子显微镜(SEM), 透射电子显微镜(TEM), 紫外-可见(UV-Vis)分光光谱, 傅里叶红外变换(FTIR)光谱, 荧光发射谱(PL)和光电流响应等技术对所制备催化剂进行相关表征. 通过可见光下(λ> 420 nm)光催化还原CO2的性能来评价样品的光催化活性, 发现不同复合比的催化剂中, 含40% (w) g-C3N4的复合催化剂表现出最高的光催化活性, 其催化活性分别为纯g-C3N4纳米片和纯BiVO4的催化活性的2倍和4倍.光催化活性增加的主要原因是g-C3N4和BiVO4之间形成了异质结, 且相互间能级匹配, 有利于光生电子和空穴的分离.  相似文献   

16.
Photocatalytic reduction of CO2 to hydrocarbon compounds is a promising method for addressing energy shortages and environmental pollution. Considerable efforts have been devoted to exploring valid strategies to enhance photocatalytic efficiency. Among various modification methods, the hybridization of different photocatalysts is effective for addressing the shortcomings of a single photocatalyst and enhancing its CO2 reduction performance. In addition, metal-free materials such as g-C3N4 and black phosphorus (BP) are attractive because of their unique structures and electronic properties. Many experimental results have verified the superior photocatalytic activity of a BP/g-C3N4 composite. However, theoretical understanding of the intrinsic mechanism of the activity enhancement is still lacking. Herein, the geometric structures, optical absorption, electronic properties, and CO2 reduction reaction processes of 2D/2D BP/g-C3N4 composite models are investigated using density functional theory calculations. The composite model consists of a monolayer of BP and a tri-s-triazine-based monolayer of g-C3N4. Based on the calculated work function, it is inferred that electrons transfer from g-C3N4 to BP owing to the higher Fermi level of g-C3N4 compared with that of BP. Furthermore, the charge density difference suggests the formation of a built-in electric field at the interface, which is conducive to the separation of photogenerated electron-hole pairs. The optical absorption coefficient demonstrates that the light absorption of the composite is significantly higher than that of its single-component counterpart. Integrated analysis of the band edge potential and interfacial electronic interaction indicates that the migration of photogenerated charge carriers in the BP/g-C3N4 hybrid follows the S-scheme photocatalytic mechanism. Under visible-light irradiation, the photogenerated electrons on BP recombine with the photogenerated holes on g-C3N4, leaving photogenerated electrons and holes in the conduction band of g-C3N4 and the valence band of BP, respectively. Compared with pristine g-C3N4, this S-scheme heterojunction allows efficient separation of photogenerated charge carriers while effectively preserving strong redox abilities. Additionally, the possible reaction path for CO2 reduction on g-C3N4 and BP/g-C3N4 is discussed by computing the free energy of each step. It was found that CO2 reduction on the composite occurs most readily on the g-C3N4 side. The reaction path on the composite is different from that on g-C3N4. The heterojunction reduces the maximum energy barrier for CO2 reduction from 1.48 to 1.22 eV, following the optimal reaction path. Consequently, the BP/g-C3N4 heterojunction is theoretically proven to be an excellent CO2 reduction photocatalyst. This work is helpful for understanding the effect of BP modification on the photocatalytic activity of g-C3N4. It also provides a theoretical basis for the design of other high-performance CO2 reduction photocatalysts.   相似文献   

17.
采用水热法合成了NiWO_4纳米粒子,然后通过混合煅烧法成功地制备了负载型催化剂NiWO_4/g-C_3N_4。采用XRD、FT-IR、EDS、SEM、BET和XPS表征了NiWO_4/g-C_3N_4的形貌和结构特征。以NiWO_4/g-C_3N_4为催化剂,过氧化氢为氧化剂,1-丁基-3-甲基咪唑四氟硼酸盐离子液体([BMIM]BF4)为萃取剂。考察了催化剂的负载量,过氧化氢、离子液体和催化剂使用量,反应温度,反应时间,不同种类的含硫化合物对脱硫效果的影响。结果表明,在5 m L模拟油,0.2 m L过氧化氢,1.0 m L的[BMIM]BF4,0.03 g的NiWO_4/g-C_3N_4,反应温度为80℃,反应时间为140 min的最佳的反应条件下,脱硫率可以达到97.35%。实验表明,NiWO_4/g-C_3N_4具有很好的催化稳定性,催化剂重复使用五次后催化活性并没有明显地降低。  相似文献   

18.
以尿素和钨酸铵为原料采用浸渍法制备了金属氧化物三氧化钨(WO3)与石墨相氮化碳(g-C3N4)异质结复合材料WO3/g-C3N4。采用XRD、UV-vis、SEM、PL和XPS表征手段考察了催化剂的理化性质,发现WO3与g-C3N4存在较好的相互作用和电子转移,保证了WO3/g-C3N4本身所具有较高的氧化脱硫活性。以WO3/g-C3N4作为催化剂,过氧化氢异丙苯为氧化剂,考察其光催化氧化脱硫性能,在反应温度80℃,O/S物质的量比为3.0的反应条件下,反应180 min,二苯并噻吩(DBT)转化率可以达到72.79%。通过游离基捕获实验,发现超氧自由基(·O2-)、电子(e-)、羟基自由基(·OH)起到了促进反应速率的作用,并对该体系的反应机理进行了探讨。  相似文献   

19.
Although metal-organic frameworks(MOFs) have been widely reported as precursors for obtaining various porous materials in recent years, the limited MOF types and monofunctional active site of MOF-based catalysts remain to be hard to crack. Herein, bimetallic MOFs, MCo-ZIFs stabilized by graphitized carbon nitride(g-C3N4) and their pyrolytic MxCo3O4/g-C3N4 hybrids(M=Zn, Cu, Fe, Ni) have been designedly synthesized. The obtained MxCo3O4/g-C3N4 hybrids display synergistic photothermal effect from both MxCo3O4 and g-C3N4 under visible light irradiation. Significantly, the solution temperature can be heated from room temperature(20℃) to 66℃ after 40 min irradiation. Therefore, the catalytic activity of MxCo3O4/g-C3N4 exceeds those of most reported catalysts under mild reaction conditions. The optimal ZnxCo3O4/g-C3N4 catalyst realizes 96% conversion and 75% selectivity toward styrene oxide within 20 min. Incredibly, the CuxCo3O4/g-C3N4 could achieve up to 89% selectivity toward styrene oxide. To our knowledge, this is the first report about the novel photothermal effect of ZIFs-derived metal oxides.  相似文献   

20.
石墨相氮化碳(g-C3N4)是一种新型的无金属材料,因其具有众多特殊的理化性质,在多相催化、光催化、燃料电池和气体储存等领域显示出了潜在的应用前景。与直接热聚合法制得的块状g-C3N4相比,介孔g-C3N4拥有高比表面和丰富的介孔孔道,能暴露更多的表面活性位,继而提升其在催化反应等应用方面的性能。热聚合法是合成g-C3N4的最为便利的方法。其中,热聚合法合成介孔g-C3N4的工艺分为硬模板法、软模板法和无模板法。本文对近十年来国内外这三种合成工艺的研究进展进行了综述。特别是针对硬模板法,从前驱体合成机理、产品理化性质等多角度评述了硬模板法合成介孔g-C3N4的关键问题。此外,针对新型的软模板法和无模板法进行了介绍,并与硬模板法进行了细致的对比和讨论。最后,对介孔g-C3N4合成工艺的未来发展趋势进行了展望。  相似文献   

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