全文获取类型
收费全文 | 5426篇 |
免费 | 364篇 |
国内免费 | 166篇 |
专业分类
电工技术 | 6篇 |
综合类 | 168篇 |
化学工业 | 3471篇 |
金属工艺 | 131篇 |
机械仪表 | 52篇 |
建筑科学 | 5篇 |
矿业工程 | 22篇 |
能源动力 | 318篇 |
轻工业 | 103篇 |
水利工程 | 2篇 |
石油天然气 | 1382篇 |
武器工业 | 3篇 |
无线电 | 51篇 |
一般工业技术 | 165篇 |
冶金工业 | 50篇 |
原子能技术 | 9篇 |
自动化技术 | 18篇 |
出版年
2024年 | 11篇 |
2023年 | 77篇 |
2022年 | 157篇 |
2021年 | 199篇 |
2020年 | 134篇 |
2019年 | 171篇 |
2018年 | 135篇 |
2017年 | 147篇 |
2016年 | 176篇 |
2015年 | 168篇 |
2014年 | 266篇 |
2013年 | 247篇 |
2012年 | 313篇 |
2011年 | 343篇 |
2010年 | 260篇 |
2009年 | 273篇 |
2008年 | 261篇 |
2007年 | 298篇 |
2006年 | 261篇 |
2005年 | 288篇 |
2004年 | 237篇 |
2003年 | 215篇 |
2002年 | 206篇 |
2001年 | 147篇 |
2000年 | 158篇 |
1999年 | 124篇 |
1998年 | 115篇 |
1997年 | 82篇 |
1996年 | 65篇 |
1995年 | 70篇 |
1994年 | 82篇 |
1993年 | 54篇 |
1992年 | 45篇 |
1991年 | 39篇 |
1990年 | 23篇 |
1989年 | 9篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1986年 | 5篇 |
1985年 | 19篇 |
1984年 | 17篇 |
1983年 | 13篇 |
1982年 | 28篇 |
1978年 | 1篇 |
1974年 | 1篇 |
1951年 | 8篇 |
排序方式: 共有5956条查询结果,搜索用时 15 毫秒
1.
《International Journal of Hydrogen Energy》2022,47(6):3550-3555
Electrocatalytic nitrogen reduction reaction (ENRR) offers a carbon-neutral process to fix nitrogen into ammonia, but its feasibility depends on the development of highly efficient electrocatalysts. Herein, we report that Fe ion grafted on MoO3 nanorods synthesized by an impregnation technique can efficiently enhance the electron harvesting ability and the selectivity of H+ during the NRR process in neutral electrolyte. In 0.1 M Na2SO4 solution, the electrocatalyst exhibited a remarkable NRR activity with an NH3 yield of 9.66 μg h?1 mg?1cat and a Faradaic efficiency (FE) of 13.1%, far outperforming the ungrafted MnO3. Density functional theory calculations revealed that the Fe sites are major activation centers along the alternating pathway. 相似文献
2.
《International Journal of Hydrogen Energy》2022,47(64):27566-27578
Electrochemical hydrogenation is an environmentally favorable alternative to chemical reduction of indigo because it performs under ambient conditions using water as the donor of hydrogen. The purpose of this work is to fabricate electrocatalysts with high activity and durability for electrocatalytic hydrogenation of indigo. This work compares the performances of a series of Ni based catalysts (Ni, NiMo, NiP and NiMoP) on the substrate of carbon felt (CF) for electrolyzing water. Both the overpotential and Tafel slop are decreased as a function of the components as Ni > NiMo > NiP > NiMoP. Hence, NiMoP/CF shows the excellent performance based on the thermodynamics (η10 = 239 mV) and kinetics (Tafel slope = 89.7 mV·dec?1) for splitting water. Further, the electrode of NiMoP/CF was used for the electrocatalytic hydrogenation of indigo. The conversion efficiency and Faradic efficiency can be improved as 26.2% and 10.7% respectively. Furthermore, the dyeing behavior of the electrohydrogenated indigo is similar to that of conventional reduction methods. Thus, the present work offers foundational results and paves the way for the design of new catalytic materials for the reduction of vat dyes. 相似文献
3.
《International Journal of Hydrogen Energy》2022,47(4):2187-2199
A superhydrophilic Ru-based 3D electrode, denoted as Ru-PA/NF, was fabricated under the assistance of phytic acid (PA) for electrocatalytic hydrogenation of p-Nitrophenol. PA serves as a multifunctional modulator to facilitate the dispersion of active Ru species in porous nickel foam (NF), meanwhile enhance the surface wettability as well as adjust the micromorphology. In alkaline media, the Ru-PA/NF electrode shows the PNP conversion of 94.68% and the PAP selectivity of 99% after 9 h, accompanied by the faraday efficiency (FE) of 73.15%. Over the superhydrophilic Ru-PA/NF the rate constant of PNP conversion into PAP is 2.62-times higher than that over the hydrophobic Ru/NF prepared without the aid of PA, and FE of Ru-PA/NF is 1.28-times higher than Ru/NF. This can be ascribed to intriguing features of Ru-PA/NF involving higher Ru loading, more exposed sites, superior electrolyte wetting along with faster charge transfer rate. 相似文献
4.
Kalli Sai Bhavani Tummala Anusha Pradeep Kumar Brahman 《International Journal of Hydrogen Energy》2021,46(13):9199-9214
In the present study, we report an eco-friendly and simple route to design and synthesize novel nanocomposite catalyst based on platinum nanoparticles anchored on binary support of graphitic carbon nitride (g-C3N4) and cobalt-metal-organic framework (ZIF-67). For this purpose, ZIF-67 was prepared by precipitation method and g-C3N4 was prepared through thermal polymerization method. Later, ZIF-67 and g-C3N4 were hybridized through sonication to get homogeneous g–C3N4–ZIF-67 nanocomposite support material. Platinum nanoparticles (PtNPs) were uniformly deposited on g–C3N4–ZIF-67 by an electrochemical method. The as-developed nanocatalyst was characterized by morphological, structural and electrochemical techniques. The electrocatalytic activity of PtNPs@g–C3N4–ZIF-67 nanocatalyst towards butanol oxidation was evaluated via CV, CA, LSV and EIS in an alkaline medium. Results revealed that the proposed catalyst showed greatly enhanced electrooxidation of butanol in terms of high magnificent current density, lower oxidation potential, excellent long-term stability, large surface area, low charge transfer resistance and less toxic ability. Enhanced catalytic performance of the proposed catalyst could be ascribed to the synergistic effect of g–C3N4–ZIF-67 nanocomposite and PtNPs. The PtNPs@g–C3N4–ZIF-67 catalyst holds promising potential applications to be used as an anodic electrocatalyst for the development of high-performance alkaline fuel cells. 相似文献
5.
《International Journal of Hydrogen Energy》2021,46(58):30061-30078
A uniform solid product layer normally assumed in the shrinking-core model cannot predict the kinetic transition behavior of the H2 adsorption reactions. In this study, the concept of a uniform solid product layer has been replaced by that of the inward growth of solid products on the solid surface. A rate equation is established to calculate the inward growth of the solid product and was implemented into the shrinking-core model to calculate the H2 adsorption kinetics for various shapes of Mg-based materials. The prediction accuracy of the developed model is verified from the detailed experimental data. To account for the external gas diffusion around the particle and the intraparticle gas diffusion, an analytical equation is derived using the Thiele modulus method. This model can be used to analyze various kinetic aspects and to analyze the effect of change in the particle microstructure on intraparticle diffusion. 相似文献
6.
Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111)
Jian Wang Cun-Qin Lv Jian-Hong Liu Rong-Rong Ren Gui-Chang Wang 《International Journal of Hydrogen Energy》2021,46(2):1592-1604
It was well known that solvent effect plays a very important role in the catalytic reaction. There are many theoretical studies on the solvent effect in homogeneous catalysis while there are few theoretical studies on the solvent effect in the heterogeneous catalytic reaction and there has been no work to investigate the solvent effect on furfural transformation in heterogeneous catalysis. In the present work, both the density functional calculations and the microkinetic analysis were performed to study the selective hydrogenation of furfural over Pt(111) in the presence of methanol as well as toluene and compared with that in the gas condition. The present results indicated that the methanol can enhance the adsorption strength of furfural and other oxygen-containing reaction species due to its relatively strong polarity properties and this can be a main reason for solvent-induced high activity and selectivity. Another reason is that reaction paths study showed that the presence of methanol solvent makes the dehydrogenation of furfural less thermochemical due to the fact that furfural is more stabilized than that of dehydrogenation species, and methanol also has an inhibition effect on the dehydrogenation of furfural in the kinetic aspect, and further energetic span theory proves highest activity and selectivity for hydrogenation in methanol solvent of vapor, methanol and toluene. Moreover, microkinetic model simulation demonstrated that the activity and selectivity of hydrogenation in methanol is both higher than that in vapor and toluene. The much higher activity in methanol is due to the stabilized adsorbed reactants in the surface, which leads to a higher surface coverage of furfural. It might be proposed based on the present work that a solvent with relatively strong polarity may be favorable for the high selective hydrogenation of furfural. 相似文献
7.
Huimin Zhao Wensi Wang Yunmei Du Yu Yang Minghui Wang Shaoxiang Li Ruixin Chen Yanru Liu Lei Wang 《International Journal of Hydrogen Energy》2021,46(18):10763-10772
In this work, we synthesized Se doped MoS2@Ni3S2 with nanosheets coated nanorods structure supported on Ni foam (MoNiSeS). Firstly, MoS2@Ni3S2 (MoNiS) nanorods was synthesized by hydrothermal method. After selenization treatment, MoSe2 successfully formed on the edge of MoS2 nanosheets and particle Ni3S2 transformed into NiSe, in which MoSe2 and NiSe acted as new phase in MoNiSeS. The obtained MoNiSeS only needs a low overpotential of 68 mV to reach the current density of 10 mA cm?2, and has a low Tafel plots of 72.77 mV dec?1 and good electrochemical durability, whose electrochemical activity is much better than that of MoNiS and NiSeS, implying the introduction of Mo and Se is beneficial to improve the electrocatalytic performance of NiS for HER. In addition, the proper amount of Mo source, which has an effect on the morphology of product, has also been investigated. For MoNiSeS, the typical nanosheets coated nanarods expose more active sites and the synergic effects is good to the improvement of the catalytic activity. Meanwhile, WNiSeS has also been prepared using the same method and the corresponding results show that the electrochemical activity of WNiSeS is much better than that of NiSeS, proving the universality of this strategy. 相似文献
8.
9.
Timothy Zurrer Kenneth Wong Jonathan Horlyck Emma C. Lovell Joshua Wright Nicholas M. Bedford Zhaojun Han Kang Liang Jason Scott Rose Amal 《Advanced functional materials》2021,31(9):2007624
The vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle-encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed-metal MOF, NiMg-MOF-74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in Ni O and Mg O coordination bond strength, Ni2+ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg2+ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO2 adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO2 methanation and are examined using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy. By preserving a segment of the Mg2+-containing MOF framework, the composite system retains a portion of its CO2 adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO2 utilization. 相似文献
10.
以废弃的流化催化裂化催化剂(简称SFCC)为载体、β-环糊精为金属络合剂、硝酸镍为镍源,采用湿法浸渍法制备β-环糊精修饰的Ni/SFCC催化剂(简称Ni/SFCC-CD催化剂),考察其对C9石油树脂的催化加氢性能。通过BET比表面积测试、H2程序升温还原、X射线光电子能谱等手段对催化剂的物相结构进行表征,研究β-环糊精的作用机理及其对催化剂加氢性能的影响。研究结果表明:在反应温度为260 ℃、反应压力为7 MPa、反应时间为2.0 h的最优条件下,采用Ni/SFCC-CD催化C9石油树脂加氢,可制得溴值为1.45 gBr/(100 g)、色号(加纳德)小于1的水白色氢化C9石油树脂,催化剂循环使用4次后仍保持良好活性;β-环糊精的作用机理是:β-环糊精与硝酸镍产生络合作用,抑制硝酸镍的分解、控制NiO的结晶过程和增强活性组分Ni与载体之间的相互作用力,从而提高了Ni/SFCC-CD的催化活性和稳定性。 相似文献