Electrocatalysis is a process dealing with electrochemical reactions in the interconversion of chemical energy and electrical energy.Precise synthesis of catalytically active nanostructures is one of the key challenge...Electrocatalysis is a process dealing with electrochemical reactions in the interconversion of chemical energy and electrical energy.Precise synthesis of catalytically active nanostructures is one of the key challenges that hinder the practical application of many important energy‐related electrocatalytic reactions.Compared with conventional wet‐chemical,solid‐state and vapor deposition synthesis,electrochemical synthesis is a simple,fast,cost‐effective and precisely controllable method for the preparation of highly efficient catalytic materials.In this review,we summarize recent progress in the electrochemical synthesis of catalytic materials such as single atoms,spherical and shaped nanoparticles,nanosheets,nanowires,core‐shell nanostructures,layered nanomaterials,dendritic nanostructures,hierarchically porous nanostructures as well as composite nanostructures.Fundamental aspects of electrochemical synthesis and several main electrochemical synthesis methods are discussed.Structure‐performance correlations between electrochemically synthesized catalysts and their unique electrocatalytic properties are exemplified using selected examples.We offer the reader with a basic guide to the synthesis of highly efficient catalysts using electrochemical methods,and we propose some research challenges and future opportunities in this field.展开更多
The fabrication of a pyrocarbon coated carbon paper and its application to the gas diffusion lay(GDL) of proton exchange membrane(PEM) fuel cell were described.This carbon paper was fabricated by using conventional ca...The fabrication of a pyrocarbon coated carbon paper and its application to the gas diffusion lay(GDL) of proton exchange membrane(PEM) fuel cell were described.This carbon paper was fabricated by using conventional carbon paper as the precursor,and coating it with pyrocarbon by pyrolyzing propylene via the chemical vapor deposition(CVD) method.For comparison,conventional carbon paper composites were also prepared by using PAN-based carbon fiber felt as the precursor followed by impregnation with resin,molding and heat-treatment.SEM characterization indicates that pyrocarbon is uniformly deposited on the surface of the fiber in the pyrocarbon coated carbon paper and made the fibers of carbon felt bind more tightly.In contrast,there are cracks in matrix and debonding of fibers due to carbonization shrinkage in the conventional carbon paper.Property measurements show that the former has much better conductivity and gas permeability than the latter.In addition,current density-voltage performance tests also reveal that the pyrocarbon coating can improve the properties of carbon paper used for electrode materials of fuel cell.展开更多
n-Si,believed as a promising photoanode candidate,has suffered from sluggish oxygen evolution reaction(OER)kinetics and poor chemical stability when exposed to aqueous electrolyte.Herein,CoO_(x)/Ni:CoOOH bilayers were...n-Si,believed as a promising photoanode candidate,has suffered from sluggish oxygen evolution reaction(OER)kinetics and poor chemical stability when exposed to aqueous electrolyte.Herein,CoO_(x)/Ni:CoOOH bilayers were successfully deposited on n-Si substrate by atomic layer-deposition(ALD)and photoassisted electrochemical deposition(PED)for stabilizing and catalyzing photoelectrochemical(PEC)water oxidation.In comparison to the n-Si/CoO_(x)photoanode as reference,the prepared n-Si/CoO_(x)/Ni:CoOOH photoanode upon the optimized PED process presents a much improved PEC performance for water splitting,with the onset potential cathodically shifted to~1.03 V vs.reversible hydrogen electrode(RHE)and the photocurrent density much increased to 20 mA cm^(−2)at 1.23 V vs.RHE.It is revealed that the introduction of Ni dopants increases the work functions of the deposited Ni:CoOOH overlayers,which gives rise to the upward band bending weakened at the n-Si/CoO_(x)/Ni:CoOOH cascading interface while strengthened at the Ni:CoOOH/electrolyte interface(with the band bending shifted from downward to upward),contributing to the decreased and the increased driving forces for charge transfer at the interfaces,respectively.Then,the balanced driving forces at the interfaces would endow the n-Si/CoO_(x)/Ni:CoOOH photoanode with the best PEC performance.Moreover,PED has been evidenced superior to ED to dope Ni into CoOOH with the formed overlayer effectively catalyzing and stabilizing PEC water splitting.展开更多
Palladium(II) and chloride ions tend to form complexes in aqueous solution. Both theoretical and experimental (by UV spec- trum) results indicate that there are four complexes formed in aqueous solution containing...Palladium(II) and chloride ions tend to form complexes in aqueous solution. Both theoretical and experimental (by UV spec- trum) results indicate that there are four complexes formed in aqueous solution containing 3 mol/L hydrochloric acid and 20 mmol/L PdC12. This work evaluates the kinetics of electrochemical deposition of palladium on a Platinum electrode. For this purpose, palladium electrodeposition was investigated by means of cyclic voltammetry (CV), potentiostatic current-time tran- sients (CTTs) and Tafel curve. By CTTs curves, the regions corresponding to the charge transfer control, mixed control and diffusion control were identified. In the diffusion control region, palladium electrodeposition mechanism was characterized as progressive nucleation with three-dimensional (3D) growth under diffusion control; as for the mixed control region, an adsorp- tion (1Ads), ion transfer (liT), and nucleation and growth (ING) model were proposed to analyze the current-time transients quan- titatively, which could separate the IAds, lit and IN~ perfectly.展开更多
The two-dimensional atomically thin insulator hexagonal boron nitride (h-BN) constitutes a new paradigm in tunnel based devices. A large band gap, along with its atomically flat nature without dangling bonds or inte...The two-dimensional atomically thin insulator hexagonal boron nitride (h-BN) constitutes a new paradigm in tunnel based devices. A large band gap, along with its atomically flat nature without dangling bonds or interface trap states, makes it an ideal candidate for tunnel spin transport in spintronic devices. Here, we demonstrate the tunneling of spin-polarized electrons through large area monolayer h-BN prepared by chemical vapor deposition in magnetic tunnel junctions. In ferromagnet/h-BN/ferromagnet heterostructures fabricated on a chip scale, we show tunnel magnetoresistance at room temperature. Measurements at different bias voltages and on multiple devices with different ferromagnetic electrodes establish the spin polarized tunneling using h-BN barriers. These results open the way for integration of 2D monolayer insulating barriers in active spintronic devices and circuits operating at ambient temperature, and for further exploration of their properties and prospects.展开更多
When spins are injected through graphene layers from a transition metal ferromagnet, high spin polarization can be achieved. When detected by another ferromagnet, the spin-polarized current makes high- and low-resista...When spins are injected through graphene layers from a transition metal ferromagnet, high spin polarization can be achieved. When detected by another ferromagnet, the spin-polarized current makes high- and low-resistance states in a ferromagnet/graphene/ferromagnet junction. Here, we report manifest spin valve effects from room temperature to 10 K in junctions comprising NiFe electrodes and an interlayer made of double-layer or single-layer graphene grown by chemical vapor deposition. We have found that the spin valve effect is stronger with double-layer graphene than with single-layer graphene. The ratio of relative magnetoresistance increases from 0.09% at room temperature to 0.14% at 10 K for single-layer graphene and from 0.27% at room temperature to 0.48% at 10 K for double-layer graphene. The spin valve effect is perceived to retain the spin-polarized transport in the vertical direction and the hysteretic nature of magnetoresistance provides the basic functionality of a memory device. We have also found that the junction resistance decreases monotonically as temperature is lowered and the current-voltage characteristics show linear behaviour. These results revealed that a graphene interlayer works not as a tunnel barrier but rather as a conducting thin film between two NiFe electrodes.展开更多
Realizing low contact resistance between graphene and metal electrodes remains a well-known challenge for building high-performance graphene devices. In this work, we attempt to reduce the contact resistance in graphe...Realizing low contact resistance between graphene and metal electrodes remains a well-known challenge for building high-performance graphene devices. In this work, we attempt to reduce the contact resistance in graphene transistors and further explore the resistance limit between graphene and metal contacts. The Pd/graphene contact resistance at room temperature is reduced below the 100 Ω·μm level both on mechanically exfoliated and chemical-vapor-deposition graphene by adopting high-purity palladium and high-quality graphene and controlling the fabrication process to not contaminate the interface. After excluding the parasitic series resistances from the measurement system and electrodes, the retrieved contact resistance is shown to be systematically and statistically less than 100 Ω·μm, with a minimum value of 69 Ω·μm, which is very close to the theoretical limit. Furthermore, the contact resistance shows no clear dependence on temperature in the range of 77-300 K; this is attributed to the saturation of carrier injection efficiency between graphene and Pd owing to the high quality of the graphene samples used, which have a sufficiently long carrier mean-free-path.展开更多
Catalyst-free and scalable synthesis of graphene on various glass substrates at low temperatures is of paramount significance to numerous applications such as low-cost transparent electronics and state-of-the-art disp...Catalyst-free and scalable synthesis of graphene on various glass substrates at low temperatures is of paramount significance to numerous applications such as low-cost transparent electronics and state-of-the-art displays. However, systematic study within this promising research field has remained scarce thus far. Herein, we report the direct growth of graphene on various glasses using a low-temperature plasma-enhanced chemical vapor deposition method. Such a facile and scalable approach guarantees the growth of uniform, transfer-free graphene films on various glass substrates at a growth temperature range of 400-600 ℃. The morphological, surface wetting, optical, and electrical properties of the obtained graphene can be tailored by controlling the growth parameters. Our uniform and high-quality graphene films directly integrated with low-cost, commonly used glasses show great potential in the fabrication of multi-functional electrodes for versatile applications in solar cells, transparent electronics, and smart windows.展开更多
Field-effect transistors (FETs) have been fabricated using as-grown single-walled carbon nanotubes (SWNTs) for the channel as well as both source and drain electrodes. The underlying Si substrate was employed as t...Field-effect transistors (FETs) have been fabricated using as-grown single-walled carbon nanotubes (SWNTs) for the channel as well as both source and drain electrodes. The underlying Si substrate was employed as the back-gate electrode. Fabrication consisted of patterned catalyst deposition by surface modification followed by dip-coating and synthesis of SWNTs by alcohol chemical vapor deposition (CVD). The electrodes and channel were grown simultaneously in one CVD process. The resulting FETs exhibited excellent performance, with an I ON/I OFF ratio of 10^6 and a maximum ON-state current (/ON) exceeding 13 uA. The large I ON is attributed to SWNT bundles connecting the SWNT channel with the SWNT electrodes. Bundling creates a large contact area, which results in a small contact resistance despite the presence of Schottky barriers at metallic-semiconducting interfaces. The approach described here demonstrates a significant step toward the realization of metal-free electronics.展开更多
文摘Electrocatalysis is a process dealing with electrochemical reactions in the interconversion of chemical energy and electrical energy.Precise synthesis of catalytically active nanostructures is one of the key challenges that hinder the practical application of many important energy‐related electrocatalytic reactions.Compared with conventional wet‐chemical,solid‐state and vapor deposition synthesis,electrochemical synthesis is a simple,fast,cost‐effective and precisely controllable method for the preparation of highly efficient catalytic materials.In this review,we summarize recent progress in the electrochemical synthesis of catalytic materials such as single atoms,spherical and shaped nanoparticles,nanosheets,nanowires,core‐shell nanostructures,layered nanomaterials,dendritic nanostructures,hierarchically porous nanostructures as well as composite nanostructures.Fundamental aspects of electrochemical synthesis and several main electrochemical synthesis methods are discussed.Structure‐performance correlations between electrochemically synthesized catalysts and their unique electrocatalytic properties are exemplified using selected examples.We offer the reader with a basic guide to the synthesis of highly efficient catalysts using electrochemical methods,and we propose some research challenges and future opportunities in this field.
基金Project(50772134) supported by the National Natural Science Foundation of ChinaProject(2006CB600901) supported by the National Basic Research Program of China
文摘The fabrication of a pyrocarbon coated carbon paper and its application to the gas diffusion lay(GDL) of proton exchange membrane(PEM) fuel cell were described.This carbon paper was fabricated by using conventional carbon paper as the precursor,and coating it with pyrocarbon by pyrolyzing propylene via the chemical vapor deposition(CVD) method.For comparison,conventional carbon paper composites were also prepared by using PAN-based carbon fiber felt as the precursor followed by impregnation with resin,molding and heat-treatment.SEM characterization indicates that pyrocarbon is uniformly deposited on the surface of the fiber in the pyrocarbon coated carbon paper and made the fibers of carbon felt bind more tightly.In contrast,there are cracks in matrix and debonding of fibers due to carbonization shrinkage in the conventional carbon paper.Property measurements show that the former has much better conductivity and gas permeability than the latter.In addition,current density-voltage performance tests also reveal that the pyrocarbon coating can improve the properties of carbon paper used for electrode materials of fuel cell.
基金supported by the National Key Research and Development Program of China (2018YFB1502003)the National Natural Science Foundation of China (21875183)+3 种基金the Natural Science Basic Research Program of Shaanxi Province (2019JCW-10)the National Program for the Support of Top-notch Young Professionalsthe Fundamental Research Funds for the Central UniversitiesThe Youth Innovation Team of Shaanxi Universities
文摘n-Si,believed as a promising photoanode candidate,has suffered from sluggish oxygen evolution reaction(OER)kinetics and poor chemical stability when exposed to aqueous electrolyte.Herein,CoO_(x)/Ni:CoOOH bilayers were successfully deposited on n-Si substrate by atomic layer-deposition(ALD)and photoassisted electrochemical deposition(PED)for stabilizing and catalyzing photoelectrochemical(PEC)water oxidation.In comparison to the n-Si/CoO_(x)photoanode as reference,the prepared n-Si/CoO_(x)/Ni:CoOOH photoanode upon the optimized PED process presents a much improved PEC performance for water splitting,with the onset potential cathodically shifted to~1.03 V vs.reversible hydrogen electrode(RHE)and the photocurrent density much increased to 20 mA cm^(−2)at 1.23 V vs.RHE.It is revealed that the introduction of Ni dopants increases the work functions of the deposited Ni:CoOOH overlayers,which gives rise to the upward band bending weakened at the n-Si/CoO_(x)/Ni:CoOOH cascading interface while strengthened at the Ni:CoOOH/electrolyte interface(with the band bending shifted from downward to upward),contributing to the decreased and the increased driving forces for charge transfer at the interfaces,respectively.Then,the balanced driving forces at the interfaces would endow the n-Si/CoO_(x)/Ni:CoOOH photoanode with the best PEC performance.Moreover,PED has been evidenced superior to ED to dope Ni into CoOOH with the formed overlayer effectively catalyzing and stabilizing PEC water splitting.
基金supported by the National Natural Science Foundation of China(91026019,91126006)
文摘Palladium(II) and chloride ions tend to form complexes in aqueous solution. Both theoretical and experimental (by UV spec- trum) results indicate that there are four complexes formed in aqueous solution containing 3 mol/L hydrochloric acid and 20 mmol/L PdC12. This work evaluates the kinetics of electrochemical deposition of palladium on a Platinum electrode. For this purpose, palladium electrodeposition was investigated by means of cyclic voltammetry (CV), potentiostatic current-time tran- sients (CTTs) and Tafel curve. By CTTs curves, the regions corresponding to the charge transfer control, mixed control and diffusion control were identified. In the diffusion control region, palladium electrodeposition mechanism was characterized as progressive nucleation with three-dimensional (3D) growth under diffusion control; as for the mixed control region, an adsorp- tion (1Ads), ion transfer (liT), and nucleation and growth (ING) model were proposed to analyze the current-time transients quan- titatively, which could separate the IAds, lit and IN~ perfectly.
文摘The two-dimensional atomically thin insulator hexagonal boron nitride (h-BN) constitutes a new paradigm in tunnel based devices. A large band gap, along with its atomically flat nature without dangling bonds or interface trap states, makes it an ideal candidate for tunnel spin transport in spintronic devices. Here, we demonstrate the tunneling of spin-polarized electrons through large area monolayer h-BN prepared by chemical vapor deposition in magnetic tunnel junctions. In ferromagnet/h-BN/ferromagnet heterostructures fabricated on a chip scale, we show tunnel magnetoresistance at room temperature. Measurements at different bias voltages and on multiple devices with different ferromagnetic electrodes establish the spin polarized tunneling using h-BN barriers. These results open the way for integration of 2D monolayer insulating barriers in active spintronic devices and circuits operating at ambient temperature, and for further exploration of their properties and prospects.
文摘When spins are injected through graphene layers from a transition metal ferromagnet, high spin polarization can be achieved. When detected by another ferromagnet, the spin-polarized current makes high- and low-resistance states in a ferromagnet/graphene/ferromagnet junction. Here, we report manifest spin valve effects from room temperature to 10 K in junctions comprising NiFe electrodes and an interlayer made of double-layer or single-layer graphene grown by chemical vapor deposition. We have found that the spin valve effect is stronger with double-layer graphene than with single-layer graphene. The ratio of relative magnetoresistance increases from 0.09% at room temperature to 0.14% at 10 K for single-layer graphene and from 0.27% at room temperature to 0.48% at 10 K for double-layer graphene. The spin valve effect is perceived to retain the spin-polarized transport in the vertical direction and the hysteretic nature of magnetoresistance provides the basic functionality of a memory device. We have also found that the junction resistance decreases monotonically as temperature is lowered and the current-voltage characteristics show linear behaviour. These results revealed that a graphene interlayer works not as a tunnel barrier but rather as a conducting thin film between two NiFe electrodes.
基金This work was supported by the Ministry of Sdence and Technology of China (Grant Nos. 2011CB933001 and 2011CB933002), National Natural Science Foundation of China (Grant Nos. 61322105, 61271051, 61321001, and 61390504), and Beijing Municipal Science and Technology Commission (Grant Nos. Z131100003213021 and D141100000614001).
文摘Realizing low contact resistance between graphene and metal electrodes remains a well-known challenge for building high-performance graphene devices. In this work, we attempt to reduce the contact resistance in graphene transistors and further explore the resistance limit between graphene and metal contacts. The Pd/graphene contact resistance at room temperature is reduced below the 100 Ω·μm level both on mechanically exfoliated and chemical-vapor-deposition graphene by adopting high-purity palladium and high-quality graphene and controlling the fabrication process to not contaminate the interface. After excluding the parasitic series resistances from the measurement system and electrodes, the retrieved contact resistance is shown to be systematically and statistically less than 100 Ω·μm, with a minimum value of 69 Ω·μm, which is very close to the theoretical limit. Furthermore, the contact resistance shows no clear dependence on temperature in the range of 77-300 K; this is attributed to the saturation of carrier injection efficiency between graphene and Pd owing to the high quality of the graphene samples used, which have a sufficiently long carrier mean-free-path.
基金Acknowledgements This work was financially supported by the National Basic Research Program of China (Nos. 2013CB932603, 2012CB933404, 2011CB921903, and 2013CB934600), the National Natural Science Foundation of China (Nos. 51432002, 51290272, 51121091, 51~201, and 11222434), the Ministry of Education (No. 20120001130010) and the Beijing Municipal Sdence and Technology Planning Project (No. Z151100003315013).
文摘Catalyst-free and scalable synthesis of graphene on various glass substrates at low temperatures is of paramount significance to numerous applications such as low-cost transparent electronics and state-of-the-art displays. However, systematic study within this promising research field has remained scarce thus far. Herein, we report the direct growth of graphene on various glasses using a low-temperature plasma-enhanced chemical vapor deposition method. Such a facile and scalable approach guarantees the growth of uniform, transfer-free graphene films on various glass substrates at a growth temperature range of 400-600 ℃. The morphological, surface wetting, optical, and electrical properties of the obtained graphene can be tailored by controlling the growth parameters. Our uniform and high-quality graphene films directly integrated with low-cost, commonly used glasses show great potential in the fabrication of multi-functional electrodes for versatile applications in solar cells, transparent electronics, and smart windows.
文摘Field-effect transistors (FETs) have been fabricated using as-grown single-walled carbon nanotubes (SWNTs) for the channel as well as both source and drain electrodes. The underlying Si substrate was employed as the back-gate electrode. Fabrication consisted of patterned catalyst deposition by surface modification followed by dip-coating and synthesis of SWNTs by alcohol chemical vapor deposition (CVD). The electrodes and channel were grown simultaneously in one CVD process. The resulting FETs exhibited excellent performance, with an I ON/I OFF ratio of 10^6 and a maximum ON-state current (/ON) exceeding 13 uA. The large I ON is attributed to SWNT bundles connecting the SWNT channel with the SWNT electrodes. Bundling creates a large contact area, which results in a small contact resistance despite the presence of Schottky barriers at metallic-semiconducting interfaces. The approach described here demonstrates a significant step toward the realization of metal-free electronics.