ACS Nano
·
2025
·
IF 16
Yaxi Gan,Ataollah Kalantari Osgouei,Alexander Ahrens,Bofang Wang,Jingyi Zhou,Jun-Zheng Zhan,Dan Zeng,Shengqiang Nie,Xinyuan Zhao,Guangxu Chen,Peter Nordlander,Linan Zhou
Plasmonic photocatalysis is promising for solar-driven chemical transformations under mild conditions; however, conventional materials like aluminum, copper, silver, and gold are resonant at short wavelengths, limiting their use in the red to near-infrared sunlight spectrum. In this study, we have developed a class of antenna-reactor (AR) photocatalyst based on two-dimensional (2D) plasmonic materials, Ti3C2Tx, also known as MXenes. A Ru-loaded Ti3C2Tx plasmonic photocatalyst achieves a turnover frequency of approximately 2 s–1 and energy efficiency of 10% for hydrogen production under 660 nm light excitation, being 2–3 orders of magnitude superior to the performance achieved in thermocatalysis. This 2D plasmonic antenna demonstrates superiority over the benchmark CuRu surface-alloy AR structure in hot-electron-driven processes under red light excitation. Kinetic studies suggest that the rate-determining step in both photo- and thermocatalysis is nitrogen’s associative desorption. Hot electrons enhance activity by promoting the removal of adsorbed nitrogenous species.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
IEEE TRANSACTIONS ON ELECTRON DEVICES
·
2024
·
IF 2.9
Chenning Wang,Xiaoyu Zhou,Tianqi Jiang,Zhenrui Xu,Esmond A. Balfour,Hao Fu
The high content of Ba and Sc in Ba
$_{\text{3}}$
ScGa
$_{\text{2}}$
O
$_{\text{7.5}}$
and its suitable melting point suggest that it is a candidate for thermionic emission in vacuum electron devices. To study its electron emission capacity, this compound was synthesized at 1300
$^{\circ}$
C by a high-temperature solid-phase method with the stoichiometric mole ratio of BaCO
$_{\text{3}}$
:Sc
$_{\text{2}}$
O
$_{\text{3}}$
:Ga
$_{\text{2}}$
O
$_{\text{3}}$
$=$
6:1:2. The test cathode impregnated with this material had a high emission capacity with the full-space charge current density of 10.2 A/cm
$^{\text{2}}$
at 850
$^{\circ}$
C in the dc mode. The sintered mixture of the compound and tungsten powder reveals that the formation of Ba
$_{\text{3}}$
Sc
$_{\text{2}}$
WO
$_{\text{9}}$
on the cathode surface leads to reduced work function and thus enhanced emission performance. The titled compound is environmentally stable with a low weight gain percentage (4.51%) and a steady phase in the air for 288 h. Coupled with the high emission current density at low temperatures, the cathode impregnated with Ba
$_{\text{3}}$
ScGa
$_{\text{2}}$
O
$_{\text{7.5}}$
compound has superior thermionic cathode properties and promising applications in vacuum electron devices.
研究领域:
材料科学
·
真空电子学
✓ 已验证
产品关联
DOI
高影响因子
Nano Energy
·
2019
·
IF 15.548
Bang Lin Li,Hao Lin Zou,Jie Kang Tian,Guo Chen,Xiao Hu Wang,Huan Duan,Xiao Lin Li,Yan Shi,Jing Rong Chen,Ling Jie Li,Jing Lei Lei,Hong Qun Luo,Nian Bing Li
Defects in layered semiconductors cause large variation of electric and catalysis properties, and exploiting defect-involved reaction can deeply excavate unearthed characteristics with significant performances. Mo-terminated defects of MoS 2 spontaneously guide the oriented growths of ultrasmall Au nanocrystals on specific sites of liquid-exfoliated (LE) nanosheets , which are experimentally and theoretically performed with programmable heterostructures . The conjugated construction of Au plasmonics and MoS 2 semiconductors is manipulated with the aim of the optimal synergistic activity. Additionally, with photonic irradiation, hot electrons excited from attached plasmonic nanostructures are injected into MoS 2 semiconductors, which remarkably increases the carrier density of catalyst to match the energy level of hydrogen evolution reaction (HER). Obeying the principle of proximity, localized MoS 2 defect-adjacent Au plasmonics exhibit a more valid pathway, transferring hot electrons from donators to receptors of catalytic sites, in comparison to planar Au decoration. Meanwhile, Au nanostructures located at basal planes are essential for accelerated electron transport rates between catalysts and electrodes, and high stabilities in plasmonic-motivated electrocatalytic performances are guaranteed. The dual function of location-discriminated Au nanostructures accounts for superior electrocatalytic HER performances with photonic excitation, which imparts high inspiration in expanded heterostructures and integrated plasmonic techniques for catalysis and devices.
研究领域:
材料科学
·
纳米技术
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Physical Chemistry C
·
2023
·
IF 3.7
Ting Qu,Xue Hu,Ying Ou,Jie Wang,Fuqiang Hu,Jing Ni,Fan Cheng,Chunli Gong,Hai Liu
Robust metallic doped semiconducting networks of precise organization, over large scales and small dimensionality, hold great application potential in the basis of photocatalytic materials. Herein, a facile method to fabricate robust Au@TiO2 hierarchical nanoporous network films is reported, which is templated by thermally stable poly(4-vinylpyridine)-block-poly{11-[4-(4-butylphenylazo)phenoxy]undecyl methacrylate} (P4VP-b-PMA(11C)Az) liquid crystalline (LC) block copolymers (BCPs). A P4VP100-b-PMA(11C)Az15 thin film can self-assemble to form ∼50 nm orderly packed PMA(11C)Az periodic spheres in the P4VP matrix via a solvent-annealing process. When these spherical P4VP100-b-PMA(11C)Az15 films with different thicknesses were exposed to the sol–gel titania precursors alcohol solutions with titanium(IV) isopropoxide (TIPT) and titanium tetrachloride (TiCl4; mass ratio, 3:1), titania was well-formed in the P4VP phase during the calcination process. After a further deposition–precipitation (DP) process, ∼10 nm Au nanoparticles were homogeneously doped in robust TiO2 nanoporous network films. The photocatalytic performance of the obtained robust Au@TiO2 films was studied in detail. It displays significantly enhanced visible light photocatalytic activity. The enhancement mechanism was ascribed to the injection of hot electrons of photoexcited Au nanoparticles to robust porous TiO2 films, which was confirmed by 420 nm Xe laser-induced fast photodegradation of rhodamine B.
研究领域:
材料科学
·
化学工程
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2017
·
IF 9.446
Qingqing Lang,Yaohan Chen,Tianlong Huang,Lining Yang,Shuxian Zhong,Lanju Wu,Jianrong Chen,Song Bai
The integration of plasmonic metal with wide-bandgap semiconductor is a promising approach to utilize the visible light without compromise of the redox ability of photogenerated charge carriers. However, a larger work function of metal than that of semiconductor is indispensable to enable the injection of hot electrons from plasmonic metal to semiconductor. In this paper, we demonstrated that reduced graphene oxide (rGO) nanosheets as conductive “bridge” can breakthrough the restriction and transfer hot electrons from Ag of smaller work function to TiO 2 of larger work function. In the design, both of the Ag nanocubes and TiO 2 nanosheets are co-deposited on the surface of rGO nanosheets to form Ag-rGO-TiO 2 structure, which was characterized by XRD, TEM, Raman and XPS spectra. On one hand, the Ag-rGO interface facilitates the transfer of hot electrons from Ag to rGO through conductor–conductor contact. On the other hand, the new formed Schottky junction on the rGO-TiO 2 interface further pumps the transferred electrons to the surface of TiO 2 for photocatalytic reduction reaction resulted from the larger work function of rGO than that of TiO 2 . Enabled by this unique design, the hydrogen production activity achieved under visible light irradiation is dramatically enhanced in comparison with that of Ag-TiO 2 counterpart with the direct contact between the same Ag nanocubes and TiO 2 nanosheets. This work represents a step toward the rational interfacial design of plasmonic metal-semiconductor hybrid structures for broad-spectrum photocatalysis.
研究领域:
材料科学
·
光化学
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2021
·
IF 5.316
Xi Wang,Kaili Yao,Lihua Liu,Changxu Liu,Hongyan Liang
Constructing plasmonic-semiconductor nanoarchitecture provides a photocatalytic platform for enhancing solar energy conversion. The excitation and extraction of energetic carriers are critical for improving energy efficiency, which can be affected by the geometric features of plasmonic structures. An extensive study on morphology dependent hot electron utilization is desirable but challenging. In this paper, we applied photocurrent response from the microscale reaction region on Au-TiO 2 photoanode to evaluate the influence of plasmonic morphology in water splitting. We compared the photocurrent of two structures, gold nanospheres and nanorods , under visible illumination. We experimentally proved that the nanorods demonstrate better energy performance. The possible origins of this enhancement are ascribed to the sharp curvature at tips, where strong hot spots boost the generation and injection efficiency of hot electrons. These results may pave a way for a rational geometry design for plasmonic enhanced photocatalysis .
研究领域:
材料科学
·
光催化
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Xiangyang Ji,Xiao Sun,Shaojia Song,Kun Yang,Yumeng Fo,Luyuan Yang,Xinxin Zhang,Hongyin Chen,Weixin Huang,Chunming Xu,Jian Liu,Weiyu Song
Balancing kinetics behavior is a significant priority in chemical reactions especially involving two or more elementary steps. Propane dehydrogenation (PDH), usually involves a slower 2nd C-H activation step at a low temperature, resulting in heat waste for overcoming a higher energy barrier of the 2nd dehydrogenation. Herein, we develop one Photo-assisted Thermal PDH process (PTPDH) based on PtZn clusters encapsulated in porous MFI zeolite, which effectively balances the kinetic elementary steps via exciting the ground state electrons of the active sites to the positively charged -C 3 H 7 fragments, achieving a 23.4 % growth ratio (from 39.6 to 51.3 · 10 −8 mol·g −1 ·s −1 ) with the assistance of ∼5 suns light intensity at 400 °C. The comparison between the temperature-dependent and light intensity-dependent kinetic parameters confirmed that the non-thermal effect instead of the photo-to-thermal effect dominates the PTPDH process. Furthermore, the Lewis acidity-activity correlation experiments, in-situ radiation mass spectrometry and the H 2 co-feeds experiment indicate that the hot electrons instead of the holes play a more significant role in propylene production. Last, the in-situ Drifts-MS technique and DFT calculations demonstrate light radiation conduce to the electron transition from metal to the unpopulated electronic states of -C 3 H 7 fragments, while not conducing to the adsorbed C 3 H 8 molecule, thus selectively promoting the 2nd dehydrogenation process and achieving a balanced chemical kinetic condition. Our findings demonstrate that Photo-assisted Thermal PDH is a promising method for balancing the 1st and 2nd dehydrogenation processes.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CHEMICAL PHYSICS
·
2021
·Vol. 34
·期 4
·413-418
·
IF 1.114
Niu Xiao-you,Jiang Shen-long,Zhang Qun
Photocatalytic N 2 fixation has attracted substantial attention in
recent years, as it represents a green and sustainable development route toward
efficiently converting N 2 to NH 3 for industrial
applications. How to rationally design catalysts in this regard remains a
challenge. Here we propose a strategy that uses plasmonic hot electrons in the
highly doped TiO 2 to activate the inert N 2 molecules. The
synthesized semiconductor catalyst Mo-doped TiO 2 shows a
NH 3 production efficiency as high as 134
µmol · g −1 · h −1 under
ambient conditions, which is comparable to that achieved by the conventional
plasmonic gold metal. By means of ultra-fast spectroscopy we reveal that the
plasmonic hot electrons in the system are responsible for the activation of
N 2 molecules, enabling improvement the catalytic activity of
TiO 2 . This work opens a new avenue toward semiconductor
plasmon-based photocatalytic N 2 fixation.
研究领域:
材料科学
·
环境科学
·
化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Peng Zhang,Yongfang Rao,Yu Huang,Meijuan Chen,Tingting Huang,Wingkei Ho,Shuncheng Lee,Junbo Zhong,Junji Cao
The inevitable amorphous Bi 2 O 3 on the surface of plasmonic Bi nanospheres serving as the recombination center of hot electron-hole pairs, hindered the transfer of photo-generated hot electrons and production of reactive oxygen species (ROS) seriously. In this study, Bi@amorphous Bi 2 O 3 was transformed to Bi@crystal Bi 2 O 2 CO 3 by secondary hydrothermal reaction. Bi@Bi 2 O 2 CO 3 core–shell photocatalyst exhibited higher visible-light catalytic activity (34.1%) than Bi@Bi 2 O 3 did (12.3%) in terms of NO x removal. Photoelectrochemical, surface photovoltage spectroscopy spectra and Kelvin probe force microscopy measurement results indicate that Bi 2 O 2 CO 3 shell reduced the transmission resistance of hot electrons excited from Bi core. O 2 -TPD, trapping experiments and density functional theory further confirmed that the transferred hot electrons were a help for ROS generation and •O 2 − radicals were the major contributor. This study not only addresses the unsettled issue of surface amorphous Bi 2 O 3 , but also provides a facile method to transform the amorphous shell to crystal phase of core–shell photocatalyst and new insights into the hot electrons separation and the formation of main ROS over the surface crystal transition of plasmonic Bi.
研究领域:
材料科学
·
环境科学
·
化学
✓ 已验证
DOI
高影响因子
APPLIED ORGANOMETALLIC CHEMISTRY
·
2024
·
IF 3.7
Xiaohua Zhao,Xiaoxiao Liu,Xiang Liu,Weiyi Li,Ping Wang
Integration of localized surface plasmon resonance (LSPR) metallic nanocrystals into photocatalysis is an intriguing approach for light-driven organic transformations. However, uncertain direction of hot carriers is a grand challenge, which fails to take full advantage of the LSPR excitation. In this work, core–shell gold@ceria nanosphere–supported segregated palladium species (Au@CeO 2 –Pd) have developed to steer the light absorption capability and charge carrier migration. Under simulated solar light irradiation, the core–shell–satellite Au@CeO 2 –Pd exhibited efficient light harvesting and colossal activity in the Suzuki coupling reaction. The plasmon-induced hot electrons overpassed the Schottky barrier at the Au@CeO 2 interfaces and migrated from Au core to CeO 2 shell accordingly. Subsequently, the photogenerated electrons and hot electrons migrated from Au@CeO 2 core–shells to Pd, which acted as an electron acceptor. Detailed photocatalytic mechanism studies revealed that both photoexcited electrons and holes were the main active species involved in the photocatalytic Suzuki coupling reaction process. In particular, the diphenyl yield over Au@CeO 2 –Pd catalyst was ~1.7 times higher than that of core–shell–satellite Au@SiO 2 –Pd, where a 19-nm-thick SiO 2 shell was introduced to prevent the migration of hot electrons. This distinctly certified that the hot electrons transfer in the core–shell–satellite Au@CeO 2 –Pd under illumination played an important role to drive Suzuki reaction. Overall, this design of core–shell–satellite Au@CeO 2 –Pd plasmonic photocatalyst has the potential in the field of photo-driven organic transformations.
研究领域:
材料科学
·
化学工程
·
光化学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Optical Materials
·
2024
·
IF 8
Le Wang,Tiepei Geng,Ningneng Hu,Hao Li,Kaiyu Wang,Lishuai Hao,Weihai Ni
In hot electron (HE)-driven photocatalysis, plasmonic metal nanocrystals with small size, or even nanoclusters, are preferrable. Antenna–reactor mechanism has been utilized to further boost the photocatalytic performance of the small reactor nanoparticles. The construction of a metal–semiconductor–metal core–shell–satellite (CSS) superstructure is demonstrated for highly efficient HE generation of the entire CSS architecture, where a mesoporous TiO 2 (mTiO 2 ) shell spatially separates the Au nanohelicoid (AuNH) antenna core and Au nanocluster (AuNC) reactor satellites. Individual AuNH@mTiO 2 @AuNC CSS superstructures are optically characterized using dark field scattering and circular differential scattering spectroscopies. The HE and circular differential HE photocurrent responses of the CSS superstructures are measured using a photoelectrochemical cell, where 12.4- and 8.3-fold enhancements are respectively achieved with respect to that of the AuNHs. Electromagnetic simulations reveal that the contribution from the satellites with a small accumulative volume is almost equal to that from the core. Therefore, the specific-volume HE rate of the satellites exhibit a high amplification ratio, 350, with respect to that of the core, being attributed to the antenna–reactor mechanism in the CSS architecture. Key factors are optimized, which includes small size of the plasmonic satellites, E-field enhancement, and mesoporous semiconductor shell for efficient separation and collection of hot carriers.
研究领域:
材料科学
·
光学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of the American Chemical Society
·
2023
·
IF 15
Jiakuan Zhang,Jiongzhao Li,Zikang Ye,Jiting Cui,Xiaogang Peng
Using CdSe/ZnSe core–shell quantum dots (QDs) as a model, we systematically investigate the photochemical properties of QDs with the ZnSe shells under an ambient environment, which show almost opposite responses to either oxygen or water in comparison with CdSe/CdS core/shell QDs. While the ZnSe shells provide an efficient potential barrier for photoinduced electron transfer from the core to the surface-adsorbed oxygen, they also act as a stepping stone for hot-electron transfer directly from the ZnSe shells to oxygen. The latter process is so effective and competes favorably with ultrafast relaxation of hot electrons from the ZnSe shells to the core QDs, which can completely quench the photoluminescence (PL) with saturated adsorption of oxygen (1 bar) and initiate oxidation of the surface anion sites. Water can slowly eliminate the excess hole to neutralize the positively charged QDs, partially canceling the photochemical effects of oxygen. Alkylphosphines─through two distinctive reaction pathways with oxygen─stop the photochemical effects of oxygen and completely recover PL. With limited thickness (around two monolayers), the ZnS outer shells substantially slow down photochemical effects on CdSe/ZnSe/ZnS core/shell/shell QDs but cannot fully stop PL quenching by oxygen.
研究领域:
材料科学
·
光化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
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