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1.
Nano Lett ; 24(12): 3590-3597, 2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38489112

RESUMO

The deuteration of organic molecules is considerably important in organic and medicinal chemistry. An electrochemical membrane reactor using proton-conducting graphene oxide (GO) nanosheets was developed to synthesize valuable deuterium-labeled products via an efficient hydrogen-to-deuterium (H/D) exchange under mild conditions at ambient temperature and atmospheric pressure. Deuterons (D+) formed by the anodic oxidation of heavy water (D2O) at the Pt/C anode permeate through the GO membrane to the Pt/C cathode, where organic molecules with functional groups (C≡C and C═O) are deuterated with adsorbed atomic D species. Deuteration occurs in outstanding yields with high levels of D incorporation. We also achieved the electrodeuteration of a drug molecule, ibuprofen, demonstrating the promising feasibility of the GO membrane reactor in the pharmaceutical industry.

2.
Nano Lett ; 24(6): 2087-2093, 2024 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-38314714

RESUMO

The exceptional point (EP) is the critical phase transition point in parity-time (PT) symmetry systems, offering many unique physical phenomena, such as a chiral response. Achieving chiral EP in practical applications has been challenging due to the delicate balance required between gain and loss and complicated fabrication, limiting both working band and device miniaturization. Here, we proposed a nonlocal metasurface featuring orthogonal gold nanorods, where loss modulation is achieved through rod size and lattice pitch. By tuning the coupling strength, we experimentally observed the PT symmetry phase transition and chiral EP in the telecom-band. The experimental and simulated circular conversion dichroism at EP reach 0.79 and 0.99, respectively. We also demonstrated an abrupt phase flip of a specific component near EP theoretically. This work provides a feasible scheme for exploring EP in polarized space within the telecom-band, which may find applications in polarization control, wavelength division multiplexing, ultrasensitive sensing, imaging, etc.

3.
Nano Lett ; 24(4): 1392-1398, 2024 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-38227481

RESUMO

Nanoparticle sintering has long been a major challenge in developing catalytic systems for use at elevated temperatures. Here we report an in situ electron microscopy study of the extraordinary sinter resistance of a catalytic system comprised of sub-2 nm Pt nanoparticles on a Se-decorated carbon support. When heated to 700 °C, the average size of the Pt nanoparticles only increased from 1.6 to 2.2 nm, while the crystal structure, together with the {111} and {100} facets, of the Pt nanoparticles was well retained. Our electron microscopy analyses suggested that the superior resistance against sintering originated from the Pt-Se interaction. Confirmed by energy-dispersive X-ray elemental mapping and electron energy loss spectra, the Se atoms surrounding the Pt nanoparticles could survive the heating. This work not only offers an understanding of the physics behind the thermal behavior of this catalytic material but also sheds light on the future development of sinter-resistant catalytic systems.

4.
Nano Lett ; 24(4): 1261-1267, 2024 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-38242169

RESUMO

This work evaluates the feasibility of alkaline hydrogen evolution reaction (HER) using Pt single-atoms (1.0 wt %) on defect-rich ceria (Pt1/CeOx) as an active and stable dual-site catalyst. The catalyst displayed a low overpotential and a small Tafel slope in an alkaline medium. Moreover, Pt1/CeOx presented a high mass activity and excellent durability, competing with those of the commercial Pt/C (20 wt %). In this picture, the defective CeOx is active for water adsorption and dissociation to create H* intermediates, providing the first site where the reaction occurs. The H* intermediate species then migrate to adsorb and react on the Pt2+ isolated atoms, the site where H2 is formed and released. DFT calculations were also performed to obtain mechanistic insight on the Pt1/CeOx catalyst for the HER. The results indicate a new possibility to improve the state-of-the-art alkaline HER catalysts via a combined effect of the O vacancies on the ceria support and Pt2+ single atoms.

5.
Rep Prog Phys ; 87(7)2024 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-38957897

RESUMO

Non-Hermitian matrices are ubiquitous in the description of nature ranging from classical dissipative systems, including optical, electrical, and mechanical metamaterials, to scattering of waves and open quantum many-body systems. Seminal line-gap and point-gap classifications of non-Hermitian systems using K-theory have deepened the understanding of many physical phenomena. However, ample systems remain beyond this description; reference points and lines do not in general distinguish whether multiple non-Hermitian bands exhibit intriguing exceptional points, spectral braids and crossings. To address this we consider two different notions: non-Hermitian band gaps and separation gaps that crucially encompass a broad class of multi-band scenarios, enabling the description of generic band structures with symmetries. With these concepts, we provide a unified and comprehensive classification of both gapped and nodal systems in the presence of physically relevant parity-time (PT) and pseudo-Hermitian symmetries using homotopy theory. This uncovers new stable topology stemming from both eigenvalues and wave functions, and remarkably also implies distinct fragile topological phases. In particular, we reveal different Abelian and non-Abelian phases inPT-symmetric systems, described by frame and braid topology. The corresponding invariants are robust to symmetry-preserving perturbations that do not induce (exceptional) degeneracy, and they also predict the deformation rules of nodal phases. We further demonstrate that spontaneousPTsymmetry breaking is captured by Chern-Euler and Chern-Stiefel-Whitney descriptions, a fingerprint of unprecedented non-Hermitian topology previously overlooked. These results open the door for theoretical and experimental exploration of a rich variety of novel topological phenomena in a wide range of physical platforms.

6.
J Comput Chem ; 45(16): 1352-1363, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38376255

RESUMO

Vibrational spectroscopy enables critical insight into the structural and dynamic properties of molecules. Presently, the majority of theoretical approaches to spectroscopy employ wavefunction-based ab initio or density functional methods that rely on the harmonic approximation. This approximation breaks down for large molecules with strongly anharmonic bonds or for molecules with large internuclear separations. An alternative to these methods involves generating molecular anharmonic potential energy surfaces (potentials) and using them to extrapolate the vibrational frequencies. This study examines the efficacy of density functional theory (DFT) and the correlation consistent Composite Approach (ccCA) in generating anharmonic frequencies from potentials of small main group molecules. Vibrational self-consistent field Theory (VSCF) and post-VSCF methods were used to calculate the fundamental frequencies of these molecules from their potentials. Functional choice, basis set selection, and mode-coupling are also examined as factors in influencing accuracy. The absolute deviations for the calculated frequencies using potentials at the ccCA level of theory were lower than the potentials at the DFT level. With DFT resulting in bending modes that are better described than those of ccCA, a multilevel DFT:ccCA approach where DFT potentials are used for single vibrational mode potentials and ccCA is used for vibrational mode-mode couplings can be utilized for larger polyatomic systems. The frequencies obtained with this multilevel approach using VCIPSI-PT2 were closer to experimental frequencies than the scaled harmonic frequencies, indicating the success of utilizing post-VSCF methods to generate more accurate representations of computed infrared spectra.

7.
Small ; 20(25): e2309427, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38240468

RESUMO

As cost-effective catalysts, platinum (Pt) single-atom catalysts (SACs) have attracted substantial attention. However, most studies indicate that Pt SACs in acidic hydrogen evolution reaction (HER) follow the slow Volmer-Heyrovsky (VH) mechanism instead of the fast kinetic Volmer-Tafel (VT) pathway. Here, this work propose that the VH mechanism in Pt SACs can be switched to the faster VT pathway for efficient HER by correlating Pt single atoms (SAs) with Pt clusters (Cs). Our calculations reveal that the correlation between Pt SAs and Cs significantly impacts the electronic structure of exposed Pt atoms, lowering the adsorption barrier for atomic hydrogen and enabling a faster VT mechanism. To validate these findings, this work purposely synthesize three catalysts: l-Pt@MoS2, m-Pt@MoS2 and h-Pt@MoS2 with low, moderate, and high Pt-loading, having different distributions of Pt SAs and Cs. The m-Pt@MoS2 catalyst with properly correlating Pt SAs and Cs exhibits outstanding performance with an overpotential of 47 mV and Tafel slope of 32 mV dec-1. Further analysis of the Tafel values confirms that the m-Pt@MoS2 sample indeed follows the VT reaction mechanism, aligning with the theoretical findings. This study offers a deep understanding of the synergistic mechanism, paving a way for designing novel-advanced catalysts.

8.
Small ; 20(29): e2310465, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38366001

RESUMO

The modification of metal oxides with noble metals is one of the most effective means of improving gas-sensing performance of chemiresistors, but it is often accompanied by unintended side effects such as sensor resistance increases up to unmeasurable levels. Herein, a carbonization-oxidation method is demonstrated using ultrasonic spray pyrolysis technique to realize platinum (Pt) single atom (SA) substitutional doping into SnO2 (named PtSA-SnO2). The substitutional doping strategy can obviously enhance gas-sensing properties, and meanwhile decrease sensor resistance by two orders of magnitude (decreased from ≈850 to ≈2 MΩ), which are attributed to the tuning of band gap and fermi-level position, efficient single atom catalysis, and the raising of adsorption capability of formaldehyde, as validated by the state-of-the-art characterizations, such as spherical aberration-corrected scanning transmission electron microscopy (Cs-corrected STEM), in situ diffuse reflectance infrared Fourier transformed spectra (in situ DRIFT), CO temperature-programmed reduction (CO-TPR), and theoretical calculations. As a proof of concept, the developed PtSA-SnO2 sensor shows humidity-independent (30-70% relative humidity) gas-sensing performance in the selective detection of formaldehyde with high response, distinguishable selectivity (8< Sformaldehyde/Sinterferant <14), and ultra-low detection limit (10 ppb). This work presents a generalized and facile method to design high-performance metal oxides for chemical sensing of volatile organic compounds (VOCs).

9.
Small ; : e2403098, 2024 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-39162110

RESUMO

To meet the ever-increasing demand of proton exchange membrane fuel cell (PEMFC), it is necessary to carry out structure optimization for low-cost and high-stability oxygen reduction reaction (ORR) catalysts. Herein, a zeolitic imidazolate framework (ZIF)-derived carbon material with a mass of heteroatoms and defects is developed and serves as advanced support for nano-Pt-based ORR catalysts. This unique structure enhances the interaction between nano-Pt and support, leading to higher ORR intrinsic activity. During fuel cell applications, it demonstrates impressive water-retaining capacity and electrochemical stability. Under H2-O2 supply without cathode humidification, this catalyst achieves high mass activity of 0.475 A mgPt -1, with only 7.4% attenuation in maximum power density after 20 000 cycles of accelerated durability test, highlighting its remarkable potential for fuel cell applications. Physicochemical characterization and theoretical simulation reveal the crucial anchoring effect of heteroatom-doped defects to nano-Pt, providing valuable insights for further ORR catalyst design and PEMFC applications.

10.
Small ; : e2311260, 2024 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-38634299

RESUMO

Vapor-based deposition techniques are emerging approaches for the design of carbon-supported metal powder electrocatalysts with tailored catalyst entities, sizes, and dispersions. Herein, a pulsed CVD (Pt-pCVD) approach is employed to deposit different Pt entities on mesoporous N-doped carbon (MPNC) nanospheres to design high-performance hydrogen evolution reaction (HER) electrocatalysts. The influence of consecutive precursor pulse number (50-250) and deposition temperature (225-300 °C) are investigated. The Pt-pCVD process results in highly dispersed ultrasmall Pt clusters (≈1 nm in size) and Pt single atoms, while under certain conditions few larger Pt nanoparticles are formed. The best MPNC-Pt-pCVD electrocatalyst prepared in this work (250 pulses, 250 °C) reveals a Pt HER mass activity of 22.2 ± 1.2 A mg-1 Pt at -50 mV versus the reversible hydrogen electrode (RHE), thereby outperforming a commercially available Pt/C electrocatalyst by 40% as a result of the increased Pt utilization. Remarkably, after optimization of the Pt electrode loading, an ultrahigh Pt mass activity of 56 ± 2 A mg-1 Pt at -50 mV versus RHE is found, which is among the highest Pt mass activities of Pt single atom and cluster-based electrocatalysts reported so far.

11.
Small ; : e2404274, 2024 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-38966895

RESUMO

In this work, a highly accurate neural network potential (NNP) is presented, named PtNNP, and the exploration of the reconstruction of the Pt(001) surface and its vicinal surfaces with it. Contrary to the most accepted understanding of the Pt(001) surface reconstruction, the study reveals that the main driving force behind Pt(001) quasi-hexagonal reconstruction is not the surface stress relaxation but the increased coordination number of the surface atoms resulting in stronger intralayer binding in the reconstructed surface layer. In agreement with experimental observations, the optimized supercell size of the reconstructed Pt(001) surface contains (5 × 20) unit cells. Surprisingly, the reconstruction of the vicinal Pt(001) surfaces leads to a smooth shell-like surface layer covering the whole surface and diminishing sharp step edges.

12.
Small ; 20(24): e2309457, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38150624

RESUMO

Highly efficient and durable Pt electrocatalysts are the key to boost the performance of fuel cells. The high-index facets (HIF) Pt nanocrystals are regarded as excellent catalytic activity and stability catalysts. However, nucleation, growth and evolution of high-index facets Pt nanocrystals induced by defective sites is still a challenge. In this work, tetrahexahedron (THH) and hexactahedron (HOH) Pt nanocrystals are synthesized, which are loaded on the nitrogen-doped reduced graphene oxide (N-rGO) support of the integrated electrodes by the square wave pulse method. Experimental investigations and density functional theory (DFT) calculations are conducted to analyze the growth and evolution mechanism of HIF Pt nanocrystals on the graphene-derived carbon supports. It shows that the H adsorption on the N-rGO/CFP support can induce evolution of Pt nanocrystals. Moreover, the N-defective sites on the surface of N-rGO can lead to a slower growth of Pt nanocrystals than that on the surface of reduced graphene oxide (rGO). Pt/N-rGO/CFP (20 min) shows the highest specific activity in methanol oxidation, which is 1.5 times higher than that of commercial Pt/C. This research paves the way on the design and synthesis of HIF Pt nanocrystal using graphene-derived carbon materials as substrates in the future.

13.
Small ; 20(22): e2309823, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38109127

RESUMO

Electrocatalysts with low Pt loading mass to achieve high current density (≥1 A cm-2) for hydrogen evolution reaction (HER) are still extremely challenging due to the limited intrinsic activity and weak stability of catalytic sites. The modulation of the electronic microenvironment of the support-Pt structure is crucial to enhance the intrinsic activity and stability of catalytic sites. Herein, an innovative titanium oxycarbide (TiVCO) solid solution with Ti vacancies (TiV) is proposed as support to anchor sub-nanoscale Pt atomic clusters (Pt ACs) and a stable "TiV-Pt ACs" structure is carefully designed. The electronic microenvironment of "TiV-Pt ACs" is indirectly optimized by an unsaturated C/O site near TiV. Thanks to this, novel "TiV-Pt ACs" structure (Pt@TiVCO) with low Pt loading mass (2.44 wt.%) exhibits excellent HER activity in acidic solution and the mass activity is more than ten times that of commercial 20% Pt/C at the overpotentials of 50 and 100 mV. Particularly, Pt@TiVCO shows amazing stability at high and fluctuating current density of 1-2 A cm-2 for 120 h. This work provides a novel and promising method to develop stable and low-loading Pt-based catalysts adapting to high current density.

14.
Small ; 20(22): e2307135, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38126901

RESUMO

Achieving high catalytic activity with a minimum amount of platinum (Pt) is crucial for accelerating the cathodic hydrogen evolution reaction (HER) in proton exchange membrane (PEM) water electrolysis, yet it remains a significant challenge. Herein, a directed dual-charge pumping strategy to tune the d-orbital electronic distribution of Pt nanoclusters for efficient HER catalysis is proposed. Theoretical analysis reveals that the ligand effect and electronic metal-support interactions (EMSI) create an effective directional electron transfer channel for the d-orbital electrons of Pt, which in turn optimizes the binding strength to H*, thereby significantly enhancing HER efficiency of the Pt site. Experimentally, this directed dual-charge pumping strategy is validated by elaborating Sb-doped SnO2 (ATO) supported Fe-doped PtSn heterostructure catalysts (Fe-PtSn/ATO). The synthesized 3%Fe-PtSn/ATO catalysts exhibit lower overpotential (requiring only 10.5 mV to reach a current density of 10 mA cm- 2), higher mass activity (28.6 times higher than commercial 20 wt.% Pt/C), and stability in the HER process in acidic media. This innovative strategy presents a promising pathway for the development of highly efficient HER catalysts with low Pt loading.

15.
Small ; : e2404608, 2024 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-39177179

RESUMO

Elaborated structural modulation of Pt-based artificial nanozymes can efficiently improve their catalytic activity and expand their applications in clinical diagnosis and biochemical sensing. Herein, a highly efficient dual-site peroxidase mimic composed of highly dispersed Pt and Mo atoms is reported. The obtained Mo-Pt/CeO2 exhibits exceptional peroxidase-like catalytic activity, with a Vmax as high as 34.16 × 10-8 m s-1, which is 37.5 times higher than that of the single-site counterpart. Mechanism studies suggest that the Mo atoms can not only serve as adsorption and activation sites for the H2O2 substrate but also regulate the charge density of Pt centers to promote the generation ability of •OH. As a result, the synergistic effect between the dual active sites significantly improves the catalytic efficiency. Significantly, the application of the Mo-Pt/CeO2 catalyst's excellent peroxidase-like activity is extended to various biochemical detection applications, including the trace detection of glucose and cysteine, as well as the assessment of antioxidants' antioxidant capacity. This work reveals the great potential of rational design dual-site active centers for constructing high-performance artificial nanozymes.

16.
Small ; : e2403314, 2024 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-39152932

RESUMO

Efficient and durable electrocatalysts for the hydrogen evolution reaction (HER) in alkaline seawater environments are essential for sustainable hydrogen production. Zeolitic imidazolate framework-8 (ZIF-8) is synthesized through pulsed laser ablation in liquid, followed by pyrolysis, producing N-doped porous carbon (NC). NC matrix serves as a self-template, enabling Pt nanocluster decoration (NC-Pt) via pulsed laser irradiation in liquid. NC-Pt exhibits a large surface area, porous structure, high conductivity, N-rich carbon, abundant active sites, low Pt content, and a strong NC-Pt interaction. These properties enhance efficient mass transport during the HER. Remarkably, the optimized NC-Pt-4 catalyst achieves low HER overpotentials of 52, 57, and 53 mV to attain 10 mA cm-2 in alkaline, alkaline seawater, and simulated seawater, surpassing commercial Pt/C catalysts. In a two-electrode system with NC-Pt-4(-)ǀǀIrO2(+) as cathode and anode, it demonstrates excellent direct seawater electrolysis performance, with a low cell voltage of 1.63 mV to attain 10 mA cm-2 and remarkable stability. This study presents a rapid and efficient method for fabricating cost-effective and highly effective electrocatalysts for hydrogen production in alkaline and alkaline seawater environments.

17.
Small ; : e2404064, 2024 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-39155415

RESUMO

Recently, the use of Pt in the form of single atoms (SA) has attracted considerable attention to promote the cathodic hydrogen production reaction from water in electrochemical or photocatalytic settings. First, produce suitable electrodes by Pt SA deposition on Direct current (DC)-sputter deposited titania (TiO2) layers on graphene-these electrodes allow to characterization of the electrochemical properties of Pt single atoms and their investigation in high-resolution HAADF-STEM. For Pt SAs loaded on TiO2, electrochemical H2 evolution shows only a very small overpotential. Concurrent with the onset of H2 evolution, agglomeration of the Pt SAs to clusters or nanoparticles (NPs) occurs. Potential cycling can be used to control SA agglomeration to variable-size NPs. The electrochemical activity of the electrode is directly related to the SA surface density (up to reaching the activity level of a plain Pt sheet). In contrast, for photocatalytic H2 generation already a minimum SA density is sufficient to reach control by photogenerated charge carriers. In electrochemical and photocatalytic approaches a typical TOF of ≈100-150 H2 molecules per second per site can be reached. Overall, the work illustrates a straightforward approach for reliable electrochemical and photoelectrochemical investigations of SAs and discusses the extraction of critical electrochemical factors of Pt SAs on titania electrodes.

18.
Small ; 20(32): e2311738, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38477695

RESUMO

Metal silicide/Si photoelectrodes have demonstrated significant potential for application in photoelectrochemical (PEC) water splitting to produce H2. To achieve an efficient and economical hydrogen evolution reaction (HER), a paramount consideration lies in attaining exceptional catalytic activity on the metal silicide surface with minimal use of noble metals. Here, this study presents the design and construction of a novel Ni0.95Pt0.05Si/p-Si photocathode. Dopant segregation is used to achieve a Schottky barrier height as high as 1.0 eV and a high photovoltage of 420 mV. To achieve superior electrocatalytic activity for HER, a dissolution-induced surface reconstruction (SR) strategy is proposed to in situ convert surface Ni0.95Pt0.05Si to highly active Pt2Si. The resulting SR Ni0.95Pt0.05Si/p-Si photocathode exhibits excellent HER performance with an onset potential of 0.45 V (vs RHE) and a high maximum photocurrent density of 40.5 mA cm-2 and a remarkable applied bias photon-to-current efficiency (ABPE) of 5.3% under simulated AM 1.5 (100 mW cm-2) illumination. The anti-corrosion silicide layer effectively protects Si, ensuring excellent stability of the SR Ni0.95Pt0.05Si/p-Si photoelectrode. This study highlights the potential for achieving efficient PEC HER using bimetallic silicide/Si photocathodes with reduced Pt consumption, offering an auspicious perspective for the cost-effective conversion of solar energy to chemical energy.

19.
Small ; 20(33): e2400240, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38593333

RESUMO

In this work, Pt3Fe nanoparticles (Pt3Fe NPs) with the ordered internal structure and Pt-rich shells surrounded by plenty of Fe single atoms (Fe SAs) as active species (Pt3Fe NP-in-Fe SA) loaded in the carbon materials are successfully fabricated, which are abbreviated as island-in-sea structured (IISS) Pt3Fe NP-in-Fe SA catalysts. Moreover, the synergistic effect of O-bridging between Pt3Fe NPs and Fe SAs, and the ordered internal structured Pt3Fe NPs with Pt-rich shells of an optimal thickness contributes to the achievement of the local acidic environments on the surfaces of Pt3Fe NPs in the alkaline hydrogen evolution reaction (HER) and the enhancement of the desorption rate of *OH intermediate in the acidic oxygen reduction reaction (ORR). In addition, the electronic interactions between Pt3Fe NPs and dispersed Fe SAs cannot only provide efficient electrons transfer, but also prevent the aggregation and dissolution of Pt3Fe NPs. Furthermore, the overpotential and the half wave potential of the as-prepared IISS Pt3Fe NP-in-Fe SA catalysts toward the alkaline HER and toward the acidic ORR are 8 mV at a current density of 10 mA cm-2 and 0.933 V, respectively, which is 29 lower and 86 mV higher than those (37 mV and 0.847 V) of commercial Pt/C catalysts.

20.
Small ; 20(31): e2400617, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38441279

RESUMO

Photocatalytic lignocellulose reforming for H2 production presents a compelling solution to solve environmental and energy issues. However, achieving scalable conversion under benign conditions faces consistent challenges including insufficient active sites for H2 evolution reaction (HER) and inefficient lignocellulose oxidation directly by photogenerated holes. Herein, it is found that Pt single atom-loaded CdS nanosheet (PtSA-CdS) would be an active photocatalyst for lignocellulose-to-H2 conversion. Theoretical and experimental analyses confirm that the valence band of CdS shifts downward after depositing isolated Pt atoms, and the slope of valence band potential on pH for PtSA-CdS is more positive than Nernstian equation. These characteristics allow PtSA-CdS to generate large amounts of •OH radicals even at pH 14, while the capacity is lacking with CdS alone. The employment of •OH/OH- redox shuttle succeeds in relaying photoexcited holes from the surface of photocatalyst, and the •OH radicals can diffuse away to decompose lignocellulose efficiently. Simultaneously, surface Pt atoms, featured with a thermoneutral Δ G H ∗ $\Delta G_{\mathrm{H}}^{\mathrm{*}}$ , would collect electrons to expedite HER. Consequently, PtSA-CdS performs a H2 evolution rate of 10.14 µmol h-1 in 1 m KOH aqueous solution, showcasing a remarkable 37.1-fold enhancement compared to CdS. This work provides a feasible approach to transform waste biomass into valuable sources.

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