Exploring the Effect of Pd on the Oxygen Reduction Performance of Pt by In Situ Raman Spectroscopy.

Directly monitoring the oxygen reduction reaction (ORR) process in situ is very important to deeply understand the reaction mechanism and is a critical guideline for the design of high-efficiency catalysts, but there is still lack of definite in situ evidence to clarify the effect between adsorbed intermediates and the strain/electronic effect for enhanced ORR performance. Herein, in situ surface-enhanced Raman spectroscopy (SERS) was employed to detect the intermediates during the ORR process on the Au@Pd@Pt core/shell heterogeneous nanoparticles (NPs). Direct spectroscopic evidence of the *OOH intermediate was obtained, and an obvious red shift of the *OOH frequency was identified with the controllable shell thickness of Pd. Detailed experimental characterizations and density functional theory (DFT) calculations demonstrated that such improved ORR activity after inducing Pd into Au@Pt NPs can be attributed to the optimized adsorbate-substrate interaction due to the strain and electronic effect, leading to a higher Pt-O binding energy and a lower O-O binding energy, which was conducive to O-O dissociation and promoted the subsequent reaction. Notably, this work illustrates a relationship between the performance and strain/electronic effect via the intermediate detected by SERS and paves the way for the construction of ORR electrocatalysts with high performance.

Unmasking the Critical Role of the Ordering Degree of Bimetallic Nanocatalysts on Oxygen Reduction Reaction by In Situ Raman Spectroscopy.

Precise control and accurate understanding of the ordering degree of bimetallic nanocatalysts (BNs) are challenging yet crucial to acquire advanced materials for the oxygen reduction reaction (ORR). AuCu BNs with various ordering degrees were synthesized to evaluate the influence of ordering degree on the ORR at a molecular level using in situ Raman spectroscopy. The activity of AuCu BNs was improved by over 2 times after a disorder-to-order transition, making the performance of highly ordered AuCu BNs exceed that of benchmark Pt/C. Direct Raman spectroscopic evidence of key intermediate (*OH) demonstrates that the active site is the combination site of Au and Cu. Moreover, two distinct *OH species are observed on the ordered and disordered structure, and the ordered site is more beneficial for ORR due to its lower affinity to *OH. This work deepens the understanding on the important role of ordering degree on BNs and enables the design of improved catalysts.

In Situ Raman Probing of Hot-Electron Transfer at Gold-Graphene Interfaces with Atomic Layer Accuracy.

Plasmonic metals under photoexcitation can generate energetic hot electrons to directly induce chemical reactions. However, the capability and fundamental insights of the transportation of these hot electrons at plasmonic metal-2D material interfaces remain unclear. Herein, hot-electron transfer at Au-graphene interfaces has been in situ studied using surface-enhanced Raman spectroscopy (SERS) with atomic layer accuracy. Combining in situ SERS studies with density functional theory calculations, it is proved that hot electrons can be injected from plasmonic Au nanoparticles to graphene and directly penetrate graphene to trigger photocatalytic reactions. With increasing graphene layers, the transportation of hot electrons decays rapidly and would be completely blocked after five layers of graphene. Moreover, the transfer of hot electrons can be modulated by applying an external electric field, and the hot-electron transfer efficiency under electrochemical conditions is improved by over three times in the presence of a monolayer of graphene.

In Situ Raman Observation of Oxygen Activation and Reaction at Platinum-Ceria Interfaces during CO Oxidation.

Understanding the fundamental insights of oxygen activation and reaction at metal-oxide interfaces is of significant importance yet remains a major challenge due to the difficulty in in situ characterization of active oxygen species. Herein, the activation and reaction of molecular oxygen during CO oxidation at platinum-ceria interfaces has been in situ explored using surface-enhanced Raman spectroscopy (SERS) via a borrowing strategy, and different active oxygen species and their evolution during CO oxidation at platinum-ceria interfaces have been directly observed. In situ Raman spectroscopic evidence with isotopic exchange experiments demonstrate that oxygen is efficiently dissociated to chemisorbed O on Pt and lattice Ce-O species simultaneously at interfacial Ce3+ defect sites under CO oxidation, leading to a much higher activity at platinum-ceria interfaces compared to that at Pt alone. Further in situ time-resolved SERS studies and density functional theory simulations reveal a more efficient molecular pathway through the reaction between adsorbed CO and chemisorbed Pt-O species transferred from the interfaces. This work deepens the fundamental understandings on oxygen activation and CO oxidation at metal-oxide interfaces and offers a sensitive technique for the in situ characterization of oxygen species under working conditions.

Direct S-H Evidence Revealing the Photo-electrocatalytic Hydrogen Evolution Reaction Mechanism on CdS Using Surface-Enhanced Raman Spectroscopy.

Photoelectrocatalytic water splitting using metal sulfides is a promising method for green hydrogen production. However, in situ probing of the hydrogen evolution reaction (HER) on sulfides with excellent performance remains a challenge. Here, we construct Au@CdS core-shell nanoparticles to study the HER on CdS, a typical HER catalyst, by surface-enhanced Raman spectroscopy (SERS) using a "borrowing" strategy. We directly capture the spectroscopic evidence of S-H intermediate under HER condition, further verified by isotopic experiments. Moreover, the population of S-H intermediates is improved by injecting charge carriers through light illumination and the S-H bond is weakened by introducing Pt to form a Au@Pt@CdS structure to change the interfacial electronic structure, both of them resulting in significant HER performance improvement. These findings can deepen the understanding of the HER mechanism and offer strategies for designing of cost-effective HER catalyst with high performance.

Direct Capturing and Regulating Key Intermediates for High-Efficiency Oxygen Evolution Reactions.

Developing efficient oxygen evolution reaction (OER) electrocatalysts can greatly advance the commercialization of proton exchange membrane (PEM) water electrolysis. However, the unclear and disputed reaction mechanism and structure-activity relationship of OER pose significant obstacles. Herein, the active site and intermediate for OER on AuIr nanoalloys are simultaneously identified and correlated with the activity, through the integration of in situ shell-isolated nanoparticle-enhanced Raman spectroscopy and X-ray absorption spectroscopy. The AuIr nanoalloys display excellent OER performance with an overpotential of only 246 mV to achieve 10 mA cm-2 and long-term stability under strong acidic conditions. Direct spectroscopic evidence demonstrates that * OO adsorbed on IrOx sites is the key intermediate for OER, and it is generated through the O-O coupling of adsorbed oxygen species directly from water, providing clear support for the adsorbate evolution mechanism. Moreover, the Raman information of the * OO intermediate can serve as a universal "in situ descriptor" that can be obtained both experimentally and theoretically to accelerate the catalyst design. It unveils that weakening the interactions of * OO on the catalysts and facilitating its desorption would boost the OER performance. This work deepens the mechanistic understandings on OER and provides insightful guidance for the design of more efficient OER catalysts.

In situ Raman spectroscopy reveals the structure evolution and lattice oxygen reaction pathway induced by the crystalline-amorphous heterojunction for water oxidation.

One of the most successful approaches for balancing the high stability and activity of water oxidation in alkaline solutions is to use amorphous and crystalline heterostructures. However, due to the lack of direct evidence at the molecular level, the nano/micro processes of amorphous and crystalline heterostructure electrocatalysts, including self-reconstruction and reaction pathways, remain unknown. Herein, the Leidenfrost effect assisted electrospray approach combined with phase separation was used for the first time to create amorphous NiO x /crystalline α-Fe2O3 (a-NiO x /α-Fe2O3) nanowire arrays. The results of in situ Raman spectroscopy demonstrate that with the increase of the potential at the a-NiO x /α-Fe2O3 interface, a significant accumulation of OH can be observed. Combining with XAS spectra and DFT calculations, we believe that more OH adsorption on the Ni centers can facilitate Ni2+ deprotonation to achieve the high-valence oxidation of Ni4+ according to HSAB theory (Fe3+ serves as a strong Lewis acid). This result promotes the electrocatalysts to follow the lattice oxygen activation mechanism. This work, for the first time, offers direct spectroscopic evidence for deepening the fundamental understanding of the Lewis acid effect of Fe3+, and reveals the synergistic effect on water oxidation via the unique amorphous and crystalline heterostructures.

Ultrafast and field-based detection of methamphetamine in hair with Au nanocake-enhanced Raman spectroscopy.

The disaster and devastation from abuse of Methamphetamine (MAMP) have a serious impact on people's mental and physical health. Developing a rapid and accurate method to screen drug suspects and thus control MAMP abuse is essential to social security. Hair analysis for MAMP detection is considered to be one of the most potential methods for monitoring drug abuse due to its convenient sample collection, easy for storage and long traceability period. However, the current accurate detection of MAMP in hair primarily utilizes hyphenated mass spectrometry (MS) techniques, but it is not suitable for field-based detection due to the bulky instrument. Hence, developing alternative portable detection techniques for rapid on-site detection of MAMP in hair is an urgent problem to be solved. Here, the high-performance Au nanocakes (Au NCs) were constructed as surface-enhanced Raman spectroscopy (SERS) substrates to detect MAMP in hair, realizing 5 min ultrafast and ultrasensitive detection utilizing a portable Raman spectrometer. Experiments and finite-difference time-domain (FDTD) simulations show that Au NCs have stronger enhancement than Au nanospheres (Au NPs), and 0.5 ppb (3.35 × 10-9 M) MAMP standard is stably detected by Au NCs as an enhanced substrate. A strategy of liquid-liquid microextraction was exploited to eliminate the interference of complex matrices in hair. This method exhibited excellent reproducibility and temporal stability across different drug addicts (relative standard deviation was 5.14% within 160 s). Our approach shows great promise in public safety, providing a rapid and accurate method to detect in hair by SERS.