Spatial configuration of Fe-Co dual-sites boosting catalytic intermediates coupling toward oxygen evolution reaction.

Oxygen evolution reaction (OER) is the pivotal obstacle of water splitting for hydrogen production. Dual-sites catalysts (DSCs) are considered exceeding single-site catalysts due to the preternatural synergetic effects of two metals in OER. However, appointing the specific spatial configuration of dual-sites toward more efficient catalysis still remains a challenge. Herein, we constructed two configurations of Fe-Co dual-sites: stereo Fe-Co sites (stereo-Fe-Co DSC) and planar Fe-Co sites (planar-Fe-Co DSC). Remarkably, the planar-Fe-Co DSC has excellent OER performance superior to stereo-Fe-Co DSC. DFT calculations and experiments including isotope differential electrochemical mass spectrometry, in situ infrared spectroscopy, and in situ Raman reveal the *O intermediates can be directly coupled to form *O-O* rather than *OOH by both the DSCs, which could overcome the limitation of four electron transfer steps in OER. Especially, the proper Fe-Co distance and steric direction of the planar-Fe-Co benefit the cooperation of dual sites to dehydrogenate intermediates into *O-O* than stereo-Fe-Co in the rate-determining step. This work provides valuable insights and support for further research and development of OER dual-site catalysts.

General Synthesis of a Diatomic Catalyst Library via a Macrocyclic Precursor-Mediated Approach.

Heterogeneous catalysts containing diatomic sites are often hypothesized to have distinctive reactivity due to synergistic effects, but there are limited approaches that enable the convenient production of diatomic catalysts (DACs) with diverse metal combinations. Here, we present a general synthetic strategy for constructing a DAC library across a wide spectrum of homonuclear (Fe2, Co2, Ni2, Cu2, Mn2, and Pd2) and heteronuclear (Fe-Cu, Fe-Ni, Cu-Mn, and Cu-Co) bimetal centers. This strategy is based on an encapsulation-pyrolysis approach, wherein a porous material-encapsulated macrocyclic complex mediates the structure of DACs by preserving the main body of the molecular framework during pyrolysis. We take the oxygen reduction reaction (ORR) as an example to show that this DAC library can provide great opportunities for electrocatalyst development by unlocking an unconventional reaction pathway. Among all investigated sites, Fe-Cu diatomic sites possess exceptional high durability for ORR because the Fe-Cu pairs can steer elementary steps in the catalytic cycle and suppress the troublesome Fenton-like reactions.

Bulk-like Pt(100)-oriented Ultrathin Surface: Combining the Merits of Single Crystals and Nanoparticles to Boost Oxygen Reduction Reaction.

Single crystal surfaces with highly coordinated sites very often hold high specific activities toward oxygen reduction reaction (ORR) and others. Transposing their high specific activity to practical high-surface-area electrocatalysts remains challenging. Here, ultrathin Pt(100) alloy surface is constructed via epitaxial growth. The surface shows 3.1-6.9 % compressive strain and bulk-like characteristics as demonstrated by site-probe reactions and different spectroscopies. Its ORR activity exceeds that of bulk Pt3 Ni(100) and Pt(111) and presents a 19-fold increase in specific activity and a 13-fold increase in mass activity relative to commercial Pt/C. Moreover, the electrochemically active surface area (ECSA) is increased by 4-fold compared to traditional thin films (e.g. NSTF), which makes the catalyst more tolerant to voltage loss at high current densities under fuel cell operation. This work broadens the family of extended surface catalysts and highlights the knowledge-driven approach in the development of advanced electrocatalysts.

Recent strategies for triplet-state emission regulation toward non-lead organic-inorganic metal halides.

Organic-inorganic metal halides (OIMHs) have strengthened the development of triplet-state emission materials due to their excellent luminescence performance. Due to the inherent toxicity of lead (Pb) significantly limiting its further advancement, numerous studies have been conducted to regulate triplet-state emission of non-Pb OIMHs, and several feasible strategies have been proposed. However, most of the non-Pb OIMHs reported have a relatively short lifetime or a low luminescence efficiency, not in favor of their application. In this review, we provide a summary of recent reports on the regulation of triplet-state emissions in non-Pb OIMHs to provide benefits for the design of innovative luminescent materials. Our focus is primarily on exploring the internal and external factors that influence the triplet-state emission. Starting from the luminescence mechanism, the current strategies for regulating triplet-state emissions are summarized. Moreover, by manipulating these strategies, it becomes feasible to achieve triplet-state emissions that span a range of colors from blue to red, and even extend into the near-infrared spectrum with high luminescence efficiency, while also increasing their lifetimes. This review not only provides fresh insights into the advancement of triplet-state emissions in OIMHs but also integrates experimental and theoretical perspectives to illuminate the trajectory of future research endeavors.

Terrace-Rich Ultrathin PtCu Surface on Earth-Abundant Metal for Oxygen Reduction Reaction.

The activity and stability of the platinum electrode toward the oxygen reduction reaction are size-dependent. Although small nanoparticles have high Pt utilization, the undercoordinated Pt sites on their surface are assumed to have too strong oxygen binding strength, thus often leading to compromised activity and surface instability. Herein, we report an extended nanostructured PtCu ultrathin surface to reduce the number of low-coordination sites without sacrificing the electrochemical active surface area (ECSA). The surface shows (111)-oriented characteristics, as proven by electrochemical probe reactions and spectroscopies. The PtCu surface brings over an order of magnitude increase in specific activity relative to commercial Pt/C and nearly 4-fold enhancement in ECSA compared to traditional thin films. Moreover, due to the weak absorption of air impurities (e.g., SO2, NO, CO) on highly coordinated sites, the catalyst displays enhanced contaminant tolerance compared with nanoparticulate Pt/C. This work promises a broad screening of extended nanostructured surface catalysts for electrochemical conversions.

Gram-scale synthesis of ultra-fine Cu2O for highly efficient ozone decomposition.

Nowadays, it is necessary and challenging to prepare Cu2O in a large scale for various applications such as catalysis due to its excellent properties. Here, gram-scale Cu2O with nm size is successfully prepared using a simple liquid-phase reduction method at 25 °C. The amount of NaOH is found to be the key factor to determine the particle size of Cu2O by modifying the complexation and reduction reactions. The obtained ultra-fine Cu2O exhibits high performance of >95% efficiency for removing high-concentration (3000 ppm) ozone at 25 °C and even at a high relative humidity (RH) of 90% for more than 8 h. Furthermore, the Cu2O nanoparticles are coated onto an aluminium honeycomb substrate to form a monolithic catalyst, which shows high ozone removal efficiency of >99% in dry air and >97% in 90% RH for >10 h at a space velocity of 8000 h-1. The high performance could be attributed to the enhanced release of the ozone decomposition intermediate by the small size of Cu2O, as verified by O2 temperature-programmed desorption and X-ray photoelectron spectroscopy. All these results show the industrial promise of the large scale synthesis of ultrafine Cu2O applicable for high-performance ozone removal.