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Single‐atom catalysts (SACs) are widely studied in various chemical transformations due to their high catalytic activity and atom utilization. However, modulating the catalytic performance of catalysts by adjusting the microenvironment remains a great challenge. In this paper, a novel master‐double guest vulcanization‐assisted strategy is reported for synthesizing Fe single‐atom catalysts on N,S codoped porous hollow leaf carbon (FeSA/N,S‐PHLC) with highly exposed FeN3SOH sites. Fe(mIm) (guest I) is loaded on the surface of ZIF‐L (host) and then trithiocyanuric acid (TCA, guest II) is bonded with Fe(mIm), and the resulting ZIF‐L@Fe(mIm)@TCA precursors can be converted to FeSA/N,S‐PHLC with controllable structures. In addition, XPS analysis yield an increase in pyridine N content in FeSA/N,S‐PHLC compared to FeSA/N‐PHLC. It can be demonstrated by theoretical calculations that the N,S‐coordinated axially hydroxy‐coordinated asymmetric Fe centers synergistically with the abundance of pyridinic nitrogen facilitate the adsorption and desorption of oxygen intermediates, and the 3d orbitals of the Fe active centers can be optimized. The prepared FeSA/N,S‐PHLC catalyst has a half‐wave potential (E1/2) of 0.91 V under alkaline conditions, and E1/2 = 0.75 V under acidic conditions. It shows excellent cycle stability (882 h) and power density (217 mW cm−2) in the assembly of zinc–air battery (ZABs) devices. [ABSTRACT FROM AUTHOR]

It is a great challenge to induce the formation of the RuP4 phase and realize the construction of a metal‐rich phase/phosphorus‐rich phase‐ruthenium phosphide heterostructure by directional regulation of the proportion of P and metal atoms. The ultra‐high conductivity of Ru2P and the excellent ability of V‐doped RuP4 to absorb/desorb H* are confirmed by density functional theory (DFT) calculations, which laid a theoretical foundation for the construction of a unique Ru2P/V‐RuP4 structure to accelerate HER reaction kinetics. This work innovatively uses the V‐doping strategy to induce the formation of RuP4 phase with high intrinsic activity, and finally construct V‐RuxPy nanosheets with rich Ru/Ru2P/V‐RuP4 heterostructures. Thanks to the rich Ru/Ru2P/V‐RuP4 heterostructure and the optimization of V dopants, the V‐RuxPy catalyst only needs 180 mV to obtain an industrial‐grade current density of 1 A cm−2. In summary, this work provides a new idea for the design and performance optimization of ruthenium‐based catalysts. [ABSTRACT FROM AUTHOR]

The hydrogen energy generated by the electrocatalytic water splitting reaction has been established as a renewable and clean energy carrier with ultra‐high energy density, which can well make up for shortcomings of conventional renewable energy sources, such as geographical limitations, climatic dependence, and energy wastage. Notably, the introduction of electrocatalysts can enhance the efficiency of the water splitting process to generate hydrogen. Particularly, the heterostructure electrocatalysts constructed by coupling multiple components (or phases) have emerged as the most promising option for water splitting due to the well‐known electronic and synergistic effects. The existing reviews on interface engineering for electrocatalyst design mostly focus on the relationship between the heterostructures and specific electrocatalytic reactions. However, a comprehensive overview of the integration of model building, directional synthesis, and electrocatalytic mechanism has been rarely reported. To this end, in this review, the development of heterostructure catalysts is systematically introduced from the perspective of interface classification, interface growth and synthesis, and regulation of electrocatalytic performance based on the interfacial microenvironment (bonding, electronic configuration, lattice strain, etc.), thereby offering useful insights on the design and construction of interfacial models. Besides, combined with the current development and applications of interface engineering strategies, the challenges of future heterostructure catalysts are discussed and relevant solutions are proposed. Overall, this review can serve as a useful theoretical reference for the integration of interfacial model building, directional synthesis, and electrocatalytic mechanism, which can further promote the development of hydrogen production technologies with low energy consumption and high yield. [ABSTRACT FROM AUTHOR]

Currently, the construction of heterostructures to optimize electrocatalytic activities is a hot research topic, since there is still a certain gap between the electrocatalytic properties of these heterostructures and that of Pt/C. With this in mind, we utilized in‐situ vapor‐phase phosphorization‐sulfurization to obtain the CoP3/MoS2−Co0.75Mo3S3.75 (CoP/CoMoS, for short) heterostructure on carbon cloth (CC), which exhibits Pt‐like electrocatalytic performance and excellent stability in acid electrolyte. Activated by CoP3 active phase, the electronic configuration of CoMoS and the adsorption energy of H* (▵GH*) are greatly optimized. Meanwhile, the rapid oxidation of CoMoS phase can be effectively avoided under the protection of CoP3 layer. This work provides a reference for the design of heterostructures and their mechanism of action in electrocatalysis. [ABSTRACT FROM AUTHOR]

Transition metal phosphide is regarded as one of the most promising candidates to replace noble‐metal hydrogen evolution reaction (HER) electrocatalysts. Nevertheless, the controllable design and synthesis of transition metal phosphide electrocatalysts with efficient and stable electrochemical performance are still very challenging. Herein, a novel hierarchical HER electrocatalyst consisting of three‐dimensional (3D) coral‐like Mn‐doped Co2P@an intermediate layer of Ni2P generated in situ by phosphorization on Ni foam (MnCoP/NiP/NF) is reported. Notably, both the incorporation of Mn and introduction of the Ni2P interlayer promote Co atoms to carry more electrons, which is beneficial to reduce the force of the Co−H bond and optimize the adsorption energy of hydrogen intermediate (|ΔGH*|), thereby making MnCoP/NiP/NF exhibit outstanding HER performance with onset overpotential and Tafel slope as low as 31.2 mV and 61 mV dec−1, respectively, in 1 m KOH electrolyte. [ABSTRACT FROM AUTHOR]

Rational construction of high‐efficiency and low‐cost catalysts is one of the most promising ways to produce hydrogen but remains a huge challenge. Herein, interface engineering and heteroatom doping were used to synthesize V‐doped sulfide/phosphide heterostructures on nickel foam (V‐Ni3S2/NixPy/NF) by phosphating treatment at low temperature. The incorporation of V can adjust the electronic structure of Ni3S2, expose more active sites, and protect the 3D structure of Ni foam from damage. Meanwhile, the heterogeneous interface formed between Ni3S2 and NixPy can provide abundant active sites and accelerate electron transfer. As a result, the V‐Ni3S2/NixPy/NF nanosheet catalyst exhibits outstanding activity in the hydrogen evolution reaction (HER) with an extremely low overpotential of 90 mV at a current density of 10 mA cm−2 and stable durability in alkaline solution, which exceeds those most of the previously reported Ni‐based materials. This work shows that rational design by interfacial engineering and metal‐atom incorporation has a significant influence for efficient hydrogen evolution. [ABSTRACT FROM AUTHOR]

Platinum (Pt)‐based compounds are the benchmarked catalysts for hydrogen evolution reaction (HER) but exhibit slow kinetics in alkaline environments. The *OH accumulation on Pt surface can block active sites, affecting proton reduction and water re‐adsorption. Alloying Ruthenium (Ru) with Pt sites can significantly modulate the adsorption and desorption of water dissociation intermediates. Choosing suitable supports and utilizing metal‐support interaction (MSI) is crucial for active site optimization. PtRu alloy anchored on tungsten oxide (WO3) with rich oxygen vacancies (OV) is prepared through an ultrafast microwave‐assisted approach. Benefiting from the coupling effects between alloying and MSI, PtRu/WO3‐OV exhibits exceptionally high HER activity. In 1 m KOH, 1 m KOH + seawater, and 0.5 m H2SO4, it requires ultralow overpotentials of 9, 26, and 6 mV to achieve 10 mA cm−2, respectively. The designed catalyst surpasses commercial Pt/C in mass activity and demonstrates considerable potential for intermittent energy integration. Density functional theory reveals that alloying Ru with Pt sites significantly reduces the energy barrier of dissociating *OH, modulating blockage on the surface and then promoting the overall alkaline HER process. This study offers insights into the rapid synthesis of non‐carbon supported catalysts with Pt site modulation for alkaline hydrogen generation. [ABSTRACT FROM AUTHOR]

Background: Peripheral blood immunomarkers are associated with prognosis in patients with solid tumors receiving chemotherapy or immunotherapy. In this study, the associations of circulating neutrophil‐to‐lymphocyte ratio (NLR), monocyte‐to‐lymphocyte ratio (MLR), and platelet‐to‐lymphocyte ratio (PLR), as well as their dynamic changes were investigated in relation to the efficacy of immunotherapy in patients with primary liver cancer. Methods: Comparisons were made between NLR, MLR, and PLR among individuals exhibiting disease control (defined as the best response of partial response [PR] or stable disease [SD]) and those with progressive disease (PD). Additionally, disease control rate (DCR), overall survival (OS), and progression‐free survival (PFS) were compared between individuals with different NLR, MLR, and PLR levels before initiating palliative immunotherapy. Furthermore, comparisons were made between patients with different alterations in the ratios at the second cycle of immunotherapy compared to baseline. These analyses were performed using univariate and multivariate approaches. A total of 119 Chinese patients with liver cancer who underwent immunotherapy were included in this study, which focused on hepatocellular carcinoma (HCC). Results: In cases with HCC (n = 104), the cutoffs of NLR, MLR, and PLR to differentiate treatment responders from nonresponders were 3.38, 0.28, and 227.18, respectively. Patients with the best response of PR or SD had significantly lower NLR and MLR. Patients with NLR <3.38 and those with MLR <0.28 significantly had longer OS and PFS than their counterparts, and those with PLR <227.18 had significantly longer PFS, both in overall patients and in various patient subgroups. Lower NLR, MLR, or PLR was associated with earlier BCLC stage, fewer metastatic sites, less frequent extrahepatic metastasis, or better performance status. For individuals who had an unfavorable baseline NLR ≥3.38, MLR ≥0.28, or a favorable baseline PLR <227.18 prior to first immunotherapy, a decrease in NLR, MLR, or PLR at Cycle 2 of immunotherapy was significantly associated with a higher DCR. Conclusions: Among patients with HCC who received immunotherapy, lower NLR, and MLR at baseline in overall patients were significantly associated with better disease control and more favorable survival outcomes (both OS and PFS), and lower PLR was significantly associated with longer PFS. The findings of this research may offer useful hints foranoptimized selection of patients with liver cancer who may benefit more from immunotherapy. [ABSTRACT FROM AUTHOR]