Cascaded orbital-oriented hybridization of intermetallic Pd3Pb boosts electrocatalysis of Li-O2 battery.

Catalysts with a refined electronic structure are highly desirable for promoting the oxygen evolution reaction (OER) kinetics and reduce the charge overpotentials for lithium-oxygen (Li-O2) batteries. However, bridging the orbital interactions inside the catalyst with external orbital coupling between catalysts and intermediates for reinforcing OER catalytic activities remains a grand challenge. Herein, we report a cascaded orbital-oriented hybridization, namely alloying hybridization in intermetallic Pd3Pb followed by intermolecular orbital hybridization between low-energy Pd atom and reaction intermediates, for greatly enhancing the OER electrocatalytic activity in Li-O2 battery. The oriented orbital hybridization in two axes between Pb and Pd first lowers the d band energy level of Pd atoms in the intermetallic Pd3Pb; during the charging process, the low-lying 4dxz/yz and 4dz2 orbital of the Pd further hybridizes with 2π* and 5σ orbitals of lithium superoxide (LiO2) (key reaction intermediate), eventually leading to lower energy levels of antibonding and, thus, weakened orbital interaction toward LiO2. As a consequence, the cascaded orbital-oriented hybridization in intermetallic Pd3Pb considerably decreases the activation energy and accelerates the OER kinetics. The Pd3Pb-based Li-O2 batteries exhibit a low OER overpotential of 0.45 V and superior cycle stability of 175 cycles at a fixed capacity of 1,000 mAh g-1, which is among the best in the reported catalysts. The present work opens up a way for designing sophisticated Li-O2 batteries at the orbital level.

Correction: Understanding antibody-dependent enhancement in dengue: Are afucosylated IgG1s a concern?

[This corrects the article DOI: 10.1371/journal.ppat.1011223.].

Deep learning predicts DNA methylation regulatory variants in the human brain and elucidates the genetics of psychiatric disorders.

There is growing evidence for the role of DNA methylation (DNAm) quantitative trait loci (mQTLs) in the genetics of complex traits, including psychiatric disorders. However, due to extensive linkage disequilibrium (LD) of the genome, it is challenging to identify causal genetic variations that drive DNAm levels by population-based genetic association studies. This limits the utility of mQTLs for fine-mapping risk loci underlying psychiatric disorders identified by genome-wide association studies (GWAS). Here we present INTERACT, a deep learning model that integrates convolutional neural networks with transformer, to predict effects of genetic variations on DNAm levels at CpG sites in the human brain. We show that INTERACT-derived DNAm regulatory variants are not confounded by LD, are concentrated in regulatory genomic regions in the human brain, and are convergent with mQTL evidence from genetic association analysis. We further demonstrate that predicted DNAm regulatory variants are enriched for heritability of brain-related traits and improve polygenic risk prediction for schizophrenia across diverse ancestry samples. Finally, we applied predicted DNAm regulatory variants for fine-mapping schizophrenia GWAS risk loci to identify potential novel risk genes. Our study shows the power of a deep learning approach to identify functional regulatory variants that may elucidate the genetic basis of complex traits.

Carbon-Extraction-Induced Biaxial Strain Tuning of Carbon-Intercalated Iridium Metallene for Hydrogen Evolution Catalysis.

Metallene materials with atomic thicknesses are receiving increasing attention in electrocatalysis due to ultrahigh surface areas and distinctive surface strain. However, the continuous strain regulation of metallene remains a grand challenge. Herein, taking advantage of autocatalytic reduction of Cu2+ on biaxially strained, carbon-intercalated Ir metallene, we achieve control over the carbon extraction kinetics, enabling fine regulation of carbon intercalation concentration and continuous tuning of (111) in-plane (-2.0%-2.6%) and interplanar (3.5%-8.8%) strains over unprecedentedly wide ranges. Electrocatalysis measurements reveal the strain-dependent activity toward hydrogen evolution reaction (HER), where weakly strained Ir metallene (w-Ir metallene) with the smallest lattice constant presents the highest mass activity of 2.89 A mg-1Ir at -0.02 V vs reversible hydrogen electrode (RHE). Theoretical calculations validated the pivotal role of lattice compression in optimizing H binding on carbon-intercalated Ir metallene surfaces by downshifting the d-band center, further highlighting the significance of strain engineering for boosted electrocatalysis.

Silapillar[n]arenes: Their Enhanced Electronic Conjugation and Conformational Versatility.

During recent decades, methylene-bridged macrocyclic arenes have been widely used in supramolecular chemistry. However, their π-conjugations are very weak, as the methylene bridges disrupt the electronic communication between π orbitals of the aromatic units. Herein, we successfully synthesized a series of silapillar[n]arenes (n = 4, 6, and 8) using silylene bridging. These showed enhanced electronic conjugation compared with the parent pillar[n]arenes because of σ*-π* conjugation between σ* (Si-C) orbitals and π* orbitals of the benzenes. Owing to the longer Si-C bond compared with the C-C bond, silylene-bridging provides additional structural flexibility into the pillar[n]arene scaffolds; a strained silapillar[4]arene was formed, which is unavailable in the parent pillar[n]arenes because of the steric requirements. Furthermore, silapillar[n]arenes displayed interesting size-dependent structural and optical properties.

High-Volumetric Density Atomic Cobalt on Multishell ZnxCd1-xS Boosts Photocatalytic CO2 Reduction.

The volumetric density of the metal atomic site is decisive to the operating efficiency of the photosynthetic nanoreactor, yet its rational design and synthesis remain a grand challenge. Herein, we report a shell-regulating approach to enhance the volumetric density of Co atomic sites onto/into multishell ZnxCd1-xS for greatly improving CO2 photoreduction activity. We first establish a quantitative relation between the number of shell layers, specific surface areas, and volumetric density of atomic sites on multishell ZnxCd1-xS and conclude a positive relation between photosynthetic performance and the number of shell layers. The triple-shell ZnxCd1-xS-Co1 achieves the highest CO yield rate of 7629.7 µmol g-1 h-1, superior to those of the double-shell ZnxCd1-xS-Co1 (5882.2 µmol g-1 h-1) and single-shell ZnxCd1-xS-Co1 (4724.2 µmol g-1 h-1). Density functional theory calculations suggest that high-density Co atomic sites can promote the mobility of photogenerated electrons and enhance the adsorption of Co(bpy)32+ to increase CO2 activation (CO2 → CO2* → COOH* → CO* → CO) via the S-Co-bpy interaction, thereby enhancing the efficiency of photocatalytic CO2 reduction.

Childhood urbanicity is associated with emotional episodic memory-related striatal function and common variation in NTRK2.

BACKGROUND: Childhoods in urban or rural environments may differentially affect the risk of neuropsychiatric disorders, possibly through memory processing and neural response to emotional stimuli. Genetic factors may not only influence individuals' choices of residence but also modulate how the living environment affects responses to episodic memory. METHODS: We investigated the effects of childhood urbanicity on episodic memory in 410 adults (discovery sample) and 72 adults (replication sample) with comparable socioeconomic statuses in Beijing, China, distinguishing between those with rural backgrounds (resided in rural areas before age 12 and relocated to urban areas at or after age 12) and urban backgrounds (resided in cities before age 12). We examined the effect of childhood urbanicity on brain function across encoding and retrieval sessions using an fMRI episodic memory paradigm involving the processing of neutral or aversive pictures. Moreover, genetic association analyses were conducted to understand the potential genetic underpinnings that might contribute to memory processing and neural mechanisms influenced by early-life urban or rural environments. RESULTS: Episodic memory retrieval accuracy for more difficult neutral stimuli was similar between those with urban and rural childhoods, whereas aversive stimuli elicited higher retrieval accuracy in the urban group (P = 0.023). For aversive stimuli, subjects with urban childhood had relatively decreased engagement of the striatum at encoding and decreased engagement of the hippocampus at retrieval. This more efficient striatal encoding of aversive stimuli in those with urban childhoods was associated with common variation in neurotrophic tyrosine kinase receptor type 2 (NTRK2) (right striatum: P = 1.58×10-6). These findings were confirmed in the replication sample. CONCLUSIONS: We suggest that this differential striatal processing of aversive stimuli observed in individuals with urban or rural childhoods may represent mechanisms by which childhood urbanicity may affect brain circuits, heightening behavioral responses to negative stressors associated with urban environments. NTRK2-associated neural processes in the striatum may play a role in these processes.

One-Pot Synthesis of MOF@MOF: Structural Incompatibility Leads to Core-Shell Structure and Adaptability Control Makes the Sequence.

Core-shell metal-organic frameworks (MOF@MOF) are promising materials with sophisticated structures that cannot only enhance the properties of MOFs but also endow them with new functions. The growth of isotopic lcore-shell MOFs is mostly limited to inconvenient stepwise seeding strategies with strict requirements, and by far one-pot synthesis is still of great challenge due to the interference of different components. Through two pairs of isoreticular MOFs, it reveals that the structural incompatibility is a prerequisite for the formation of MOFs@MOFs by one-pot synthesis, as illustrated by PMOF-3@HHU-9. It further unveils that the adaptability of the shell-MOF is a more key factor for nucleation kinetic control. MOFs with flexible linkers has comparably slower nucleation than MOFs with rigid linkers (forming PMOF-3@NJU-Bai21), and structural-flexible MOFs built by flexible linkers show the lowest nucleation and the most adaptability (affording NJU-Bai21@HHU-9). This degree of adaptability variation controls the sequence and further facilitates the synthesis of a first triple-layered core-shell MOF (PMOF-3@NJU-Bai21@HHU-9) by one-pot synthesis. The insight gained from this study will aid in the rational design and synthesis of other multi-shelled structures by one-pot synthesis and the further expansion of their applications.

Characterizing utilization patterns and reoperation risk factors of interspinous process devices: analysis of a national claims database.

INTRODUCTION: Interspinous process devices (IPDs) were developed as minimally invasive alternatives to open decompression surgery for spinal stenosis. However, given high treatment failure and reoperation rates, there has been minimal adoption by spine surgeons. This study leveraged a national claims database to characterize national IPD usage patterns and postoperative outcomes after IPD implantation. METHOD: Using the PearlDiver database, we identified all patients who underwent 1- or 2-level IPD implantation between 2010 and 2018. Univariate and multivariable logistic regression was performed to identify predictors of the number of IPD levels implanted and reoperation up to 3 years after the index surgery. Right-censored Kaplan-Meier curves were plotted for duration of reoperation-free survival and compared with log-rank tests. RESULTS: Patients (n = 4865) received 1-level (n = 3246) or 2-level (n = 1619) IPDs. Patients who were older (adjusted odds ratio [aOR] 1.02, 95% confidence interval [CI] 1.01-1.03, P < .001), male (aOR 1.31, 95% CI 116-1.50, P < .001), and obese (aOR 1.19, 95% CI 1.05-1.36, P < .01) were significantly more likely to receive a 2-level IPD than to receive a 1-level IPD. The 3-year reoperation rate was 9.3% of patients when mortality was accounted for during the follow-up period. Older age decreased (aOR 0.97, 95% CI 0.97-0.99, P = .0039) likelihood of reoperation, whereas 1-level IPD (aOR 1.37, 95% CI 1.01-1.89, P = .048), Charlson Comorbidity Index (aOR 1.07, 95% CI 1.01-1.14, P = .018), and performing concomitant open decompression increased the likelihood of reoperation (aOR 1.68, 95% CI 1.35-2.09, P = .0014). CONCLUSION: Compared with 1-level IPDs, 2-level IPDs were implanted more frequently in older, male, and obese patients. The 3-year reoperation rate was 9.3%. Concomitant open decompression with IPD placement was identified as a significant risk factor for subsequent reoperation and warrants future investigation.

Evaluating the reliability of the lateral femoral condyle measuring methods by different modalities for patients with lateral patellar dislocation.

BACKGROUND: A variety of measurement methods and imaging modalities are in use to quantify the morphology of lateral femoral condyle (LFC), but the most reliable method remains elusive in patients with lateral patellar dislocation (LPD). The purpose of this study was to determine the intra- and inter-observer reliability of different measurement methods for evaluating the morphology of LFC on different imaging modalities in patients with LPD. METHODS: Seventy-three patients with LPD were included. Four parameters for quantifying the morphology of LFC were retrospectively measured by three observers on MRI, sagittal CT image, conventional radiograph (CR), and three-dimensional CT (3D-CT). The intra-class correlation coefficient was calculated to determine the intra- and inter-observer reliability. Bland-Altman analysis was conducted to identify the bias between observers. RESULTS: The lateral femoral condyle index (LFCI) showed better intra- and inter-observer reliability on MRI and 3D-CT than on CR and sagittal CT images. The mean difference in the LFCI between observers was lowest on 3D-CT (0.047), higher on MRI (0.053), and highest on sagittal CT images (0.062). The LFCI was associated with the lateral femoral condyle ratio (ρ = 0.422, P = 0.022), lateral condyle index (r = 0.413, P = 0.037), and lateral femoral condyle distance (r = 0.459, P = 0.014). The LFCI could be reliably measured by MRI and 3D-CT. CONCLUSION: The LFCI could be reliably measured by MRI and 3D-CT. The LFCI was associated with both the height and length of LFC and could serve as a comprehensive parameter for quantifying the morphology of LFC in patients with LPD.

Air pollution interacts with genetic risk to influence cortical networks implicated in depression.

Air pollution is a reversible cause of significant global mortality and morbidity. Epidemiological evidence suggests associations between air pollution exposure and impaired cognition and increased risk for major depressive disorders. However, the neural bases of these associations have been unclear. Here, in healthy human subjects exposed to relatively high air pollution and controlling for socioeconomic, genomic, and other confounders, we examine across multiple levels of brain network function the extent to which particulate matter (PM2.5) exposure influences putative genetic risk mechanisms associated with depression. Increased ambient PM2.5 exposure was associated with poorer reasoning and problem solving and higher-trait anxiety/depression. Working memory and stress-related information transfer (effective connectivity) across cortical and subcortical brain networks were influenced by PM2.5 exposure to differing extents depending on the polygenic risk for depression in gene-by-environment interactions. Effective connectivity patterns from individuals with higher polygenic risk for depression and higher exposures with PM2.5, but not from those with lower genetic risk or lower exposures, correlated spatially with the coexpression of depression-associated genes across corresponding brain regions in the Allen Brain Atlas. These converging data suggest that PM2.5 exposure affects brain network functions implicated in the genetic mechanisms of depression.

Beta Oscillations in the Sensory Thalamus During Severe Facial Neuropathic Pain Using Novel Sensing Deep Brain Stimulation.

OBJECTIVE: Advancements in deep brain stimulation (DBS) devices provide a unique opportunity to record local field potentials longitudinally to improve the efficacy of treatment for intractable facial pain. We aimed to identify potential electrophysiological biomarkers of pain in the ventral posteromedial nucleus (VPM) of the thalamus and periaqueductal gray (PAG) using a long-term sensing DBS system. MATERIALS AND METHODS: We analyzed power spectra of ambulatory pain-related events from one patient implanted with a long-term sensing generator, representing different pain intensities (pain >7, pain >9) and pain qualities (no pain, burning, stabbing, and shocking pain). Power spectra were parametrized to separate oscillatory and aperiodic features and compared across the different pain states. RESULTS: Overall, 96 events were marked during a 16-month follow-up. Parameterization of spectra revealed a total of 62 oscillatory peaks with most in the VPM (77.4%). The pain-free condition did not show any oscillations. In contrast, ß peaks were observed in the VPM during all episodes (100%) associated with pain >9, 56% of episodes with pain >7, and 50% of burning pain events (center frequencies: 28.4 Hz, 17.8 Hz, and 20.7 Hz, respectively). Episodes of pain >9 indicated the highest relative ß band power in the VPM and decreased aperiodic exponents (denoting the slope of the power spectra) in both the VPM and PAG. CONCLUSIONS: For this patient, an increase in ß band activity in the sensory thalamus was associated with severe facial pain, opening the possibility for closed-loop DBS in facial pain.

Meta-analyses of motivational factors of response to natural disaster.

Response behavior of individuals is of critical importance to decrease chances of injury and death as well as ameliorate costs in property and infrastructure damage in natural disasters. Plenty of studies have examined which factors motivate individuals to respond to natural disasters. However, a systematic overview of the key motivating factors of various response behaviors is lacking. This study conducts a series of meta-analyses using data of 53,713 samples from 87 studies (77 papers) conducted in 27 different countries and regions to examine how 17 motivational factors were associated with individuals' response to natural disasters. The results indicate self-efficacy, outcome efficacy, attitudes, subjective norms, and information acquisition show the strongest effects on response behavior. Contrarily, the impact of negative affects like fear, depression, and anxiety on victims is minimal, despite the common assumption that they are significant related to response behaviour. In addition, current studies have disproportionally focused on studying risk perception, experience and information acquisition, earthquake and hurricane, and evacuation and preparation, while attention given to other types of motivational factors, disasters and response behaviors is lacking.

Efficient Photosynthesis of Hydrogen Peroxide by Cyano-Containing Covalent Organic Frameworks from Water, Air and Sunlight.

The insufficient exciton (e- -h+ pair) separation/transfer and sluggish two-electron water oxidation are two main factors limiting the H2 O2 photosynthetic efficiency of covalent organic frameworks (COFs) photocatalysts. Herein, we present an alternative strategy to simultaneously facilitate exciton separation/transfer and reduce the energy barrier of two-electron water oxidation in COFs via a dicyano functionalization. The in situ characterization and theoretical calculations reveal that the dicyano functionalization improves the amount of charge transfer channels between donor and acceptor units from two in COF-0CN without cyano functionalization to three in COF-1CN with mono-cyano functionalization and four in COF-2CN with dicyano functionalization, leading to the highest separation/transfer efficiency in COF-2CN. More importantly, the dicyano group activates the neighbouring C atom to produce the key *OH intermediate for effectively reducing the energy barrier of rate-determining two-electron water oxidation in H2 O2 photosynthesis. The simultaneously enhanced exciton separation/transfer and two-electron water oxidation in COF-2CN result in high H2 O2 yield (1601 µmol g-1 h-1 ) from water and oxygen without using sacrificial reagent under visible-light irradiation. COF-2CN can effectively yield H2 O2 in water with wide pH range, in different real water samples, in scaled-up reactor under natural sunlight irradiation, and in continuous-flow reactor for consecutively producing H2 O2 solution for water decontamination.

Friedel-Crafts Acylation for Accessing Multi-Bridge-Functionalized Large Pillar[n]arenes.

Pillar[n]arenes can be constructed using a Friedel-Crafts alkylation process. However, due to the reversible nature of the alkylation, mixture of large pillar[n]arenes (n≥7) are obtained as minor products, and thus laborious purification are necessary to isolate the larger pillar[n]arenes. Moreover, inert methylene bridges are introduced during the alkylation process, and the multi-functionalization of the bridges has never been investigated. Herein, an irreversible Friedel-Crafts acylation is used to prepare pillar[n]arenes. Due to the irreversible nature of the acylation, the reaction of precursors bearing carboxylic acids and electron-rich arene rings results in a size-exclusive formation of pillar[n]arenes, in which the ring-size is determined by the precursor length. Because of this size-selective formation, laborious separation of undesired macrocycles is not necessary. Moreover, the bridges of pillar[n]arenes are selectively installed with reactive carbonyl groups using the acylation method, whose positions are determined by the precursor used. The carbonyl bridges can be easily converted into versatile functional groups, leading to various laterally modified pillar[n]arenes, which cannot be accessed by the alkylation strategy.

Breaking the Scaling Relationship in C-N Coupling via the Doping Effects for Efficient Urea Electrosynthesis.

Electrochemical C-N coupling reaction based on carbon dioxide and nitrate have been emerged as a new "green synthetic strategy" for the synthesis of urea, but the catalytic efficiency is seriously restricted by the inherent scaling relations of adsorption energies of the active sites, the improvement of catalytic activity is frequently accompanied by the decrease in selectivity. Herein, a doping engineering strategy was proposed to break the scaling relationship of intermediate binding and minimize the kinetic barrier of C-N coupling. A thus designed SrCo0.39Ru0.61O3-δ catalyst achieves a urea yield rate of 1522 µg h-1 mgcat. -1 and faradic efficiency of 34.1 % at -0.7 V versus reversible hydrogen electrode. A series of characterizations revealed that Co doping not only induces lattice distortion but also creates rich oxygen vacancies (OV) in the SrRuO3. The oxygen vacancies weaken the adsorption of *CO and *NH2 intermediates on the Co and Ru sites respectively, and the strain effects over the Co-Ru dual sites promoting the occurrence of C-N coupling of the two monomers instead of selective hydrogenating to form by-products. This work presents an insight into molecular coupling reactions towards urea synthesis via the doping engineering on SrRuO3.

Halide Superionic Conductors with Non-Close-Packed Anion Frameworks.

Halide superionic conductors (SICs) are drawing significant research attention for their potential applications in all-solid-state batteries. A key challenge in developing such SICs is to explore and design halide structural frameworks that enable rapid ion movement. In this work, we show that the close-packed anion frameworks shared by traditional halide ionic conductors face intrinsic limitations in fast ion conduction, regardless of structural regulation. Beyond the close-packed anion frameworks, we identify that the non-close-packed anion frameworks have great potential to achieve superionic conductivity. Notably, we unravel that the non-close-packed UCl3-type framework exhibit superionic conductivity for a diverse range of carrier ions, including Li+, Na+, K+, and Ag+, which are validated through both ab initio molecular dynamics simulations and experimental measurements. We elucidate that the remarkable ionic conductivity observed in the UCl3-type framework structure stems from its significantly more distorted site and larger diffusion channel than its close-packed counterparts. By employing the non-close-packed anion framework as the key feature for high-throughput computational screening, we also identify LiGaCl3 as a promising candidate for halide SICs. These discoveries provide crucial insights for the exploration and design of novel halide SICs.

Fluorination of Covalent Organic Framework Reinforcing the Confinement of Pd Nanoclusters Enhances Hydrogen Peroxide Photosynthesis.

Metal-isolated clusters (MICs) physically confined on photoactive materials are of great interest in the field of photosynthesis of hydrogen peroxide (H2O2). Despite recent important endeavors, weak confinement of MICs in the reported photocatalytic systems leads to their low catalytic activity and stability. Herein, we report a new strategy of fluorinated covalent organic frameworks (COFs) to strongly confine Pd ICs for greatly boosting the photocatalytic activity and stability of H2O2 photosynthesis. Both experimental and theoretical results reveal that strong electronegative fluorine can increase the metal-support interaction and optimize the d-band center of Pd ICs, thus significantly enhancing the stability and activity of photocatalytic H2O2. An optimal TAPT-TFPA COFs@Pd ICs photocatalyst delivers a stable H2O2 yield rate of 2143 µmol h-1 g-1. Most importantly, the as-made TAPT-TFPA COFs@Pd ICs exhibit high catalytic stability over 100 h, which is the best among the reported materials.

Isomer of NU-1000 with a Blocking c-pore Exhibits High Water-Vapor Uptake Capacity and Greatly Enhanced Cycle Stability.

Chemically and hydrolytically stable metal-organic frameworks (MOFs) have shown great potential for many water-adsorption-related applications. However, MOFs with large pores that show high water-uptake capacity and high hydrolytic and mechanical cycle stability are rare. Through a deliberate adjustment of the linker of a typical zirconium-based MOF (Zr-MOF) (NU-1000), a new isomer of NU-1000 with blocked c-pores, but large mesopores was successfully synthesized. This new isomer, ISO-NU-1000, exhibits excellent water stability, one of the highest water vapor uptake capacities, and excellent cycle stability, making it a promising candidate for water-vapor-sorption-based applications such as water-adsorption-driven heat transfer. We find that the high water-cycling stability of ISO-NU-1000 is traceable to its blocking c-pore that hinders the hydrolysis of node-coordinating formate in the c-pore area and thereby prevents the introduction of node aqua and terminal hydroxo ligands. With the absence of these ligands and their ability to hydrogen-bond to channel-located water molecules, the strength of guest (water)/host (MOF) interactions is diminished and the absolute magnitude of the capillary force exerted by water during its evacuation from MOF channels is attenuated. The attenuation leaves the MOF capable of resisting pore collapse, capacity loss, and crystallinity loss during repetitive evaporative removal (and re-introduction) of water from pores.

Cooperative Rh-O5/Ni(Fe) Site for Efficient Biomass Upgrading Coupled with H2 Production.

Designing efficient and durable bifunctional catalysts for 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) and hydrogen evolution reaction (HER) is desirable for the co-production of biomass-upgraded chemicals and sustainable hydrogen, which is limited by the competitive adsorption of hydroxyl species (OHads) and HMF molecules. Here, we report a class of Rh-O5/Ni(Fe) atomic site on nanoporous mesh-type layered double hydroxides with atomic-scale cooperative adsorption centers for highly active and stable alkaline HMFOR and HER catalysis. A low cell voltage of 1.48 V is required to achieve 100 mA cm-2 in an integrated electrolysis system along with excellent stability (>100 h). Operando infrared and X-ray absorption spectroscopic probes unveil that HMF molecules are selectively adsorbed and activated over the single-atom Rh sites and oxidized by in situ-formed electrophilic OHads species on neighboring Ni sites. Theoretical studies further demonstrate that the strong d-d orbital coupling interactions between atomic-level Rh and surrounding Ni atoms in the special Rh-O5/Ni(Fe) structure can greatly facilitate surface electronic exchange-and-transfer capabilities with the adsorbates (OHads and HMF molecules) and intermediates for efficient HMFOR and HER. We also reveal that the Fe sites in Rh-O5/Ni(Fe) structure can promote the electrocatalytic stability of the catalyst. Our findings provide new insights into catalyst design for complex reactions involving competitive adsorptions of multiple intermediates.