Search Results (2,744)

The increasing occurrence of pharmaceutical contaminants in aquatic environments has intensified the demand for sustainable and cost-effective water treatment technologies. This study investigated the conversion of potato peel waste into carbonaceous adsorbents through hydrothermal carbonization (HTC) and conventional pyrolysis (PRYR) for the removal of carbamazepine (CBZ) from synthetic wastewater. Hydrochars and biochars were synthesized under varying processing conditions and characterized using scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), elemental analysis, and Brunauer–Emmett–Teller (BET) surface area analysis. Adsorption experiments were conducted using a 50 mg/L CBZ solution at pH 6, room temperature, and an adsorbent dosage of 1 g/L. The adsorption performance was evaluated after short contact times to assess rapid-removal capability. HTC-derived hydrochars exhibited significantly superior performance compared with pyrolysis-derived biochars, achieving up to 97% CBZ removal and adsorption capacities approaching 50 mg g⁻¹ within 1 min of contact. In contrast, pyrolysis-derived biochars achieved removal efficiencies between approximately 7 and 55% under similar conditions. Correlation analysis between adsorption behaviour and physicochemical properties revealed that adsorption performance was more strongly influenced by surface chemistry, aromaticity, and mesoporosity than by BET surface area alone. FTIR analysis suggested that hydrogen bonding, π–π electron donor–acceptor interactions, and pore filling contributed to CBZ adsorption. HTC hydrochars retained abundant oxygen-containing functional groups that promoted rapid and stable adsorption, whereas pyrolysis-derived biochars exhibited weaker adsorption interactions despite possessing higher surface areas. The findings demonstrate that hydrothermal carbonization provides an effective low-temperature route for valorising potato peel waste into efficient adsorbents for rapid pharmaceutical removal from water and highlight the critical role of adsorbent surface chemistry in determining adsorption performance. Full article

Per- and polyfluoroalkyl substances (PFASs) are persistent environmental contaminants whose mobility in soil and groundwater is strongly controlled by adsorption and desorption processes. In saturated clay-rich soils, these processes are complex because PFASs interact with hydrated mineral surfaces, organic matter, metal oxides, exchangeable cations, and pore-water constituents. This review synthesizes the current literature on PFAS adsorption and desorption in saturated soils, with an emphasis on clay mineralogy, mineral–water interfaces, pore-water chemistry, and electrochemical double layer (EDL) effects. PFAS retention is influenced by molecular properties such as chain length, functional head group, and charge state, as well as soil properties such as organic carbon content, clay mineral type, surface charge, cation exchange capacity, and Fe/Al oxide content. Longer-chain PFASs and sulfonate-based compounds generally show stronger retention, while shorter-chain PFASs tend to remain more mobile. This review focuses particularly on how an EDL affects PFAS behavior in saturated clay systems. Unlike dry clay surfaces, saturated clay surfaces are covered by structured water, exchangeable ions, and diffuse counterion layers. These hydrated interfacial conditions influence how closely anionic PFASs can approach negatively charged clay surfaces, how dissolved cations reduce electrostatic repulsion or promote cation-mediated binding, and how effectively short-range interactions such as hydrophobic association, van der Waals forces, hydrogen bonding, and surface association contribute to adsorption. Desorption is also emphasized because adsorption does not necessarily represent permanent immobilization. Changes in pH, ionic strength, cation composition, dissolved organic matter, or competing solutes can weaken retention and promote PFAS release. Overall, PFAS mobility in saturated clay-rich soils should be interpreted as a coupled interfacial process rather than simple partitioning to soil solids. Future work should better connect molecular-scale mechanisms, EDL behavior, adsorption–desorption experiments, and saturated transport studies to improve predictions of PFAS retention and long-term groundwater release. Full article

Coniferyl alcohol and coniferyl aldehyde are precursors of lignin and are used in spices and the pharmaceutical industry. In this work, antioxidant, anticholinergic, antidiabetic, and antiglaucoma effects of coniferyl alcohol and aldehyde were evaluated and compared against the standards. To determine the antioxidant capacities of coniferyl alcohol and aldehyde, ABTS^•+, DMPD^•+ and DPPH^• scavenging abilities as well as cupric ion (Cu²⁺) reduction, ferrous ions (Fe²⁺) reduction and Fe³⁺-TPTZ reduction activities were studied. Butylated hydroxytoluene (BHT), ascorbic acid, α-Tocopherol, Trolox, and butylated hydroxyanisole (BHA) were used as the standard antioxidants. When the antioxidant effects of coniferyl alcohol and coniferyl aldehyde are compared to the standards, they exhibit significant antioxidant effects. In addition, it was determined that coniferyl alcohol and coniferyl aldehyde had a high degree of inhibition effect towards carbonic anhydrase (hCA) I and II isoforms purified from human erythrocytes, α-glycosidase, butyrylcholinesterase (BChE), acetylcholinesterase (AChE), and α-amylase as in vitro and in silico. Molecular docking studies revealed favorable binding affinities of coniferyl alcohol and coniferyl aldehyde toward all investigated enzymes, with key hydrogen bonding and π–π interactions identified at the active sites. The docking findings were found to be compatible with the in vitro enzyme inhibition results, supporting the proposed multi-target biological potential of both compounds. Molecular docking studies revealed favorable binding affinities of coniferyl alcohol and coniferyl aldehyde toward all investigated enzymes. Key hydrogen bonding and π–π interactions were identified within the active sites, particularly for AChE and hCA II. The docking results were consistent with the in vitro enzyme inhibition data, supporting their multi-target biological potential. Docking demonstrated that both compounds can effectively interact with the catalytic regions of the target enzymes. The identified binding modes and interaction patterns support the observed inhibitory activities and provide a molecular basis for their multi-target biological effects. Full article

To understand glycan–protein interactions at biological interfaces, designing surfaces modified with structurally controlled glycans is highly important. In particular, naturally occurring glycosaminoglycans (GAGs) possess periodic sugar arrangements that play important roles in protein recognition, highlighting the need for the development of periodic glycopolymer model systems that can serve as GAG mimics for quantitative interaction analysis. In this study, sequence-controlled periodic glycopolymers were synthesized by reversible addition–fragmentation chain-transfer (RAFT) polymerization and immobilized onto gold surfaces to construct glycan-modified interfaces. The synthesized material was a terminally functionalized periodic glycopolymer with the most basic structure, consisting of alternating maltose-containing vinyl ether (MalVE) units and ethyl maleimide (EtMI) units, with a trithiocarbonate group at the ω-terminal. This trithiocarbonate group was converted to a thiol group for immobilization through Au–S bond formation. Structural characterization by ¹H NMR spectroscopy, size exclusion chromatography (SEC), MALDI-TOF mass spectrometry, and UV–vis spectroscopy confirmed the structure as designed. Quartz crystal microbalance (QCM) measurements verified the stable immobilization of thiol-terminated periodic glycopolymers on the gold surface, and allowed for estimation of graft density and quantitative analysis of glycan-protein interactions at the modified interface. The periodic glycopolymer-modified surfaces exhibited selective binding behavior toward concanavalin A (ConA) compared to bovine serum albumin (BSA), with apparent binding constants on the order of 10⁶–10⁷ L mol⁻¹. This enhanced binding behavior indicated that specific and multivalent interactions with proteins also occurred at periodic pendant maltose residues along the main chain. These results demonstrate that the gold surface modified with end-functional periodic glycopolymers synthesized by RAFT polymerization provides a versatile platform for quantitative analysis of glycan-protein interactions and suggests potential applications for periodic glycopolymers as functional materials. Full article

Co-contamination of biphenyl and heavy metals is widespread in industrial environments, but systematic studies on the simultaneous treatment of both pollutants using a single microbial strategy remain limited. In this study, we characterized the biphenyl degradation performance, metabolic pathway, transcriptomic response, and Cr(VI) tolerance of Rhodococcus sp. TG-1, and developed an alkali-modified biochar immobilization system to enhance its degradation efficiency for biphenyl under Cr(VI) stress. Degradation experiments were carried out under optimal conditions (30 °C, pH 7.0), and it was found that strain TG-1 degraded 76.84% of 300 mg/L biphenyl within 3 days. Intermediate metabolites were identified by LC-MS, and five key intermediates were detected, confirming that TG-1 metabolizes biphenyl via the classical 2,3-dihydroxybiphenyl dioxygenase pathway, with subsequent entry into the tricarboxylic acid cycle. Transcriptomic analysis was performed to profile gene expression, revealing 845 differentially expressed genes under biphenyl stress, including 672 upregulated genes significantly enriched in aromatic degradation pathways. Seven complete bph gene clusters responsible for biphenyl catabolism were also identified. Strain TG-1 exhibited high tolerance to Cr(VI), with a minimum inhibitory concentration (MIC) of 500 mg/L. However, its biphenyl degradation efficiency dropped to 51.32% in the presence of 200 mg/L Cr(VI). After immobilization using alkali-modified straw biochar (JBC), heavy metal toxicity was alleviated, and the biphenyl removal rate increased to 99.30% under co-contamination conditions. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) analyses confirmed that TG-1 was stably loaded onto the biochar surface through hydrogen bonding and electrostatic interactions. Altogether, this study provides a promising bacterial strain and a green immobilization strategy for enhancing biphenyl removal in the presence of Cr(VI), offering a practical approach for the treatment of environments co-contaminated with aromatic compounds and heavy metals. Full article

The valorization of phosphogypsum (PG), a byproduct of phosphoric acid production, along with waste glass (WG) and silica fume (SF) into value-added materials has attracted growing attention in recent years. The present study aims to synthesize three types of porous geopolymers (GD, GDP, and GDG) using Tunisian clay and locally available mineral wastes, and to investigate their potential as low-cost adsorbents for the removal of methylene blue (MB) dye from aqueous solutions. The physicochemical characteristics of the raw precursors and the resulting porous geopolymers were analyzed using various techniques, including FTIR, XRD, BET, and SEM. Variations in Si/Al, Na/Al, and Ca/Al ratios play a critical role in the geopolymer structure. The high Ca/Al ratio in GDP (porous geopolymer from calcined clay and phosphogypsum) promotes the formation of C-A-S-H, leading to increased macroporosity, which favors adsorption capacity despite the presence of a more heterogeneous morphology. The results indicated that the maximum adsorption capacity (Qmax) for MB dye was obtained for the GDP sample, reaching 68 mg/g. Adsorption experiments revealed the successful removal of MB dye by geopolymers, with the Langmuir isotherm and pseudo-second-order kinetic models adequately describing the adsorption process. The MB uptake by geopolymers was facilitated by weak physicochemical interactions, including electrostatic attraction, hydrogen bonding, and π–π interactions. This study proposes a simple and effective alkali activation strategy that combines different industrial wastes within a single geopolymer system, resulting in improved porosity and adsorption efficiency. Overall, the findings highlight the potential of these waste-derived geopolymers as promising and sustainable adsorbents for wastewater treatment applications. Full article

Ammonia decomposition over non-precious metal thermos-catalysts offers a viable and cost-effective pathway for sustainable hydrogen production. In this study, LaCeO₃ perovskite was synthesized using a citric acid complexation method and employed as a support for mono- and bimetallic catalysts prepared by incipient wetness impregnation, maintaining a total metal loading of 10 wt%. Structural and surface properties were systematically investigated using BET, XRD, H₂-TPR, SEM, TEM, and CO₂-TPD. Among the monometallic catalysts (Ni, Co, and Fe), 10%Ni/LaCeO₃ exhibited the highest activity, which is attributed to its enhanced reducibility and optimal surface basicity, facilitating NH₃ activation. Bimetallic systems (Ni-Co, Ni-Fe, and Co-Fe) with equal metal loadings (5 wt% each) showed better activity compared to their monometallic counterparts following the order: 5%Ni–5%Co/LaCeO₃ > 5%Ni–5%Fe/LaCeO₃ > 5%Co–5%Fe/LaCeO₃. The improved performance of the Ni-Co system is due to structural interactions between Ni and Co, which promote hydrogen desorption and accelerate N–H bond cleavage, while suppressing nitrogen recombination as the rate-limiting step. Further systematic optimization of the Ni/Co ratio showed that 8%Ni–2%Co/LaCeO₃ had the highest catalytic activity with consistent performance over 50 h. This optimal composition provides a balanced distribution of active metallic sites and moderate-to-strong basic sites, enhancing NH₃ adsorption and intermediate transformation. These findings show that LaCeO₃-supported Ni-Co catalysts are promising candidates for efficient hydrogen production from ammonia without using noble metals. Full article

Effective abatement of nitrogen oxides (NO_x) is achieved by ammonia selective catalytic reduction (NH₃-SCR). In this paper, the effects of single WO₃ doping and WO_x-VO_x co-doping into the MnO_x/TiO₂ catalyst on NH₃-SCR of NO_x removal, sulfur and water resistance, and reaction mechanisms were systematically investigated. The 5MnO_x/TiO₂, WO₃-5MnO_x/TiO₂, and WO₃-V₂O₅-5MnO_x/TiO₂ were prepared using the incipient-wetness impregnation method. Furthermore, the monolithic WO₃-V₂O₅-5MnO_x/TiO₂-CC (cordierite support) catalyst involved a coating process. The WO₃-V₂O₅-5MnO_x/TiO₂ catalyst demonstrated superior NO conversion and maintained over 80% activity following prolonged exposure to SO₂ and H₂O. Characterization results indicated that the introduction of WO₃ regulated Mn valence through the formation of W-O-Mn bonds. The synergistic effect of V₂O₅ and WO₃ further promoted electron transfer, increased surface chemisorbed oxygen and oxygen vacancies, and strengthened reactant adsorption and activation. In situ DRIFTS analysis suggested that WO₃ modulated the reaction pathway, and while 5MnO_x/TiO₂ followed the Langmuir–Hinshelwood (L-H) mechanism, both WO₃-5MnO_x/TiO₂ and WO₃-V₂O₅-5MnO_x/TiO₂ exhibited a combined L-H and Eley–Rideal (E-R) pathway. This study confirmed that WO₃ played a crucial regulatory role in both single-metal and multi-metal systems, and the synergistic interaction between V₂O₅ and WO₃ was the key to achieving superior denitration performance and poisoning resistance. Full article

4-Ethylguaiacol (4-EG) is a volatile phenolic compound associated with smoky, woody, and spicy aroma notes in fermented foods and beverages, including Baijiu. In this study, a 4-EG-producing strain, designated JN11, was obtained by screening isolates from Baijiu pit mud and identified as Bacillus coagulans based on morphological, physiological, biochemical, and 16S rRNA analyses. In sorghum juice medium, strain JN11 produced 271.6 ± 2.7 μg/L 4-EG. To investigate the upstream decarboxylation step involved in volatile phenol formation, the phenolic acid decarboxylase gene, BcPAD, was cloned and heterologously expressed in Escherichia coli BL21(DE3). The BcPAD gene comprises 504 bp and encodes a 167-amino-acid protein. Recombinant BcPAD exhibited maximal activity at pH 6.0 and 50 °C and retained more than 60% residual activity after 5 h at 30–40 °C. Fe³⁺ increased enzyme activity to 115.36% of the control, whereas Zn²⁺ markedly inhibited enzyme activity and SDS completely inactivated the enzyme. BcPAD showed the highest activity toward p-coumaric acid, with a specific activity of 460.6 ± 18.3 U/mg and a catalytic efficiency (Kcat/Km) of 12.1 ± 1.4 mM⁻¹·s⁻¹, while lower activities were observed toward caffeic acid and ferulic acid, and no activity was detected toward sinapic acid. Homology modeling and molecular docking suggested that the superior catalytic performance toward p-coumaric acid may be related to favorable hydrogen-bonding interactions and substrate orientation within the active site. Although 4-EG production was observed during fermentation by strain JN11, BcPAD was biochemically characterized as a phenolic acid decarboxylase likely responsible for the upstream formation of vinyl derivatives in the proposed pathway. These findings improve our understanding of phenolic acid decarboxylases from B. coagulans and provide a basis for further investigation of the roles of strain JN11 and BcPAD in volatile phenol formation during Baijiu production. Full article

The interfacial behavior of hybrid nanoparticles on biological substrates governs their functional performance. Here, we investigate how surface properties and colloidal stability dictate the pH-dependent adhesion of oxybenzone-loaded palygorskite nanohybrids to hair—a model biological interface. A series of hybrids with 5–50% oxybenzone loadings were prepared via melt impregnation. XRD and FTIR analyses confirm hydrogen bonding between oxybenzone and palygorskite, forming stable organic–inorganic hybrids. The colloidal stability of these nanohybrids varies non-monotonically with oxybenzone loading, governed by surface hydrophilicity and zeta potential, exhibiting a network-like behavior upon pH change. Optimal stability is achieved at an intermediate loading with a favorable balance of surface properties. While pristine hybrids show no affinity for hair, surface modification with cationic polyquaternium-7 (PQ-7) or non-ionic polyvinylpyrrolidone (PVP) enables effective deposition through distinct pH-dependent mechanisms: PQ-7 operates optimally at pH 10 via electrostatic attraction, whereas PVP performs best at pH 4 through hydrogen bonding, forming a protective coating layer on the hair surface. Deposition fails for PVP-modified hybrids at 50% loading due to excessive surface hydrophobicity. The deposited hybrids provide exceptional UV protection, significantly mitigating cuticle damage, suppressing photo-yellowing, and minimizing protein oxidation. Among the hybrids, hybrid-35 exhibited the best colloidal stability, whereas PQ-7-modified hybrid-50 gave the highest UV protection (color difference ΔE reduced from 10.51 to 1.60). The adhesion rates of the two best-performing hybrids were 2.70% and 2.85%, respectively. Beyond hair protection, we evaluate the environmental interface of these materials. While free oxybenzone is highly toxic to Chlorella vulgaris, hybridization drastically reduces its ecotoxicity. Remarkably, palygorskite and the hybrids promote algal growth, likely by acting as nutrient adsorbents and attachment sites. This work provides fundamental insights into particle–biointerface interactions and offers a strategy for designing functional hybrid materials with tailored surface properties for bio-related applications. Full article

The selective conversion of syngas (CO + H₂) to higher alcohols (C₂₊OH) via Fischer–Tropsch synthesis (FTS) is a strategically important but challenging process, requiring catalysts that can simultaneously sustain C–C chain growth and preserve C–O bonds in reactive intermediates. Over the past decade (2015–2025), perovskite-type complex oxides with the formula ABO₃ have emerged as powerful precatalysts for this application, with LaCoO₃ attracting particular attention due to its structural flexibility, controllable reducibility, and the unique catalytic role of the La₂O₃ phase formed upon reduction. This review systematically covers recent advances in synthesis strategies for LaCoO₃ and substituted perovskites, including sol–gel, co-precipitation, mechanochemical, and template-assisted (KIT-6, SBA-15) methods; effects of A-site (Sr) and B-site (Cu, Ga, Ni, Mn) substitution on reducibility, active phase dispersion, and product selectivity; alkali promotion and its interaction with the perovskite-derived active phase; mechanistic understanding of the alcohol-forming pathway, including the Co⁰/Co³⁺ bifunctional site concept, CO insertion mechanism, and the role of La₂O₃ in suppressing the Boudouard reaction; and catalyst stability and deactivation pathways under FTS conditions. Original data from LaCoO₃ catalysts prepared by co-precipitation with ethylene glycol (LCO-1: S_KOH = 90%, Y_KOH = 57 mg·g⁻¹·h⁻¹) and via citrate/KIT-6 template synthesis (LCO/KIT-6: Y_KOH = 80 mg·g⁻¹·h⁻¹, S_BET = 220 m²/g) at 240 °C and 2 MPa serve as the primary experimental reference throughout. Key challenges, including the surface area–selectivity trade-off, long-term stability under industrial conditions, and opportunities in CO₂ hydrogenation, are critically discussed. Full article

Trichothecenes are the most common Fusarium mycotoxin contaminants of grains and their related products. Searching for effective adsorbents remains a major challenge in mycotoxicology, due to the low polarity and bulky chemical structure of type A trichothecenes. This study aimed to investigate in silico chitosan binding to type A trichothecenes such as diacetoxyscirpenol (DAS), neosolaniol (NEO), T-2 toxin (T2), and HT-2 toxin (HT2) and to study in vitro the devil fish chitosan biosorption capacity under two pH conditions (pHs 3 and 8). Molecular dynamic experiments showed that the chitosan monomers D-glucosamine and N-acetyl-D-glucosamine mostly bound to trichothecenes through the O in hydroxyls and glycosidic bonds and through their functional groups containing nitrogen. DAS exhibited a 9.44-, 6.39-, and 4.54-fold increase in the number of intermolecular contacts with chitosan compared to NEO, HT2 and T2, respectively. Moreover, in vitro experiments showed that at pH 3, chitosan exhibited a significant DAS sorption efficiency of 31.60% (p < 0.005), corresponding to a mass-normalized sorption capacity of 126.4 ng/mg. In contrast, no significant differences in sorption were observed at pH 8 (p > 0.05). Regarding NEO, T2, and HT2, no significant adsorption was detected under either pH condition (p > 0.05). This study is the first attempt to elucidate chitosan’s capacity to bind DAS and propose a mechanism for that interaction. Full article

Hydroxypropyl methylcellulose hydrogels were designed as polymeric matrices for porphyrinic photosensitizer samples (5-(2-hydroxy-5-methoxyphenyl)-10,15,20-tris-(4-carboxymethylphenyl) porphyrin (P3.2) and 5,10,15,20-tetrakis-(4-carboxymethylphenyl) porphyrin (P3.1) to investigate their physicochemical behavior and structure–property relationships. Fourier transform infrared, UV–Vis, and fluorescence spectroscopy showed that both porphyrins remained monomerically dispersed in the polymeric matrix by establishing moderate interactions with HPMC by hydrogen bonding. X-ray diffraction and atomic force microscopy showed the uniform microstructural organization of the hydrogel matrix, while thermal analyses confirmed the stability of both studied systems. Rheological measurements demonstrated that the incorporation of porphyrins in the hydrogel network slightly modulates viscoelastic behavior. The swelling, density, and pH studies highlighted correlations between molecular interactions and macroscopic hydrogel properties. The swelling ratio determined after 6 h showed values of about 89% for the hydrogel of HPMC with P3.1. and about 92% for the hydrogel of HPMC with P3.2, respectively. The pH value was found to be 7.0 for both hydrogels. These results highlighted interfacial and physicochemical insights into polymer–porphyrin interactions in hydrogel matrices. All studies show that a controlled dispersion of chromophores preserves their monomeric state and controlled structure–property relationships. Full article

Bacteria-infected wounds remain a major global biomedical challenge, with persistent inflammation and the lack of real-time monitoring significantly impairing wound healing. To address the limitations of conventional dressings, which often provide single-function and static treatment, we developed a multifunctional HP@CGA hydrogel based on methacrylated hyaluronic acid (HA-MA) and polyvinyl alcohol (PVA), incorporating chlorogenic acid (CGA) and bromothymol blue (BTB). In the presence of a photoinitiator, the methacryloyl groups of HA-MA undergo UV-induced free-radical polymerization to form a covalently crosslinked network, while PVA chains interact with the HA-MA backbone through hydrogen bonding and physical entanglement, resulting in a stable interpenetrating double-network structure. This integrated “treatment + monitoring” design offers a low-cost and convenient alternative to conventional wound dressings and separate sensing systems. Material characterization and preliminary experiments demonstrated that the hydrogel enabled visual pH detection within the range of 6.0–8.0 through distinct color changes. In addition, it exhibited excellent antibacterial activity, achieving antibacterial rates of 99.9% ± 0.08% against both S. aureus and E. coli. These results demonstrate the multifunctional performance of the HP@CGA hydrogel, including bacterial inhibition, inflammation alleviation, and real-time wound pH feedback, thereby providing a favorable microenvironment for infected wound healing. This work highlights the potential of HP@CGA hydrogel for precise and intelligent wound care. Full article

Whether copper fundamentally alters Mo-centered redox thermodynamics or mainly tunes hydrogen adsorption in Ni–Mo electrocatalysts under alkaline hydrogen evolution reaction (HER) conditions remains unresolved. Density functional theory calculations combined with a field-corrected computational hydrogen electrode framework are used to evaluate the thermodynamic stability of H₃Mo, H₃MoOH, H₂Mo(OH)₂, and MoO(OH)₃ on Cu(111) and Ni(111) and to construct surface Pourbaix diagrams under electrochemical conditions. The results show that substrate identity reorganizes the redox stabilization hierarchy of these Mo intermediates. Across the examined conditions, at least one of H₃Mo, H₃MoOH, or MoO(OH)₃ is thermodynamically favored over H₂Mo(OH)₂ on both surfaces. However, only Cu(111) exhibits measurable pH-dependent free-energy shifts, reaching 0.25 eV on the reversible hydrogen electrode scale. The magnitude of this electrostatic modulation is comparable to the intrinsic substrate-dependent relative Gibbs free-energy differences, suggesting that Cu reshapes Mo redox thermodynamics rather than merely weakening hydrogen binding strength. Electronic structure and vibrational analyses further show that Cu(111) preferentially weakens Mo–O interactions, whereas Ni(111) more strongly perturbs Mo–H bonding in hydrogen-rich complexes. Overall, these results establish that substrate identity governs the electrostatic modulation of Mo redox thermodynamics under alkaline HER conditions and provide mechanistic insight into substrate effects relevant to Cu-containing Ni–Mo systems. Full article