Time-of-flight Secondary Ion Mass Spectrometry Research Articles

Biomimetics through bioconjugation of 16-methylheptadecanoic acid to damaged hair for hair barrier recovery

The primary component of the lipid barrier on human hair, which is essential for defense against aging and environmental stresses, is 18-methyleicosanoic acid (18-MEA), which provides hydrophobic properties and protective benefits. Since 18-MEA cannot be regenerated once damaged, developing technology that can permanently bind alternative materials to hair is critical. Once 18-MEA was removed from hair via X-ray photoelectron spectroscopy (XPS), pentaerythritol tetraisoosterate (PTIS) was hydrolyzed and observed via gas chromatography/mass spectrometry (GC/MS) to confirm that it mimicked 18-MEA, and 16-methylheptadecanoic acid (16-MHA) was obtained at pH 4 or lower. 16-MHA was bioconjugated to damaged hair from which 18-MEA was removed via a carbodiimide reaction using polycarbodiimide. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) confirmed that 16-MHA remained on the surface of the bioconjugated hair even after washing. Observation of the endothermic reaction of moisture in hair via a differential scanning calorimetry (DSC) and evaluation of the moisture content confirmed that the physical properties of hair enriched with 16-MHA were similar to those of virgin hair. This biomimetic approach has been shown to restore both external structural integrity and internal moisture homeostasis.

Peak-Based Machine Learning for Plastic Type Classification in Time-of-Flight Secondary Ion Mass Spectrometry.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurement data and machine learning were used in this work to classify six different types of plastics. In order to take into account the characteristics of the measurement data, the local maxima of the measurement data were first examined in a preprocessing step. Several machine learning methods were then implemented to create a model that could successfully classify the plastics. To visualize the data distribution, we applied a dimensionality reduction method, namely, principal component analysis. Finally, to distinguish between the six types of plastics, we conducted an ensemble analysis using four tree-based algorithms: decision tree, random forest, gradient boosting, and LIGHTGBM. This approach can identify the feature importance of plastic samples and allow the inference of the chemical properties of each plastic type. In this way, ToF-SIMS data could be utilized to successfully classify plastics and enhance explainability.

Longitudinal Piezoelectricity and Polarization-Insensitive Oxidation in Janus vdWs Nb3SeI7.

As a newly discovered Janus van der Waals (vdW) material, semiconducting Nb3SeI7 offers several notable advantages, including spontaneous out-of-plane polarization, facile exfoliation to the monolayer limit, and significant out-of-plane emission dipole in second harmonic generation. These properties make it a promising candidate for piezoelectric and piezophototronic applications in highly efficient energy conversion. However, Nb3SeI7 is prone to oxidation when exposed to oxygen, which can severely limit the exploration and utilization of these intriguing physical properties. Therefore, understanding the oxidation mechanism of pristine Nb3SeI7 and its correlation with electrical polarization-an area that remains largely unexplored-is highly significant. In this study, the out-of-plane piezoelectricity of Nb3SeI7 is experimentally demonstrated, with a piezoelectric coefficient (|d33 eff|) of 0.76nmV-1. Furthermore, by combining near ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS), Time-of-Flight secondary ion mass spectrometry (ToF-SIMS), and Density functional theory (DFT)calculations, it is revealed that the oxidation of Nb3SeI7 is self-limiting and independent of its electrical polarization, owing to the similar defect formation energies of Se and I atoms. This self-limiting and polarization-insensitive oxidation provides valuable insights into the stabilization mechanisms and expands the potential applications of out-of-plane piezoelectricity and other intriguing physical properties in Janus vdW Nb3SeI7.

Enhancing Counterfeit Banknote Analysis: Case Studies Using TOF-SIMS

Counterfeiting banknotes poses a significant threat to economies worldwide, particularly in developing countries where cash transactions remain predominant. Despite advancements in security features, counterfeiters continue to adapt, necessitating more sophisticated analysis methods. Time of flight Secondary Ion Mass Spectrometry (TOF-SIMS) offers a powerful approach to surface chemical imaging and depth profiling of counterfeit currencies. Real cases of five different counterfeit Lebanese banknotes are studied, using TOF-SIMS to address specific questions regarding the composition and placement of replicated security features, gaining insights into counterfeit banknote production and the raw materials used. The findings provide essential information to decision-makers at the national bank, supporting the design of future currencies through the selection of security features best suited to the local market, thereby enhancing protection against financial fraud..

Mapping active pharmaceutical ingredients Distributions in tablets using Time-of-Flight secondary ion mass spectrometry with multivariate curve resolution

This study introduces an advanced approach to identifying signals associated with indapamide, amlodipine, and perindopril in solid dosage form using time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with multivariate curve resolution (MCR). The primary objective was to obtain and characterize these signals through MCR factors, which then led to identifying unique signals specific to each active pharmaceutical ingredient (API). These unique signals were crucial for constructing detailed 2D and 3D images of the API distribution within the tablet. The results demonstrated that indapamide and amlodipine exhibited multiple unique peaks, while perindopril had only one. Additionally, the study revealed non-homogeneous distribution patterns of APIs and excipients, such as SiO2 and Mg stearate. This work highlights the significance of applying advanced analytical techniques such as ToF-SIMS and MCR in the pharmaceutical field to ensure consistent therapeutic efficacy through a better understanding of API distribution.

Microstructure evolution and hydrogen absorption characteristics of gradient-hydrogenated Ti-4.5Al-3V-2Mo-2Fe alloys

Ti-4.5Al-3V-2Mo-2Fe rolled material is a dual-phase titanium alloy with an average grain size of less than 3 μm; its optimal superplastic forming temperature of 760 °C is at least 50 °C lower than the temperature required for diffusion bonding, making it challenging to carry out superplastic forming/diffusion bonding within a process window. The promotion of hydrogen on the low-temperature diffusion bonding of the alloy was verified through thermohydrogen processing, and the absorption characteristics of hydrogen in the alloy at various temperatures, holding times, and pressures were investigated. Subsequently, a mathematical model for achieving standardized hydrogen content was developed. X-ray polycrystalline diffractometer (XRD) analysis was utilized to preliminarily explore phase differences in samples with varying levels of hydrogen content. Furthermore, scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron back scatter diffraction (EBSD) and time of flight secondary ion mass spectrometry (TOF-SIMS) were employed to analyze microstructure changes and hydrogen distribution in both the surface and core regions of the titanium alloy following hydrogenation, demonstrating its feasibility for surface hydrogenation treatment of titanium alloy sheets

Effect of D-arginine as a novel depressant on the flotation separation of chalcopyrite from pyrite at low alkalinity

Flotation separation of Cu–Fe sulfide minerals typically necessitate the addition of substantial quantities of lime to depress pyrite flotation. Because lime can harm the environment, there is an urgent need to develop novel environmentally friendly depressants that are non-toxic and biodegradable. In this study, we investigated an environmentally friendly pyrite depressant containing amino and carboxyl groups, namely D-arginine (DA). The effect of DA on the surface hydrophobicity of Cu–Fe sulfide minerals and thus collector adsorption was investigated by analyzing zeta potentials, adsorption capacities, and contact angles. Additionally, changes in the surface properties of the minerals induced by DA were examined using X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), and atomic force microscopy (AFM). Flotation tests revealed that 2 × 10–4 mol/L DA reduced the flotation recovery of pyrite to 9.96 % at low alkalinity while leaving chalcopyrite recovery unchanged. The results of mineral surface analysis indicated that DA exhibited significantly stronger adsorption on the pyrite surface than on the chalcopyrite surface. Furthermore, DA effectively reduced the adsorption of the collector on the surface of pyrite, thereby weakening pyrite floatability at low alkalinity. Therefore, DA is a promising alternative depressant for the flotation separation of chalcopyrite from pyrite.

The Application of a Random Forest Classifier to ToF-SIMS Imaging Data.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging is a potent analytical tool that provides spatially resolved chemical information on surfaces at the microscale. However, the hyperspectral nature of ToF-SIMS datasets can be challenging to analyze and interpret. Both supervised and unsupervised machine learning (ML) approaches are increasingly useful to help analyze ToF-SIMS data. Random Forest (RF) has emerged as a robust and powerful algorithm for processing mass spectrometry data. This machine learning approach offers several advantages, including accommodating nonlinear relationships, robustness to outliers in the data, managing the high-dimensional feature space, and mitigating the risk of overfitting. The application of RF to ToF-SIMS imaging facilitates the classification of complex chemical compositions and the identification of features contributing to these classifications. This tutorial aims to assist nonexperts in either machine learning or ToF-SIMS to apply Random Forest to complex ToF-SIMS datasets.

Effects of Pt doping on surface properties and quenching of band edge emission in ZnO

Pt doped ZnO thin films were synthesized on soda-lime glass substrates using a cost-effective sol-gel method, followed by spin coating and thermal annealing at various temperatures. Several characterization techniques such as UV–Vis absorption spectroscopy, photoluminescence (PL), field emission scanning electron microscopy (FESEM), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) are exploited to investigate the Pt doping effects on surface and optical properties of ZnO thin films. UV–Vis analysis demonstrated a slight decrease in the optical band gap from 3.3 eV to 3.2 eV with increased annealing, indicating enhanced suitability for optoelectronic applications. FESEM imaging revealed distinct worm-like structures and small Pt metal nanoparticles in unannealed samples, while thermal treatment supported the formation of spherical Pt nanoparticles and improved conductive pathways in the films. The Wagner diagram, coupled with Auger line transitions from XPS, quantified the oxidation states and chemical environments of Zn and Pt, respectively. Notably, the observed changes in the binding energy of the Zn-2p junction and the kinetic energy of the Zn-LMM Auger junction were significantly influenced by the Pt doping and the electronic properties of the substrate. The Wagner diagram provided a comprehensive visual representation of the parameters, facilitating a deeper understanding of electronic interactions and structural dynamics at the atomic level. XPS results confirmed the presence of ZnO, Zn(OH)2, Pt0 and PtO2 phases, indicating stability and constutient's interactions. ToF-SIMS also validated the uniform distribution of Pt nanoparticles within the ZnO thin film, confirming the effectiveness of the sol-gel method. As a result of Pt doping, PL studies revealed a large quenching effect on band edge emission in the UV and visible emission region of ZnO thin film, which is due to Pt acting as a recombination center for photogenerated carriers. Overall, our results highlight the influence of annealing and Pt incorporation on the optical and structural properties of ZnO thin films and highlight their potential applications for photonics and catalysis.

Ultra-High Adsorption Capacity of Calcium-Iron Layered Double Hydroxides for HEDP Removal through Phase Transition Processes.

Antiscalant disposal in reverse osmosis concentrate (ROC) treatment is a significant obstacle in desalination. This study investigated the adsorption performance of LDHs for removing 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP). CaFe-LDH presented a specific adsorption behavior and ultrahigh adsorption capacity for HEDP, with a maximum adsorption capacity of 335.7 mg P/g (1116.5 mg HEDP/g) at pH 7.0. X-ray diffraction (XRD) demonstrated that HEDP adsorption induced a structural transformation of CaFe-LDH from a layered configuration to a highly ordered structure, leading to a noticeable phase transition. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and Raman spectroscopy further confirmed that two distinct binding modes of HEDP, relating to chelation with Ca2+ and adsorption on Fe3+ simultaneously, are connected by phosphonic acid groups (-C-PO(OH)2), forming the CaFe-HEDP complex. X-ray fluorescence (XRF) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the CaFe-HEDP ternary complex exhibits a highly ordered arrangement in an oxygen-bridged framework. The construction of an oxygen-coordinated framework contributes to the incorporation of more HEDP into CaFe-LDH, leading to a well-aligned lattice in the new phase. These findings provide valuable insights into developing novel LDH-based adsorbents for removing phosphorus-containing antiscalants, establishing a sustainable approach to ROC management, and potential environmental risk reduction.

Development of Peptide Identification System for ToF-SIMS Spectra Using Supervised Machine Learning.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) data interpretation for organic materials is complicated because of various fragment ions produced from each molecule and the overlapping of certain mass peaks from different molecules. Fragmentation mechanisms in SIMS are complex because different sputtering and ionization processes can simultaneously occur. Therefore, a prediction system that can identify materials in a sample is required. A novel prediction system for peptides based on ToF-SIMS and amino-acid-based teaching information (labels) for supervised machine learning was developed. To develop the prediction system for general organic materials, the annotation of materials is crucial to creating effective labels for supervised learning. Peptides are composed of 20 amino acid residues, which can be used as labels. We previously developed a peptide prediction system using Random Forest, a supervised machine-learning method. However, only the amino acids contained in the target peptide were predicted, and the amino acid sequence was unable to be assumed. In this study, the amino acid sequence of the test peptide was determined by adding the information on two adjacent amino acids to the labels. Once the prediction system learned the target peptide spectra, the peptides in the newly obtained ToF-SIMS spectra could be identified. The new prediction system also provides useful information for the identification of unknown peptides. The prediction results indicate that two adjacent permutations of amino acids are effective pieces of teaching information for expressing the amino acid sequence of a peptide.

Identifying Process Differences with ToF-SIMS: An MVA Decomposition Strategy.

In time-of-flight secondary ion mass spectrometry (ToF-SIMS), multivariate analysis (MVA) methods such as principal component analysis (PCA) are routinely employed to differentiate spectra. However, additional insights can often be gained by comparing processes, where each process is characterized by its own start and end spectra, such as when identical samples undergo slightly different treatments or when slightly different samples receive the same treatment. This study proposes a strategy to compare such processes by decomposing the loading vectors associated with them, which highlights differences in the relative behavior of the peaks. This strategy identifies key information beyond what is captured by the loading vectors or the end spectra alone. While PCA is widely used, partial least-squares discriminant analysis (PLS-DA) serves as a supervised alternative and is the preferred method for deriving process-related loading vectors when classes are narrowly separated. The effectiveness of the decomposition strategy is demonstrated using artificial spectra and applied to a ToF-SIMS materials science case study on the photodegradation of N719 dye, a common dye in photovoltaics, on a mesoporous TiO2 anode. The study revealed that the photodegradation process varies over time, and the resulting fragments have been identified accordingly. The proposed methodology, applicable to both labeled (supervised) and unlabeled (unsupervised) spectral data, can be seamlessly integrated into most modern mass spectrometry data analysis workflows to automatically generate a list of peaks whose relative behavior varies between two processes, and is particularly effective in identifying subtle differences between highly similar physicochemical processes.

Revealing the Role of Ruthenium on the Performance of P2-Type Na0.67Mn1-xRuxO2 Cathodes for Na-Ion Full-Cells.

Herein, P2-type layered manganese and ruthenium oxide is synthesized as an outstanding intercalation cathode material for high-energy density Na-ion batteries (NIBs). P2-type sodium deficient transition metal oxide structure, Na0.67Mn1-xRuxO2 cathodes where x varied between 0.05 and 0.5 are fabricated. The partially substituted main phase where x = 0.4 exhibits the best electrochemical performance with a discharge capacity of ≈170mAhg-1. The in situ X-ray Absorption Spectroscopy (XAS) and time-resolved X-ray Diffraction (TR-XRD) measurements are performed to elucidate the neighborhood of the local structure and lattice parameters during cycling. X-ray photoelectron spectroscopy (XPS) revealed the oxygen-rich structure when Ru is introduced. Density of States (DOS) calculations revealed the Fermi-Level bandgap increases when Ru is doped, which enhances the electronic conductivity of the cathode. Furthermore, magnetization calculations revealed the presence of stronger Ru─O bonds and the stabilizing effect of Ru-doping on MnO6 octahedra. The results of Time-of-flight secondary-ion mass spectroscopy (TOF-SIMS) revealed that the Ru-doped sample has more sodium and oxygenated-based species on the surface, while the inner layers mainly contain Ru-O and Mn-O species. The full cell study demonstrated the outstanding capacity retention where the cell maintained 70% of its initial capacity at 1C-rate after 500 cycles.

Enhanced imaging of developed fingerprints and its contaminated substance using ToF-SIMS

Fingerprint is a common form of evidence utilized in crime cases, providing crucial information for suspect identification and the proof of key facts. However, traditional development methods are often ineffective for challenging fingerprints due to variations in information and surface characteristics, potentially causing damage to the fingerprint substance. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) offers a non-destructive approach that combines spatial imaging with mass spectrometry capabilities. This study employed ToF-SIMS to enhance natural fingerprints that showed poor visualization when treated with 1,2-indandione and ninhydrin on porous surfaces such as printing paper, kraft paper, newspaper, and thermal paper, especially on challenging textiles. We also imaged fingerprints on nonporous surfaces that were deposited over 30 days ago using ToF-SIMS, like aluminum foil, express packaging bags, and slides. We then extended the age of fingerprint detection to 3 months to explore the relationship between the aging of fingerprints and the morphological characteristics of sweat pores. Furthermore, the study examined the detection capabilities of ToF-SIMS on fingerprints contaminated with compound econazole nitrate cream after being interfered with by development agents, illustrating its effectiveness in extracting comprehensive fingerprint information.

Lanthanum doped hafnium oxide thin films deposited on a lateral high aspect ratio structure using atomic layer deposition: A comparative study of surface composition and uniformity using x-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry

Hafnium oxide (HfO2) thin films doped with lanthanum (La) can achieve ferroelectricity, making the material applicable in transistor and memory technologies. To downscale future devices in the semiconductor industry, the application of the doped HfO2 material requires deposition on complex microscopic three-dimensional (3D) structures. A widely used process for the preparation of doped HfO2 thin films is atomic layer deposition (ALD). With 3D geometries, it is challenging to deposit materials homogeneously and to effectively characterize them. To forego the difficulties in film characterization, two-dimensional (2D) PillarHall lateral high aspect ratio (LHAR) test structures are used. These structures expose a lateral surface to facilitate the conformality analysis of thin films deposited using two different ALD processes. In this work, we aim to further advance the arsenal of analysis techniques used to characterize La doped HfO2 thin films by using x-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to analyze uniformity and composition. The XPS technique can be applied and established as a method for the optimal analysis of thin films deposited on LHAR structures. Both techniques provide a complementary analysis of material formation, elemental distribution, measurement along the LHAR depth range, and can probe differences between deposition processes.

Engineering a superamphiphilic surface for enhanced interfacial bonding in metal-polymer hybrid structure

Insufficient wetting of polymer due to its poor compatibility with metals leads to non-intimate interfacial mutual contact during the thermal-direct bonding process, thus hindering the establishment of effective mechanical interlocking and substantial chemical bonding at the interface, resulting in deficient performance of metal-polymer hybrid structures. To achieve high-quality bonding between non-polar ultra-high molecular weight polyethylene (UHMWPE) and Ti6Al4V titanium alloy (TC4) for the application of artificial joint prostheses, this study innovatively engineered a superamphiphilic (simultaneously superhydrophilic and superlipophilic) TC4 surface, which was achieved through a morphology-chemistry dual regulation strategy. This pretreatment strategy aimed at improving the interfacial compatibility between in-situ oxidized UHMWPE and TC4 and ensuring intimate contact between these two materials during thermal-direct bonding, thus facilitating chemical reactions and mechanical interlocking at the interface. Defect-free and ultra-high-performance TC4-UHMWPE hybrid joints were successfully obtained via friction spot joining (FSpJ) with the lap shear strength reaching 18.05 MPa (higher than all those similar hybrid joints reported in existing literature) and the fracture was confined to the UHMWPE matrix, effectively avoiding interfacial failure. The formation of chemical bonds in the form of COTi at TC4/UHMWPE interface was solidly confirmed based on X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses. This research presents a compelling strategy for improving interfacial compatibility between polymer and metal for thermal-direct bonding, to overcome the general difficulties in achieving effective interfacial bonding between these two categories of materials with significantly different physiochemical properties.

Selective control of surface characteristics of magnesite and quartz by a novel silicophilic collector stearylamine acetate

Reverse flotation desiliconization from magnesite is significant for the exploitation of complex and barren magnesite resources. In this process, a critical issue is to find efficient and selective chemicals as flotation collectors. Herein, a cationic surfactant stearylamine acetate (SAA) was first used as a collector for the separation of magnesite and quartz. Micro-flotation experiments demonstrate that quartz can be separated from magnesite with a high Gaudin’s selectivity index of 6.51 at slurry pH 5.0 and 70 mg/L SAA. Measurements of zeta potential and contact angle show that SAA selectively increased the surface charge and hydrophobicity of quartz. Field emission scanning electron microscopy (FESEM/EDS) and atomic force microscope (AFM) imaging indicate greater adsorption density of SAA on quartz than magnesite, with significantly higher nitrogen element content and RMS surface roughness of quartz. We also used surface-sensitive time of flight secondary ion mass spectrometry (TOF-SIMS) and FTIR spectroscopy to characterize the selective adsorption of SAA on quartz from quartz-magnesite mixtures. Apart from electrostatic attraction, it is found that the selective adsorption was attributed to hydrogen bonding formed between the −N–H group of SAA and the oxygen atom of the O-Si-O group on quartz surface.

Efficient Flotation Separation of Ilmenite and Olivine in a Weak Alkaline Pulp Using a Ternary Combination Collector Centered around Al3.

Due to the similar physical and chemical properties of ilmenite and olivine, separating them is challenging. The flotation process, with the use of collectors, is an effective method. In this study, a ternary collector consisting of aluminum ion (III), benzohydroxamic acid (BHA), and sodium oleate (NaOL) was prepared for the flotation separation of ilmenite and olivine. Through micro-flotation experiments, molecular dynamics simulation (MD), density functional theory (DFT), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (TOF-SIMS) analysis, the synergistic effect between the components of the ternary collector and the adsorption configuration on the surface of ilmenite was investigated. The results revealed that at pH = 8, Al (III), BHA, and NaOL could coordinate and adsorb effectively on the surface of ilmenite, enhancing its floatability for separation from olivine. The adsorption configuration differed from previous reports, showing a co-adsorption of multiple forms on the surface of ilmenite.

Reactive Gas Cluster Ion Beams for Enhanced Drug Analysis by Secondary Ion Mass Spectrometry.

In this study, we investigate the formation and composition of Gas Cluster Ion Beams (GCIBs) and their application in Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) analysis. We focus on altering the carrier gas composition, leading to the formation of (Ar/CO2)n or (H2O)n GCIBs. Our results demonstrate that the addition of a reactive species (CO2) to water GCIBs significantly enhances the secondary ion yield of small pharmaceutical compounds in the positive ion mode. In negative ion mode, the addition of CO2 resulted in either a positive enhancement or no effect, depending on the sample. However, an excess of CO2 in the carrier gas leads to the formation of carbon dioxide clusters, resulting in reduced yields compared to that of water cluster beams. Cluster size also plays a crucial role in overall yields. In a simple two-drug system, CO2-doped water clusters prove effective in mitigating matrix effects in positive ion mode compared to pure water cluster, while in negative ion mode, this effect is limited. These clusters are also applied to the analysis of drugs in a biological matrix, leading to more quantitative measurements as shown by a better fitting calibration curve. Overall, the doping of water clusters with small amounts of a reactive gas demonstrates promising benefits for higher sensitivity, higher resolution molecular analysis, and imaging using ToF-SIMS. The effectiveness of these reactive cluster beams varies depending on the experimental parameters and sample type.

Enhanced marmatite activation by copper with ammonium sulfate: An experimental and DFT investigation

The presence of iron atoms on the marmatite surface hinders effective interaction between the activator and the mineral, leading to unsatisfactory flotation performance through direct copper (Cu) activation. Hence, this study introduced ammonium sulfate to enhance the marmatite-activation capability by Cu ions. Additionally, the reinforcement mechanism was investigated through microflotation tests, atomic force microscopy (AFM), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and density-functional theory (DFT) calculations. Microflotation results demonstrated that the addition of ammonium sulfate as a complexing reagent increased the flotation recovery of marmatite by 17.36%. AFM analysis revealed that marmatite subjected to enhanced activation (i.e., in the presence of ammonium sulfate) exhibited a considerably higher surface roughness than that subjected to direct Cu activation. Moreover, the average height of hill-shaped materials on the marmatite surface notably increased to 9.6 nm after enhanced Cu activation. SEM-EDS analysis revealed that the concentration of Cu atoms (2.2%) on the marmatite surface after enhanced Cu activation was nearly three times that (0.8%) after direct Cu activation. Additionally, XPS results indicated a considerably higher presence of the Cu–S component on the marmatite surface after enhanced Cu activation than after direct Cu activation. ToF-SIMS analysis indicated an increase in the fragment peaks of Cu+, CuOCS2+, OCS2−, and OC2H2S2− on the surface of enhanced-activated marmatite. Additionally, DFT calculations indicated that the presence of NH3 molecules enhanced electron transfer between Cu and S on the hydrated marmatite surface. The marmatite (1 1 0) surface exhibited more negative adsorption energy of Cu ions after the action of NH3 molecules, and NH3–Cu showed a more stable adsorption configuration than Cu. Therefore, the addition of ammonium sulfate enhanced the Cu activation for marmatite, thereby improving flotation performance.