Chemistry of Materials最新文献

{"title":"Energy Transfer Mechanisms in Large Low-Bandgap Polymers from Time-Resolved Experiments and Nonadiabatic Molecular Dynamics Calculations","authors":"Gabriel S. Phun,&nbsp;Dana B. Kern,&nbsp;Matthew Y. Sfeir,&nbsp;Jason D. Azoulay and Bryan M. Wong*,&nbsp;","doi":"10.1021/acs.chemmater.5c0031110.1021/acs.chemmater.5c00311","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00311https://doi.org/10.1021/acs.chemmater.5c00311","url":null,"abstract":"<p >Conjugated polymers offer unprecedented chemical tunability for modulating energy transfer in a multitude of infrared light applications. In this work, we use a combination of time-resolved spectroscopic experiments and nonadiabatic molecular dynamics calculations to probe the photochemistry and nonradiative transitions in a recently synthesized narrow bandgap donor–acceptor conjugated polymer based on alternating cyclopentadithiophene and electronegative benzothiadiazole heterocycles. Using large-scale semi-empirical nonadiabatic molecular dynamics, which can treat a large 260-atom hexamer, we calculate an S₅ → S₁ lifetime of 34.75 fs, which is consistent with our time-resolved spectroscopic data. Our simulations suggest that vibronic motions of the central carbons in the cyclopentadithiophene functional groups are predominantly involved in the nonradiative transitions, and the excitation becomes more localized on a monomer fragment over time. The combined use of time-resolved experiments and nonadiabatic molecular dynamics calculations in this work provides mechanistic insight into chemical functionalities that can be tuned to enhance energy transfer in other prospective low-bandgap polymer materials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3769–3775 3769–3775"},"PeriodicalIF":7.2,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.5c00311","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137470","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling the Reactive Sites for Electrocatalytic Conversion of Nitrate to High-Value-Added Chemicals","authors":"Yufeng Yan,&nbsp;Pengfei Guo,&nbsp;Xiaofeng Xu,&nbsp;Zhongyan Zhang,&nbsp;Haitao Lou,&nbsp;Fanfei Sun* and Meiqin Shi*,&nbsp;","doi":"10.1021/acs.chemmater.4c0341710.1021/acs.chemmater.4c03417","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03417https://doi.org/10.1021/acs.chemmater.4c03417","url":null,"abstract":"<p >CuZn catalysts with various structures were synthesized for electrocatalyzing the NO₃^– and CO₂. Among them, CuZn supported on nitrogen-doped carbon exhibited the capability for directly producing urea, while after being treated at higher temperatures, it presents the highest yield of ammonia. X-ray absorption fine structure (XAFS) analysis revealed that in the optimized sample, Zn existed as the single atom and Cu contained Cu–O(N) and Cu–Cu coordination structures. The Cu–O(N) species promoted the C–N coupling, while the Cu–Cu component played a crucial role in the reduction of nitrate to ammonia. Cu^δ+ (1 &lt; δ &lt; 2) in the catalyst contributed to the C–N coupling. In addition, in situ XAFS data indicated that under the optimal potential of −0.89 V, the valence state of Cu^δ+ decreased slightly but remained within the range of 1 &lt; δ &lt; 2. After 8 h stability tests, the catalyst maintained a stable coordination structure. This study reveals that the Cu coordination environment is a crucial parameter for selectively producing ammonia or urea.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3661–3675 3661–3675"},"PeriodicalIF":7.2,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137472","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Energy Transfer Mechanisms in Large Low-Bandgap Polymers from Time-Resolved Experiments and Nonadiabatic Molecular Dynamics Calculations","authors":"Gabriel S. Phun, Dana B. Kern, Matthew Y. Sfeir, Jason D. Azoulay, Bryan M. Wong","doi":"10.1021/acs.chemmater.5c00311","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00311","url":null,"abstract":"Conjugated polymers offer unprecedented chemical tunability for modulating energy transfer in a multitude of infrared light applications. In this work, we use a combination of time-resolved spectroscopic experiments and nonadiabatic molecular dynamics calculations to probe the photochemistry and nonradiative transitions in a recently synthesized narrow bandgap donor–acceptor conjugated polymer based on alternating cyclopentadithiophene and electronegative benzothiadiazole heterocycles. Using large-scale semi-empirical nonadiabatic molecular dynamics, which can treat a large 260-atom hexamer, we calculate an S₅ → S₁ lifetime of 34.75 fs, which is consistent with our time-resolved spectroscopic data. Our simulations suggest that vibronic motions of the central carbons in the cyclopentadithiophene functional groups are predominantly involved in the nonradiative transitions, and the excitation becomes more localized on a monomer fragment over time. The combined use of time-resolved experiments and nonadiabatic molecular dynamics calculations in this work provides mechanistic insight into chemical functionalities that can be tuned to enhance energy transfer in other prospective low-bandgap polymer materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"57 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143980167","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Advanced Multifunctional Electrocatalysts: Integrating DFT and Machine Learning for OER, HER, and ORR Reactions","authors":"Swetarekha Ram,&nbsp;Albert S. Lee,&nbsp;Seung-Cheol Lee* and Satadeep Bhattacharjee*,&nbsp;","doi":"10.1021/acs.chemmater.4c0321310.1021/acs.chemmater.4c03213","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03213https://doi.org/10.1021/acs.chemmater.4c03213","url":null,"abstract":"<p >Expanding MXene applications in energy conversion and storage offers a promising approach to developing robust, multifunctional electrocatalysts. Progress in electrochemical energy systems is strongly dependent on effective catalysts for the oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR). In this study, we used density functional theory (DFT) to investigate transition-metal-based single-atom catalysts (TM_SA) supported on Mo₂CS₂ MXene. Our findings revealed that the bifunctional overpotential for Ni_SA is 0.44 V for water splitting and 1.11 V for metal–air batteries, showcasing excellent catalytic performance. Volcano plots, based on Gibbs free energy changes for the intermediates OH*, O*, and OOH*, density of states and crystal orbital Hamilton population (COHP) effectively illustrate these results. Additionally, we utilized a multitask machine learning (MTL) approach to predict overpotentials for OER + HER and OER + ORR in the context of water splitting and metal–air batteries, respectively. Using the Sure Independence Screening and Sparsifying Operator (SISSO) method, we identified meaningful descriptors associated with catalytic activity. The key features influencing the adsorption behavior were found to include the shift of the d-band center and the difference in Bader charge upon the adsorption of O* and OH* on the TM_SA–MXene interface. This comprehensive study underscores the significant potential of Mo₂CS₂–Ni_SA as multifunctional electrocatalysts and offers crucial theoretical insights for the development of advanced catalysts capable of facilitating OER, ORR, and HER.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3608–3621 3608–3621"},"PeriodicalIF":7.2,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137471","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Deciphering Self-Assembly Mechanisms of IRMOF-n-Inspired Three-Dimensional Cubic-Symmetry Nanoporous Crystals from Multiscale Simulations","authors":"Katherine Ardila,&nbsp;Tsung-Wei Liu,&nbsp;Diego A. Gómez-Gualdrón* and Alexander J. Pak*,&nbsp;","doi":"10.1021/acs.chemmater.5c0052710.1021/acs.chemmater.5c00527","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00527https://doi.org/10.1021/acs.chemmater.5c00527","url":null,"abstract":"<p >The formation mechanisms of metal−organic frameworks (MOFs) are not fully understood. Therefore, experimental realization of potential “breakthrough” MOFs is hindered by uncertainty in the synthesis conditions that would allow the constituent nodes and linkers to self-assemble into the targeted MOF structure. Here, a multiscale endeavor using density functional theory (DFT) calculations, followed by metadynamics with DFT-informed classical atomistic potentials, followed by standard molecular dynamics (MD) and Hamiltonian replica exchange (HREX) simulations with a metadynamics-informed, coarse-grained (CG) model, was used to study the self-assembly mechanism of cubic-symmetry porous crystals inspired by the IRMOF-<i>n</i> family of MOFs. Mechanistic differences were examined for different values of node–linker coordination strength─understood as the free energy penalty for breaking a coordination bond in a solvated environment. Our integrated analyses of HREX-derived free energy surfaces and standard MD trajectories indicate that at coordination strengths typical of the IRMOF-<i>n</i> family in dimethylformamide (DMF) (i.e., 52 kJ/mol), disassembled nodes and linkers are favored to overcome a small 1.3 kJ/mol free energy barrier to first form solid amorphous clusters, which then overcome a series of barriers (the largest of which is 3.7 kJ/mol) to heal and form ordered, more stable, cubic-symmetry crystals. This healing seems to occur through the splintering/reattaching of small clusters from/to large clusters. Our analyses also suggest that if coordination strength is moderately weakened (e.g., to 40 kJ/mol), crystals form without the preliminary formation of amorphous clusters. However, further coordination strength weakening (e.g., to 36 kJ/mol) makes the formation of sizable crystals unfavorable thermodynamically. On the other hand, strengthening the coordination would increase the free energy barrier to heal the amorphous clusters into crystals. Accordingly, if coordination becomes too strong (e.g., 65+ kJ/mol), then healing may become unlikely. In practical terms, our study suggests that MOF formation is favored only when the free energy of coordination, accounting for solvent effects, falls within a relatively narrow range (approximately 40 to 65 kJ/mol), at least at 300 K, for MOFs with cubic symmetries.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3799–3812 3799–3812"},"PeriodicalIF":7.2,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137495","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling the Reactive Sites for Electrocatalytic Conversion of Nitrate to High-Value-Added Chemicals","authors":"Yufeng Yan, Pengfei Guo, Xiaofeng Xu, Zhongyan Zhang, Haitao Lou, Fanfei Sun, Meiqin Shi","doi":"10.1021/acs.chemmater.4c03417","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03417","url":null,"abstract":"CuZn catalysts with various structures were synthesized for electrocatalyzing the NO₃^– and CO₂. Among them, CuZn supported on nitrogen-doped carbon exhibited the capability for directly producing urea, while after being treated at higher temperatures, it presents the highest yield of ammonia. X-ray absorption fine structure (XAFS) analysis revealed that in the optimized sample, Zn existed as the single atom and Cu contained Cu–O(N) and Cu–Cu coordination structures. The Cu–O(N) species promoted the C–N coupling, while the Cu–Cu component played a crucial role in the reduction of nitrate to ammonia. Cu^δ+ (1 &lt; δ &lt; 2) in the catalyst contributed to the C–N coupling. In addition, in situ XAFS data indicated that under the optimal potential of −0.89 V, the valence state of Cu^δ+ decreased slightly but remained within the range of 1 &lt; δ &lt; 2. After 8 h stability tests, the catalyst maintained a stable coordination structure. This study reveals that the Cu coordination environment is a crucial parameter for selectively producing ammonia or urea.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"13 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143946151","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Phase Transition Assisted Photo-, Electro- and Photoelectrocatalytic Hydrogen Evolution in B/MoS2─Mechanistic Insight","authors":"Daria Baranowska, Tomasz Kędzierski, Grzegorz Leniec, Beata Zielińska, Ewa Mijowska","doi":"10.1021/acs.chemmater.4c03268","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03268","url":null,"abstract":"Electrocatalytic water splitting is recognized as one of the most effective methods for sustainable hydrogen production, with visible light integration recently emerging as a promising enhancement strategy. To address this, we developed a 2D/2D heterostructure of borophene and molybdenum disulfide (B/MoS₂) to investigate its efficiency in photo-(photo), electro-(HER), and photoelectro-(PEC) catalytic hydrogen evolution reactions under acidic conditions. Optimizing the MoS₂-to-boron mass ratio revealed significantly reduced overpotential, achieving 281.1 mV and a Tafel slope of 56.0 mV/dec in PEC, compared to 312.5 mV and 160.9 mV/dec in conventional HER, indicating boosted activity and kinetics of the hydrogen evolution process. Additionally, a long-term stability test at a constant current density of 10 mA/cm² confirmed the high durability of B/MoS₂ and maintained stable performance for up to 120 h. The B/MoS₂ demonstrated an improved hydrogen evolution rate reaching ∼2.5 mol/g in PEC, representing a 1.4-fold, 1.8-fold, and 3152-fold increase compared to pristine MoS₂ in photoelectro-, electro-, and photocatalytic hydrogen evolution process, respectively. Moreover, comprehensive material characterization elucidated the underlying PEC mechanism, including <i>in situ</i> and <i>ex situ</i> analyses. It highlighted the potential of borophene-enriched MoS₂ as an efficient catalyst for solar and/or electricity-driven hydrogen production, confirming that borophene presence substantially promotes the 2H-to-1T phase transition of MoS₂ by creating strain and defects, destabilizing the 2H phase, and favoring the formation of the 1T phase, thus significantly enhancing catalytic performance. Interestingly, the 2H-to-1T phase transition of MoS₂ is detected in all three processes: photo-, electro-, and photoelectrocatalytic hydrogen evolution reactions. However, its efficiency follows the order: PEC &gt; HER &gt; photo indicating that visible light irradiation is a missing activity descriptor revealing a puzzle of hydrogen evolution mechanism during PEC water splitting.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"4 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143946153","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Locating Impurity Phases in the Lithium-Ion Conductor Al-Doped Li7La3Zr2O12 through Dynamic Nuclear Polarization and Nuclear Magnetic Resonance Spectroscopy","authors":"Astrid H. Berge,&nbsp;Sundeep Vema,&nbsp;Christopher A. O’Keefe and Clare P. Grey*,&nbsp;","doi":"10.1021/acs.chemmater.5c0080710.1021/acs.chemmater.5c00807","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00807https://doi.org/10.1021/acs.chemmater.5c00807","url":null,"abstract":"<p >An understanding of the nature of the grain boundaries and impurity phases contained in complex mixed metal oxide solid electrolytes is key to the development of improved and more stable solid-state batteries with reduced grain boundary resistances and higher ionic conductivities of the bulk sample. The Li-ion solid electrolyte Li₇La₃Zr₂O₁₂ (LLZO) is one of the most researched electrolytes in the field due to its high ionic conductivity, thermal stability, and wide voltage stability window. Despite its potential, the nature of the impurity and surface phases formed during the synthesis of LLZO and their role and influence on LLZO’s performance when used as an electrolyte remain poorly understood and controlled. In addition, there are limited characterization methods available for detailed studies of these impurity phases, particularly if these phases are buried in or close to the grain boundaries of a dense sintered material. Here, we demonstrate a solid-state nuclear magnetic resonance (ssNMR) and dynamic nuclear polarization (DNP) approach that exploits both endogenous and exogenous dopants to select for either specific impurities or separate bulk vs surface/subsurface phases. Specifically, the location of Al-containing phases within an Al doped LLZO and the impurity phases that form during synthesis are mapped: by doping LLZO with trace amounts of paramagnetic metal ions (Fe³⁺ and Gd³⁺), DNP is used to selectively probe Al- and La-containing impurity phases, respectively, allowing us to enhance the signals arising from the LiAlO₂ and LaAlO₃ impurities and to confirm their identity. A ¹⁷O DNP experiment using Gd³⁺ doped LLZO is performed to identify further La³⁺-containing impurities (specifically La₂Zr₂O₇ and La₂O₃). Finally, a ⁷Li DNP irradiated ⁷Li–²⁷Al dipolar-based heteronuclear multiple quantum correlation experiment is performed by using the radical TEKPol as the polarization agent. This experiment demonstrates that the poorly crystalline LiAlO₂ that is found close to the surfaces of the LLZO composite is coated by a thin Li-containing impurity layer and thus not directly present at the surface.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3842–3852 3842–3852"},"PeriodicalIF":7.2,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.5c00807","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Atomic Layer Etching of Tantalum with NbCl5 and O2","authors":"Juha Ojala*,&nbsp;Pekka Pykäläinen,&nbsp;Mykhailo Chundak,&nbsp;Anton Vihervaara,&nbsp;Marko Vehkamäki and Mikko Ritala*,&nbsp;","doi":"10.1021/acs.chemmater.5c0059310.1021/acs.chemmater.5c00593","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00593https://doi.org/10.1021/acs.chemmater.5c00593","url":null,"abstract":"<p >Tantalum has been used in the semiconductor industry as a diffusion barrier for metal interconnects. The current etching processes for this metal are mostly wet etching and reactive ion etching, and also one plasma enhanced atomic layer etching process has been reported. This paper reports development of a thermally activated atomic layer etching (ALE) process based on oxidation with O₂ and removal of the oxide with NbCl₅. The process was found to be somewhat selective toward the tetragonal β-phase of tantalum over the bcc α-Ta. Phase pure α-Ta films were used to study the ALE process, and EPC of 0.6–5.5 Å was obtained at the temperature range of 200–300 °C. Saturation of the etchant pulses was verified at 250 °C with an EPC of 2.8 Å. Some subsurface oxidation of the tantalum films was seen with XRD after etching at high temperatures, but otherwise, residues from the etching were minimal. The etching mechanism was studied using <i>in vacuo</i> XPS measurements at different stages of the process.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3822–3829 3822–3829"},"PeriodicalIF":7.2,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.5c00593","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Phase Transition Assisted Photo-, Electro- and Photoelectrocatalytic Hydrogen Evolution in B/MoS2─Mechanistic Insight","authors":"Daria Baranowska*,&nbsp;Tomasz Kędzierski,&nbsp;Grzegorz Leniec,&nbsp;Beata Zielińska and Ewa Mijowska*,&nbsp;","doi":"10.1021/acs.chemmater.4c0326810.1021/acs.chemmater.4c03268","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03268https://doi.org/10.1021/acs.chemmater.4c03268","url":null,"abstract":"<p >Electrocatalytic water splitting is recognized as one of the most effective methods for sustainable hydrogen production, with visible light integration recently emerging as a promising enhancement strategy. To address this, we developed a 2D/2D heterostructure of borophene and molybdenum disulfide (B/MoS₂) to investigate its efficiency in photo-(photo), electro-(HER), and photoelectro-(PEC) catalytic hydrogen evolution reactions under acidic conditions. Optimizing the MoS₂-to-boron mass ratio revealed significantly reduced overpotential, achieving 281.1 mV and a Tafel slope of 56.0 mV/dec in PEC, compared to 312.5 mV and 160.9 mV/dec in conventional HER, indicating boosted activity and kinetics of the hydrogen evolution process. Additionally, a long-term stability test at a constant current density of 10 mA/cm² confirmed the high durability of B/MoS₂ and maintained stable performance for up to 120 h. The B/MoS₂ demonstrated an improved hydrogen evolution rate reaching ∼2.5 mol/g in PEC, representing a 1.4-fold, 1.8-fold, and 3152-fold increase compared to pristine MoS₂ in photoelectro-, electro-, and photocatalytic hydrogen evolution process, respectively. Moreover, comprehensive material characterization elucidated the underlying PEC mechanism, including <i>in situ</i> and <i>ex situ</i> analyses. It highlighted the potential of borophene-enriched MoS₂ as an efficient catalyst for solar and/or electricity-driven hydrogen production, confirming that borophene presence substantially promotes the 2H-to-1T phase transition of MoS₂ by creating strain and defects, destabilizing the 2H phase, and favoring the formation of the 1T phase, thus significantly enhancing catalytic performance. Interestingly, the 2H-to-1T phase transition of MoS₂ is detected in all three processes: photo-, electro-, and photoelectrocatalytic hydrogen evolution reactions. However, its efficiency follows the order: PEC &gt; HER &gt; photo indicating that visible light irradiation is a missing activity descriptor revealing a puzzle of hydrogen evolution mechanism during PEC water splitting.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3622–3634 3622–3634"},"PeriodicalIF":7.2,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c03268","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137565","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}