Chemistry of Materials最新文献

{"title":"Synthesis of ZSM-5 Zeolite Nanosheets Using Fluorine-Free Additives","authors":"Jiaxing Zhang,&nbsp;Ajuan Zhou,&nbsp;Fang Hao,&nbsp;Kexin Yang,&nbsp;Yiren Yu,&nbsp;Yucai Qin,&nbsp;Xiongfu Zhang,&nbsp;Limin Ren*,&nbsp;Anfeng Zhang*,&nbsp;Guanghui Zhang,&nbsp;Chunshan Song and Xinwen Guo*,&nbsp;","doi":"10.1021/acs.chemmater.5c0030010.1021/acs.chemmater.5c00300","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00300https://doi.org/10.1021/acs.chemmater.5c00300","url":null,"abstract":"<p >The green synthesis of <i>b</i>-axis-oriented ZSM-5 nanosheets (NSs) is essential for facilitating their industrial production. Here, a set of cost-effective and eco-friendly additives is introduced for the tailored synthesis of thin ZSM-5 NSs with a <i>b</i>-axis thickness of 40 nm with the assistance of small seeds. Through a comprehensive exploration of synthesis methods and electron microscopy analysis, this work elucidates the pivotal roles of seeds and additives in controlling the crystal size and steering anisotropic growth kinetics during the crystallization process. The shortened straight channels of the thin ZSM-5 NSs along the <i>b</i>-axis significantly enhance the rapid transport of molecules within the micropores, thus manifesting a distinct catalytic advantage in the alkylation of benzene with methanol and methanol-to-propylene (MTP) conversion. Notably, the utilization of fluorine-free additives in the synthesis of thin ZSM-5 NSs marks an important step forward in zeolite materials, bridging the gap between laboratory experimentation and industrial scale-up.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3757–3768 3757–3768"},"PeriodicalIF":7.2,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137548","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":"Synthesis of ZSM-5 Zeolite Nanosheets Using Fluorine-Free Additives","authors":"Jiaxing Zhang, Ajuan Zhou, Fang Hao, Kexin Yang, Yiren Yu, Yucai Qin, Xiongfu Zhang, Limin Ren, Anfeng Zhang, Guanghui Zhang, Chunshan Song, Xinwen Guo","doi":"10.1021/acs.chemmater.5c00300","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00300","url":null,"abstract":"The green synthesis of <i>b</i>-axis-oriented ZSM-5 nanosheets (NSs) is essential for facilitating their industrial production. Here, a set of cost-effective and eco-friendly additives is introduced for the tailored synthesis of thin ZSM-5 NSs with a <i>b</i>-axis thickness of 40 nm with the assistance of small seeds. Through a comprehensive exploration of synthesis methods and electron microscopy analysis, this work elucidates the pivotal roles of seeds and additives in controlling the crystal size and steering anisotropic growth kinetics during the crystallization process. The shortened straight channels of the thin ZSM-5 NSs along the <i>b</i>-axis significantly enhance the rapid transport of molecules within the micropores, thus manifesting a distinct catalytic advantage in the alkylation of benzene with methanol and methanol-to-propylene (MTP) conversion. Notably, the utilization of fluorine-free additives in the synthesis of thin ZSM-5 NSs marks an important step forward in zeolite materials, bridging the gap between laboratory experimentation and industrial scale-up.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"126 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143931261","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":"Bulk Synthesis and Superconductivity of Rock Salt-Type, Nitrogen-Rich, Zirconium-Deficient Nitrides, Zr1–xN","authors":"Masashi Tanaka, Masaya Fujioka, Duncan H. Gregory, Kei Inumaru","doi":"10.1021/acs.chemmater.5c00175","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00175","url":null,"abstract":"Zirconium nitrides were derived from crystalline powders of layer-structured ZrNCl via ammonothermal dechlorination at various temperatures under flowing ammonia gas. Regardless of which polymorph of ZrNCl was employed as a starting material, the products of the ammonothermal dechlorination reactions were zirconium nitride powders with the rock salt structure. The size of the cubic lattice parameter was found to be dependent on the ammonia flow rate. Each of the synthesized zirconium nitrides is nonstoichiometric and nitrogen-rich (zirconium-deficient), Zr_1–<i>x</i>N, and some exhibit superconductivity at subambient temperature. The superconducting transition temperature (<i>T</i>_c) of each of the nitrides scales linearly with the corresponding cubic unit cell volume (lattice parameter, <i>a</i>) and the N/Zr ratio. This paper represents the first report of a superconducting dome in bulk nitrogen-rich zirconium nitrides with a rock-salt-type structure; to date, a unique characteristic among superconducting rock salt phases.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"68 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143932578","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":"Bulk Synthesis and Superconductivity of Rock Salt-Type, Nitrogen-Rich, Zirconium-Deficient Nitrides, Zr1–xN","authors":"Masashi Tanaka*,&nbsp;Masaya Fujioka,&nbsp;Duncan H. Gregory and Kei Inumaru,&nbsp;","doi":"10.1021/acs.chemmater.5c0017510.1021/acs.chemmater.5c00175","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00175https://doi.org/10.1021/acs.chemmater.5c00175","url":null,"abstract":"<p >Zirconium nitrides were derived from crystalline powders of layer-structured ZrNCl via ammonothermal dechlorination at various temperatures under flowing ammonia gas. Regardless of which polymorph of ZrNCl was employed as a starting material, the products of the ammonothermal dechlorination reactions were zirconium nitride powders with the rock salt structure. The size of the cubic lattice parameter was found to be dependent on the ammonia flow rate. Each of the synthesized zirconium nitrides is nonstoichiometric and nitrogen-rich (zirconium-deficient), Zr_1–<i>x</i>N, and some exhibit superconductivity at subambient temperature. The superconducting transition temperature (<i>T</i>_c) of each of the nitrides scales linearly with the corresponding cubic unit cell volume (lattice parameter, <i>a</i>) and the N/Zr ratio. This paper represents the first report of a superconducting dome in bulk nitrogen-rich zirconium nitrides with a rock-salt-type structure; to date, a unique characteristic among superconducting rock salt phases.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3747–3756 3747–3756"},"PeriodicalIF":7.2,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.5c00175","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137440","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":"Tetracyanidoborates of Divalent Eu and Yb 3D Metal–Organic Frameworks with Cubic Structure. Thermochromic Luminescence and Slow Relaxation of Magnetization of Eu[B(CN)4]2","authors":"Vasily A. Ilichev, Anton F. Rogozhin, Tatyana V. Balashova, Svetlana K. Polyakova, Nikolay N. Efimov, Pavel N. Vasilev, Elena A. Ugolkova, Eduard Bernhardt, Roman V. Rumyantcev, Georgy K. Fukin, Mikhail N. Bochkarev","doi":"10.1021/acs.chemmater.4c03507","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03507","url":null,"abstract":"Tetracyanidoborates of divalent lanthanides, Ln[B(CN)₄]₂·THF (Ln = Eu (<b>1</b>), Yb (<b>2</b>)), were obtained by a salt metathesis reaction of lanthanide diiodides and ammonium tetracyanidoborate. Unlike known tetracyanidoborates of alkaline-earth metals and trivalent lanthanides, compounds <b>1</b> and <b>2</b> are 3D metal–organic frameworks (MOFs) with a cubic structure. MOF <b>1</b> demonstrates air stability and thermal stability up to 400 °C. At 298 K, <b>1</b> shows bright broadband photoluminescence (PL) of Eu²⁺ ions that peaked at 650 nm with 80% absolute quantum yield (QY). When the temperature increases from 77 to 500 K, the maximum of PL spectra of <b>1</b> exhibit a blue shift from 13900 to 16350 cm^–1. Quantum chemical calculations and X-ray diffraction studies of <b>1</b> at 100 and 390 K reveal that observed PL thermochromism is accompanied by changes in the geometry of the Eu–N–C fragment and electronic structure of the [B(CN)₄]⁻ anion. Europium-containing MOF <b>1</b> exhibits slow relaxation of magnetization at temperatures up to 4 K. The magnetic relaxation dynamics of MOF <b>1</b> is dominated by an Orbach-like mechanism with an effective energetic barrier estimated as 16.7 K. Removal of THF from the pores of MOF <b>1</b> leads to the same changes in structure and luminescent behavior as heating but significantly reduces its stability in air. The singularity of structural, magnetic, and luminescent behavior, as well as extraordinary stability of europium MOF <b>1</b>, are due to specifics in europium–tetracyanidoborate bonding. The reported tetracyanidoborates <b>1</b> and <b>2</b> are the porous 3D MOFs based on divalent lanthanide ions: europium and ytterbium.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"118 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143926896","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":"Tetracyanidoborates of Divalent Eu and Yb 3D Metal–Organic Frameworks with Cubic Structure. Thermochromic Luminescence and Slow Relaxation of Magnetization of Eu[B(CN)4]2","authors":"Vasily A. Ilichev*,&nbsp;Anton F. Rogozhin,&nbsp;Tatyana V. Balashova,&nbsp;Svetlana K. Polyakova,&nbsp;Nikolay N. Efimov,&nbsp;Pavel N. Vasilev,&nbsp;Elena A. Ugolkova,&nbsp;Eduard Bernhardt*,&nbsp;Roman V. Rumyantcev,&nbsp;Georgy K. Fukin and Mikhail N. Bochkarev,&nbsp;","doi":"10.1021/acs.chemmater.4c0350710.1021/acs.chemmater.4c03507","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03507https://doi.org/10.1021/acs.chemmater.4c03507","url":null,"abstract":"<p >Tetracyanidoborates of divalent lanthanides, Ln[B(CN)₄]₂·THF (Ln = Eu (<b>1</b>), Yb (<b>2</b>)), were obtained by a salt metathesis reaction of lanthanide diiodides and ammonium tetracyanidoborate. Unlike known tetracyanidoborates of alkaline-earth metals and trivalent lanthanides, compounds <b>1</b> and <b>2</b> are 3D metal–organic frameworks (MOFs) with a cubic structure. MOF <b>1</b> demonstrates air stability and thermal stability up to 400 °C. At 298 K, <b>1</b> shows bright broadband photoluminescence (PL) of Eu²⁺ ions that peaked at 650 nm with 80% absolute quantum yield (QY). When the temperature increases from 77 to 500 K, the maximum of PL spectra of <b>1</b> exhibit a blue shift from 13900 to 16350 cm^–1. Quantum chemical calculations and X-ray diffraction studies of <b>1</b> at 100 and 390 K reveal that observed PL thermochromism is accompanied by changes in the geometry of the Eu–N–C fragment and electronic structure of the [B(CN)₄]⁻ anion. Europium-containing MOF <b>1</b> exhibits slow relaxation of magnetization at temperatures up to 4 K. The magnetic relaxation dynamics of MOF <b>1</b> is dominated by an Orbach-like mechanism with an effective energetic barrier estimated as 16.7 K. Removal of THF from the pores of MOF <b>1</b> leads to the same changes in structure and luminescent behavior as heating but significantly reduces its stability in air. The singularity of structural, magnetic, and luminescent behavior, as well as extraordinary stability of europium MOF <b>1</b>, are due to specifics in europium–tetracyanidoborate bonding. The reported tetracyanidoborates <b>1</b> and <b>2</b> are the porous 3D MOFs based on divalent lanthanide ions: europium and ytterbium.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3685–3695 3685–3695"},"PeriodicalIF":7.2,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137542","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":"Mechanisms for Improved Anode Performance in Titanium Niobate via Neodymium Doping","authors":"J. Michael Sieffert,&nbsp;Zhenzhe Zhang,&nbsp;Ning Chen,&nbsp;Stephanie Bazylevych,&nbsp;Janine Richter,&nbsp;Galal Nasser,&nbsp;Jan Kopyscinski,&nbsp;Rustam Z. Khaliullin* and Eric McCalla*,&nbsp;","doi":"10.1021/acs.chemmater.5c0038710.1021/acs.chemmater.5c00387","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00387https://doi.org/10.1021/acs.chemmater.5c00387","url":null,"abstract":"<p >High-powered Li-ion battery anodes are a rapidly developing class of materials, being essential to the success of various applications, such as medical devices and heavy machinery. One material of significant recent interest is TiNb₂O₇, which is attractive due to its high theoretical capacity of 388 mA h g^–1. This capacity is not typically achieved, but our recent efforts to improve the performance of TiNb₂O₇ by substitutional doping with Nd have increased the capacity by 19% over the undoped material to 321 mA h g^–1 with only a 1.2% substitution. In this work, experimental investigations of lithium and electron transport properties revealed that the enhanced performance of Nd-doped TiNb₂O₇ is primarily due to an increased number of lithium storage sites and improved accessibility through more efficient diffusion pathways. X-ray absorbance spectroscopy and computational modeling were used to understand the mechanism behind these improvements. The two methods suggest that Nd in the TiNb₂O₇ lattice increases the size of certain channels for lithium diffusion while decreasing the size of others. The fact that this results in faster diffusion and increased lithium storage capacity demonstrates that those paths that increased in size act as bottlenecks in the undoped TiNb₂O₇. This complement of experiment and computation guides the further design of these materials by identifying the key structural limitations in the material.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3776–3787 3776–3787"},"PeriodicalIF":7.2,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137422","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":"Mechanisms for Improved Anode Performance in Titanium Niobate via Neodymium Doping","authors":"J. Michael Sieffert, Zhenzhe Zhang, Ning Chen, Stephanie Bazylevych, Janine Richter, Galal Nasser, Jan Kopyscinski, Rustam Z. Khaliullin, Eric McCalla","doi":"10.1021/acs.chemmater.5c00387","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00387","url":null,"abstract":"High-powered Li-ion battery anodes are a rapidly developing class of materials, being essential to the success of various applications, such as medical devices and heavy machinery. One material of significant recent interest is TiNb₂O₇, which is attractive due to its high theoretical capacity of 388 mA h g^–1. This capacity is not typically achieved, but our recent efforts to improve the performance of TiNb₂O₇ by substitutional doping with Nd have increased the capacity by 19% over the undoped material to 321 mA h g^–1 with only a 1.2% substitution. In this work, experimental investigations of lithium and electron transport properties revealed that the enhanced performance of Nd-doped TiNb₂O₇ is primarily due to an increased number of lithium storage sites and improved accessibility through more efficient diffusion pathways. X-ray absorbance spectroscopy and computational modeling were used to understand the mechanism behind these improvements. The two methods suggest that Nd in the TiNb₂O₇ lattice increases the size of certain channels for lithium diffusion while decreasing the size of others. The fact that this results in faster diffusion and increased lithium storage capacity demonstrates that those paths that increased in size act as bottlenecks in the undoped TiNb₂O₇. This complement of experiment and computation guides the further design of these materials by identifying the key structural limitations in the material.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"146 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143920786","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":"Change in Magnetic Order in NiPS3 Single Crystals Induced by a Molecular Intercalation","authors":"Nirman Chakraborty,&nbsp;Adi Harchol,&nbsp;Beatriz Costa Arnold,&nbsp;Kusha Sharma,&nbsp;Diksha Prabhu Gaonkar,&nbsp;Azhar Abu-Hariri,&nbsp;Rajesh Kumar Yadav,&nbsp;Muhamed Dawod,&nbsp;Anna Eyal,&nbsp;Yaron Amouyal,&nbsp;Thomas Brumme,&nbsp;Thomas Heine,&nbsp;Doron Naveh and Efrat Lifshitz*,&nbsp;","doi":"10.1021/acs.chemmater.4c0272410.1021/acs.chemmater.4c02724","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02724https://doi.org/10.1021/acs.chemmater.4c02724","url":null,"abstract":"<p >Intercalation is a robust method for tuning the physical properties of a vast number of van der Waals (vdW) materials. However, the prospects of using intercalation to modify magnetism in van der Waals (vdW) systems and the associated mechanisms have not been adequately studied. In this work, we modulated magnetic order in XY antiferromagnet NiPS₃ single crystals by introducing pyridine molecules into the vdW’s gap under different thermal conditions. X-ray diffraction measurements indicated pronounced changes in the lattice parameter <i>β</i>, while magnetization measurements at in-plane and out-of-plane configurations exposed reversal trends in the crystals’ Néel temperatures through intercalation/deintercalation processes. The changes in magnetic ordering were also supported by three-dimensional thermal diffusivity experiments. The preferred orientation of the pyridine dipoles within the vdW gaps was deciphered <i>via</i> polarized Raman spectroscopy. The results highlighted the relationship between the preferential alignment of the intercalants, thermal transport, and crystallographic disorder, along with the modulation of anisotropy in the magnetic order. DFT + <i>U</i> calculations indicated that the varying interlayer exchange interactions, regulated by intercalants, were responsible for modulating samples’ magnetic ordering. The study uncovers the possible merit of intercalation for manipulating spin orientations in spin electronics and advanced quantum devices.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3594–3607 3594–3607"},"PeriodicalIF":7.2,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137360","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":"Second-Harmonic Generation Response in Nitridophosphates MP2N4 (M = Ge, Sn, Pb) and the Role of Stereochemically Active Lone Pairs","authors":"Xiyue Cheng*,&nbsp;Victor Trinquet,&nbsp;Bohan Ding,&nbsp;Gian-Marco Rignanese,&nbsp;Xavier Gonze and Shuiquan Deng*,&nbsp;","doi":"10.1021/acs.chemmater.5c0010910.1021/acs.chemmater.5c00109","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00109https://doi.org/10.1021/acs.chemmater.5c00109","url":null,"abstract":"<p >The recent synthesis of two noncentrosymmetric (NCS) nitridophosphates, GeP₂N₄ and Sn₆[P₁₂N₂₄], featuring stereochemically active lone pairs (SCALPs), provides an opportunity to explore their role in nonlinear optical (NLO) properties and assess the potential of nitridophosphates for NLO applications. Through high-throughput screening of all nitridophosphate compounds in the Materials Project database and Inorganic Crystal Structure Database, we identify 23 NCS nitridophosphates with nonzero second-harmonic generation (SHG) responses. In comparison, <i>M</i>P₂N₄ (M = Ge, Sn, Pb) family, in both <i>Pna</i>2₁ and <i>R</i>3<i>m</i> structures, emerges as the only nitridophosphates that combines significant SHG response and sizable birefringence within a band gap range suitable for infrared NLO applications. First-principles calculations reveal that <i>Pna</i>2₁ phases of <i>M</i>P₂N₄ generally exhibit larger SHG responses than the <i>R</i>3<i>m</i> ones and substituting Ge²⁺ with more polarizable Sn²⁺ or Pb²⁺ enhances the SHG response to 4.1 and 7.2 pm/V (∼12 and 22 × KDP), respectively. Our atom response theory analysis indicates that the SHG response is predominantly driven by nonbonding N 2p states, while SCALPs provide a positive but secondary contribution, as the SHG magnitude inversely correlates with SCALP strength. Additionally, we reveal that NaPN₂ and HPN₂ exhibit impressive SHG response (∼10 × KDP) combined with remarkable band gaps exceeding 6.2 eV, making them promising candidates for ultraviolet (UV) or visible NLO applications. This study sheds light on the mechanisms driving the NLO behavior in <i>M</i>P₂N₄ and highlights nitridophosphates as a promising platform for developing advanced NLO materials.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 10","pages":"3709–3719 3709–3719"},"PeriodicalIF":7.2,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144137411","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}