02018nas a2200229   4500008004100000022001400041245013100055210006900186260000800255490000700263520115500270653002201425653002101447653002901468653003201497653002301529653002401552653003201576100002401608700002601632856013001658       2025                        eng d  a1439-423500aGraphitic carbon nitride supported boron quantum dots: a transition metal free alternative for di-nitrogen to ammonia reaction0 aGraphitic carbon nitride supported boron quantum dots a transiti  cMAR0 v263 a<p>
	Presently, a sustainable electrochemical Nitrogen Reduction Reaction (NRR) has been essentially found to be viable on transition metal-based catalysts. However, being cost-effective and non-corrosive, metal-free catalysts present an ideal solution for a sustainable world. Herein, through a DFT-based study, we demonstrate metal-free NRR catalysts, boron quantum dots with 13 atoms as a case study and their chemically modified counterparts when anchored on graphitic carbon nitride (g-C3N4) surface. The best catalyst among the studied, a silicon-doped boron quantum dot with a cagelike structure, is found to favour the dinitrogen to ammonia reaction pathway with a low liming potential and potential rate-determining step (PDS) of -0.11 V and 0.27 eV, respectively. The present work demonstrates as to how boron quantum dots, which are reported to be experimentally synthesised, can be exploited for ammonia synthesis when supported on the surface. These catalysts effectively suppress the HER, thus establishing its suitability as an ideal catalyst. The work also represents a futuristic pathway towards a metal-free catalyst for NRR.</p>
10aBoron quantum dot10aElectro-catalyst10aGraphitic carbon nitride10ahydrogen evolution reaction10aLimiting potential10ametal free catalyst10aNitrogen Reduction Reaction1 aSamudre, Nikhil, S.1 aKrishnamurty, Sailaja  uhttps://library.ncl.res.in/content/graphitic-carbon-nitride-supported-boron-quantum-dots-transition-metal-free-alternative-di02223nas a2200241   4500008004100000022001400041245009300055210006900148260000800217300001400225490000700239520137500246653001501621653001601636653002101652653003201673653004501705653003101750100002401781700002901805700002601834856012101860       2026                        eng d  a2168-048500aSilico imine-based ligand engineering of CALF-20 for electrocatalytic ammonia production0 aSilico iminebased ligand engineering of CALF20 for electrocataly  cAPR  a7217-72280 v143 a<p>
	Electrocatalytic ammonia synthesis is emerging as a globally compelling, sustainable alternative to the Haber-Bosch process under ambient conditions. As a result, active-site engineering has taken center stage in the development of stable and effective electrocatalysts. In this work, we report how the introduction of an imine group in the ligand backbone of CALF-20, a Zn-based, moisture-stable MOF with high surface area, results in the formation of an N-4 macrocycle for transition-metal anchoring. PBE + D3 calculations, supported by spectroscopic, ab initio molecular dynamics, and electronic analyses, identify Fe-bound modified CALF-20 as the most stable configuration among the Mn-, Fe-, Co-, Ni-, Cu-, Ru-, Rh-, Ag-, and Au-anchored within the modified CALF-20 framework. Upon modification, the d-band center shifts from -5.08 to -4.44 eV in M-Fe-CALF-20. Adsorption studies confirm activation of both N-2 and NO2, reflected by bond elongation and red-shifted IR peaks. Mechanistic studies show that M-Fe-CALF-20 selectively facilitates NH3 formation, exhibiting PDS values of 0.69 and 0.62 eV for the NRR and NO2RR, respectively, while a competitive adsorption shows a clear preference over HER. Our study illustrates how functionalization tunes CALF-20 for dual application as an adsorbent and as an electrocatalyst for NH3 synthesis and storage.</p>
10aAdsorption10aCALF-20 MOF10aelectrocatalysis10ahydrogen evolution reaction10anitrogen oxide reductionreaction (NO2RR)10anitrogen reductionreaction1 aSamudre, Nikhil, S.1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja  uhttps://library.ncl.res.in/content/silico-imine-based-ligand-engineering-calf-20-electrocatalytic-ammonia-production