02821nas a2200313 4500008004100000245018800041210006900229260000800298300001600306490000600322520168400328653002302012653001802035653003302053653003202086653002002118653003302138653002202171100002002193700001602213700001702229700001702246700002002263700001902283700002402302700002602326700002402352856013102376 2022 eng d00aFirst-principles investigation of the electrocatalytic reduction of CO2 on zirconium-based single-, double-, and triple-atom catalysts anchored on a graphitic carbon nitride monolayer0 aFirstprinciples investigation of the electrocatalytic reduction  cOCT a15409-154170 v53 a

Conversion of carbon dioxide (CO2) with the help of an appropriate electrocatalyst with high stability, low onset potential, and exceptional selectivity is still one of the great tasks in the electrocatalytic reduction of CO2 to valuable chemicals. Herein, by means of systematic first-principles simulations, we investigate the CO2 reduction reaction (CO2RR) activity of zirconium-based single-, double-, and triple-atom (Zrn@C2N; n = 1-3) catalysts anchored on a graphitic carbon-nitride monolayer. In tune with the Sabatier principle, our results reveal that a moderate CO2 binding is vital for a low onset potential for the CO2RR. Consequently, based on rigorous free energy calculations, the Zr-based single-atom catalyst (SAC) is found to be most effective to convert CO2 to valuable products such as HCOOH and CH3OH. It is worth noting that CO2 reduction to HCOOH is spontaneous via the *HCOO intermediate on Zr1@C2N and involves a low onset potential of -0.23 V with respect to the reversible hydrogen electrode from the *COOH intermediate. Among all the catalysts evaluated computationally, the Zr SAC further reveals the lowest onset potential of -0.89 V for CH3OH formation. The results show that the Zr-based catalysts especially Zr1@C2N are found to effectively suppress the competitive hydrogen evolution reaction and promote the CO2RR. Moreover, all three catalysts exhibit high kinetic and thermal stability with negligible distortion due to which their structures can be retained very well up to 600 K. Thus, the current work may provide effective catalyst-design strategies for enhancing the electrocatalytic CO2RR performance of Zr-based materials.

10aC1 and C2 products10aCO2 reduction10afirst-principles simulations10ahydrogen evolution reaction10aonset potential10asingle-atom catalysts (SACs)10aZrn@C2N catalysts1 aHassan, Afshana1 aAnis, Insha1 aShafi, Sadaf1 aAssad, Assif1 aRasool, Anjumun1 aKhanam, Romana1 aBhat, Gulzar, Ahmad1 aKrishnamurty, Sailaja1 aDar, Manzoor, Ahmad uhttps://library.ncl.res.in/content/first-principles-investigation-electrocatalytic-reduction-co2-zirconium-based-single-double02018nas 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

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.

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

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.

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