Effects of catalyst composition on methanol synthesis from CO2/H2

Selective Hydrogenation of CO2 to CH3OH on Supported Cu Nanoparticles Promoted by Isolated TiIV Surface Sites on SiO2

“…The most prominent catalysts for selective CO 2 hydrogenation to CH 3 OH are Cu-based, although their activity and CH 3 OH selectivityd ramatically depend on the oxide support. [9] In fact, Cu nanoparticles supported on SiO 2 decorated with isolated Zr IV sites show CO 2 hydrogenationa ctivity andC H 3 OH selectivity nearly identicalt ot hose for Cu/ZrO 2 , [13] underscoring the importance of these Lewis acid sites at the periphery of Cu nanoparticles for the selective hydrogenation of CO 2 to CH 3 OH.In contrast, Cu/TiO 2 has been observed to be av ery poor CO 2 hydrogenation catalystw ith low reaction rates and low CH 3 OH selectivity, [7,8,14] in spiteo ft he ability of Ti IV metal cen- [a] Dr. [9][10][11][12] Whereas SiO 2 can be considered as an inert support for the Cu nanoparticles that catalyzet he reaction, ZrO 2 provides Zr IV sites interfacing Cu nanoparticles that act as Lewis acid sites andp romote CH 3 OH synthesis.…”

“…[9][10][11][12] Whereas SiO 2 can be considered as an inert support for the Cu nanoparticles that catalyzet he reaction, ZrO 2 provides Zr IV sites interfacing Cu nanoparticles that act as Lewis acid sites andp romote CH 3 OH synthesis. [9] In fact, Cu nanoparticles supported on SiO 2 decorated with isolated Zr IV sites show CO 2 hydrogenationa ctivity andC H 3 OH selectivity nearly identicalt ot hose for Cu/ZrO 2 , [13] underscoring the importance of these Lewis acid sites at the periphery of Cu nanoparticles for the selective hydrogenation of CO 2 to CH 3 OH.In contrast, Cu/TiO 2 has been observed to be av ery poor CO 2 hydrogenation catalystw ith low reaction rates and low CH 3 OH selectivity, [7,8,14] in spiteo ft he ability of Ti IV metal cen- [a] Dr.…”

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Small and narrowly distributed Cu nanoparticles, supported on SiO 2 decorated with isolated Ti IV sites, prepared through surface organometallic chemistry,s howeds ignificantly improved CO 2 hydrogenationa ctivity and CH 3 OH selectivity compared to the corresponding Cu nanoparticles supportedo nS iO 2 .T hese isolated Lewis acid Ti IV sites, evidenced by UV/Vis spectroscopy, are proposed to stabilize surface intermediates at the interface between Cu nanoparticlesa nd the support.

The selective hydrogenation of CO 2 to CH 3 OH, together with the production of H 2 from renewable energy sources (e.g.,i ntermittent excesse nergy generatedf rom wind or solarp ower) is essential to av irtuous sustainable closed-carbon fuel cycle. [5][6][7][8] Cu supportedo nZ rO 2 (Cu/ZrO 2 ,i nw hich "Cu/X"d enotes Cu nanoparticles dispersed on support X) has shown promising activity and high CH 3 OH selectivity compared to Cu/ SiO 2 . The most prominent catalysts for selective CO 2 hydrogenation to CH 3 OH are Cu-based, although their activity and CH 3 OH selectivityd ramatically depend on the oxide support.

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“…The most prominent catalysts for selective CO 2 hydrogenation to CH 3 OH are Cu-based, although their activity and CH 3 OH selectivityd ramatically depend on the oxide support. [5][6][7][8] Cu supportedo nZ rO 2 (Cu/ZrO 2 ,i nw hich "Cu/X"d enotes Cu nanoparticles dispersed on support X) has shown promising activity and high CH 3 OH selectivity compared to Cu/ SiO 2 . [9][10][11][12] Whereas SiO 2 can be considered as an inert support for the Cu nanoparticles that catalyzet he reaction, ZrO 2 provides Zr IV sites interfacing Cu nanoparticles that act as Lewis acid sites andp romote CH 3 OH synthesis.…”

“…In contrast, Cu/TiO 2 has been observed to be av ery poor CO 2 hydrogenation catalystw ith low reaction rates and low CH 3 OH selectivity, [7,8,14] in spiteo ft he ability of Ti IV metal cen- [a] Dr.…”