Inspirational perspectives and principles on the use of catalysts to create sustainability

Ca alysis Today xxx (xxxx) xxx Please ci e his a icle as: Juan Ga cía-Se na, Ca alysis Today, h ps://doi.o g/10.1016/j.ca od.2021.11.021 A ailable online 19 No embe 2021 This is an open access a icle unde he CC BY license (h p://c ea i ecommons.o g/licenses/by/4.0/). Inspi a ional pe spec i es and p inciples on he use o ca alys s o c ea e sus ainabili y Juan Ga cía-Se na a , * , Raúl Pi˜ ne o-He nanz b , Desi ´ ee Du ´ an-Ma ín b a G upo de Tecnologías a P esi´ on (P essTech), Ins i u o de Bioeconomía de la Uni e sidad de Valladolid (BioEcoUVa), Depa amen o de Ingenie ía Química y Tecnología del Medio Ambien e, Escuela de Ingenie ías Indus iales, Uni e sidad de Valladolid, 47011 Valladolid, Spain b Bio echnology and Sus ainable Chemis y A ea, Cen e o Technology CARTIF, Pa que Tecnol´ ogico de Boecillo, 205, 47151 Boecillo, Valladolid, Spain ARTICLE INFO Keywo ds: Ca alysis p inciples G een chemis y G een enginee ing Sus ainable ca alysis Cleane p ocesses ABSTRACT Mos o he p oduc s on which ou wel a e s a e is based a e composed o chemicals. The g ow h o he wo ld’s popula ion, i s ageing and he con inuous imp o emen o wel a e s a e aspi a ions augu an inc ease in he needs o all hese e e yday p oduc s in ou li es. A high pe cen age o hese chemicals a e syn hesised using ca alysis. In his pe spec i e pape , we highligh he impo ance o ca alysis, which is a he hea o chemical p ocesses, and he e o e one o he ools o c ea ing p oduc s ha d i e sus ainabili y. We ha e compiled wel e me hodological bes p ac ices in ca alys design and concep ion ha can se e as inspi a ion o he c ea ion and imp o emen o ca alys s. We include some applica ion examples o illus a e his. 1. In oduc ion The idea o sus ainabili y has been a ound o a long ime bu has gained conside able momen um in he las i e yea s wi h he global campaign o he 17 Sus ainable De elopmen Goals (SDGs). Sus ain- abili y does no jus mean li ing well and allowing ou u u e gene a- ions o do he same. I is a p o ound concep ha akes in o accoun h ee basic pilla s: he economy, he en i onmen and socie y. These pilla s ha e o be based on a le el playing ield, no only o u u e gene a ions bu also o oday’s gene a ion. These pilla s a e unde - pinned by equali y and a e cons an ly e ol ing h ough he my iad disciplines o science, enginee ing, a chi ec u e, medicine, poli ics, he a s, humani ies and cul u e o he ulles ex en . By ge ing down o ea h, e e y discipline can play a pa in pa ing he way owa ds a sus ainable socie y. Chemis y and chemical enginee ing a e a he basis o ou daily li es, p o iding he main p oduc s ha mee ou demands and needs o main ain and imp o e ou s a e o well-being. The p inciples o g een chemis y es ablished a use - iendly amewo k o sus ainable p ocess design wi h a co e in chemis y. In 1998 Paul Anas as and John Wa ne we e able o dis il om he bes p ac ices o chemis y, eal and a o dable p ac ices ha we e al eady in applica ion [1]. Mo e han wen y yea s la e , g een chemis y is al eady a co e discipline in mos chemis y acul ies and companies a ound he wo ld, al hough a eal push is s ill needed o make i a pe manen eali y. Among he p inciples o g een chemis y, one ha inco po a es conside able imp o emen s in all he o he s is ca alysis. Ca alysis makes i possible o make ma e ials eac ha did no p e iously do so, opening up he possibili y o using enewable, sa e o mo e eadily a ailable ma e ials. I also makes i possible o educe ope a ing condi ions in e ms o p essu e and empe a u e, wi h consequen ene gy sa ings. Ca alysis is a he hea o mos chemical p ocesses. Nine y- i e pe cen o chemicals in indus y, which is equi alen o 80 pe cen o hei added alue, a e syn hesised using ca alys s. O hese, he e ogeneous ca alysis accoun s o almos 80%, homogeneous ca alysis o 15% and he es is bioca alysis [2]. In many cases, he op imisa ion o hese p ocesses is so e ined ha i is e y di icul o imp o e hem u he . In such ci cums ances we mus ind he b eak h ough by app oaching he hea , he ca alys . In his pe spec i e pape , we would like o ecapi ula e on wel e cu en ends ha can be o g ea use o he de ini ion o new ou -o - he-box ca alys s ha in insically p omo e sus ainabili y om wi hin p ocesses. Wi h he help o hese basis and a dash o c ea i i y, we belie e ha exis ing ca alys s can be imp o ed, bu also new, game- changing ca alys s can be c ea ed. * Co esponding au ho . E-mail add ess: [email p o ec ed] (J. Ga cía-Se na). Con en s lis s a ailable a ScienceDi ec Ca alysis Today jou nal homepage: www.else ie .com/loca e/ca od h ps://doi.o g/10.1016/j.ca od.2021.11.021 Recei ed 27 Sep embe 2021; Recei ed in e ised o m 2 No embe 2021; Accep ed 9 No embe 2021 Ca alysis Today xxx (xxxx) xxx 2 2. Basic p inciples o ca alysis owa ds sus ainabili y 2.1. Ac i e me al Use ac i e me als ha a e accessible, s able and low-cos . A oid he use o endange ed, oxic o dange ous me als. In mos ca alys s, me als a e a he co e o hei ca aly ic ac i i y and pe o mance. The e o e, e o s o de elop a mo e sus ainable ca alysis mus conside he sus ainabili y o ac i e me als. The assessmen o his cha ac e is ic can be ocused on h ee main aspec s: i) a ailabili y, ii) low cos , and iii) oxici y. In e ms o a ailabili y and cos , he e a e majo di e ences depending on he ype o me als, being hose called p ecious me als a less a ailable and mo e expensi e han hose e e ed as base me als. P ecious me als a e in he second and hi d ows o he pe iodic able and hose commonly used as ansi ion-me al ca - alys s a e P , Pd, Rh, Ru, Os, I , Au and Ag. They lack abundance in he Ea h c us al, and ha de e mines hei high cos and luc ua ions in p ice and supply. Fo example, in he pe iod be ween 2018 and 2019, a e age palladium and hodium p ices we e up 20% and 83% espec- i ely, while he pla inum p ice declined 11% compa ed o he same pe iod las yea [3]. The B i ish Geological Socie y eleased a lis o me als a isk o supply dis up ion whe e he pla inum-g oup me als ( u henium, hodium, palladium, osmium, i idium, and pla inum) a e es ima ed o be a he highes isk [4]. In addi ion o he ob ious economical and supply conce ns ela ed o p ecious me als, hey also ha e en i onmen al implica ions. Ac ually, mining and e inemen o hese ma e ials equi e a la ge use o ene gy and emi la ge amoun s o CO 2 [5]. E en hough hei high demand and sca ci y, i is es ima ed ha less han 1% o p ecious me als a e ecycled o euse. This low pe - cen age is due o he low economic iabili y o ecycling p ocesses, which o en equi e la ge amoun s o wa e and highly co osi e acids, while gene a ing la ge amoun s o was e. In his scena io, a cu en app oach in he de elopmen o mo e sus ainable ac i e me als elies on he use o high c us al abundan me als e e ed as base me als. Ti anium, anadium, ch omium, man- ganese, i on, cobal , nickel, and coppe , ep esen base me als wi h ad an ages o e he use o pla inum-g oup me als such as low cos , global a ailabili y and lowe oxici y. P og ess is being made in ecen yea s o enhance he eac i i y o base me als and o e come disad an- ages like lowe s abili y, selec i i y and changing oxida ion [5]. Despi e base me al ca alys s ha e been p o ed eliable o some eac ions, u he esea ch is needed o con i m hei easibili y in o he eac ions adi ionally pe o med wi h p ecious me als, which will lead o sub- s an ial bene i s o he u u e socie y and en i onmen . Rega ding oxici y, base me als a e o en conside ed less oxic han p ecious me als wi h minimal sa e y conce ns. Howe e , he assessmen o oxici y is complex. Ac ually, se e al wo ks epo ed ha widely conside ed hea y and oxic me als such as palladium, pla inum, and gold compounds may no be so dange ous, while complexes o nickel and coppe , gene ally assumed as g een and sus ainable op ions, may be signi ican ly oxic (i.e., due o hei solubili y in wa e and biological luids) [6]. A pionee wo k ecen ly epo ed a comp ehensi e com- pa ison o he oxici y o 18 me als ypically used in ca alysis based on mul ic i e ia analysis conside ing pa ame e s such as he oxici y o pu e me als and me al sal s owa d ish, Daphnia magna, and algae/plan s, me al oxici y owa d a s ia inges ion, ca cinogenici y, he endan- ge men deg ee o me als, he boiling poin and ene gy o a om de achmen [7]. Thei conclusions we e simila o hose ound in p e- ious wo ks [6] and showed u henium, molybdenum, pla inum and manganese as he mos a ou able (less oxic) ac i e me als, in con as o nickel, cobal , and palladium as he mos oxic. 2.2. Designed in-silico Design he ca alys using he bes a ailable in-silico echniques o op imise esou ces dedica ed o es ing and speed-up he de elopmen . He e ogeneous ca alysis exhibi s an inhe en design, in en ion di - icul y and equi ed e o as i combines a omic, mic oscopic, meso- scopic, and mac oscopic scales. I in ol es he modynamics, eac ion, adso p ion/deso p ion and mass ans e . The obse a ion o he eac ion can be done by compu a ional me hods, bu eaching chemical accu acy (e o lowe han 1 kcal⋅mol −1 ) is limi ed o ew a oms. The calcula ion can be simpli ied by using Densi y Func ional Theo y (DFT), which allows he simula ion o up o 100 a oms, a he cos o conside ably educed accu acy. La ge a eas canno be simula ed due o he high compu a ional powe equi ed [8]. Fu he mo e, he e a e a numbe o g and challenges in he compu a ional ca alysis ha s ill ha e o be sol ed, e.g. exponen ially o a e o eac ion wi h ene gy ba ie , complexi y o ligands in homoge- neous ca alysis, su ace in e ac ions wi h he ac i e me al in he e oge- neous ca alysis o he di icul y o modelling elec on and p o on ans e s eps in elec o-ca alysis [9]. Ab ini io a omis ic he modynamics can be used oge he wi h DFT o in es iga e he in luence o empe a u e, p essu e o composi ion in he su ace ee ene gies. The unde s anding o he eac ion implies he p edic ion o eac ion mechanism and eac ion pa hway, oge he wi h he kine ics. Mic o- kine ic modelling can be done, o ins ance, by combining he La ice- gas Hamil onian (LGH) wi h Mon e-Ca lo (MC) simula ions [10]. Machine Lea ning (ML) and Deep Lea ning (DL) echniques allow o he as calcula ion o hese a omis ic p ope ies, e.g. binding ene gy, using p e ious da a om DFT o MC simula ions. Saxena e al. sc eened he ca aly ic op ions o e hanol decomposi- ion and non- oxida i e dehyd ogena ion eac ions [11]. Single a om alloys and bime allic alloys we e analysed using ML, op imising he binding ene gies o oxygen and ca bon s a ing om well-known p op- e ies. A e selec ing a p ope alloy an ab ini io mic okine ic model was applied o es ima e he pe o mance ( u n o e equency, TOF). The calcula ion ook less han a second. Kine ic expe imen s will in many cases be una oidable, bu he use o compu a ional echniques can g ea ly educe esou ces and ime spen . The igh combina ion o simula ion p edic ion and expe imen al e i- ica ion is he key o imp o emen in he medium and long e m. 2.3. Scalable ab ica ion New imp o ed ca alys s suppo s/s uc u es and hei manu ac u ing echniques a e aimed o acili a e he pe o mance o eac o s a la ge/in- dus ial scale. Some examples o scalable-easy-manu ac u ing ca alys s may be ocused on he enhancemen o design and ab ica ion o he ca alys a mac o-le el in o de o op imise he mass/hea ans e and o e all pe o mance o he ca aly ic eac o sys em [12]. Mo eo e , he applicabili y o he ca alys is inc eased i i can be p epa ed in di e en o ma s, i.e. powde , pelle s, oams, monoli hs, e c. 3D p in ing allows o a e y speci ic and ailo ed design o mass ans e and low p essu e d op. Special a en ion has o be aken o he binde s used [13]. 2.4. Fas induc ion and in-si u ac i a ion Fas induc ion pe iods a e desi ed, sa ing ime and ma e ials. In-si u ac i a ion eases he handling and ac i i y. Fas induc ion a es allow ca alys s o each hei op imum ac i i y (highes con e sion and selec i i y) in sho pe iod imes since hey a e ac i a ed, which bene i he pe o mance o he eac ion and inc ease he p oduc i i y, sa ing ime and ma e ials. In-si u ac i a ion also eases ca alys handling and ac i i y. Thus, a speci ic ca alys design/p epa a ion aimed a sho ening he induc ion pe iod o he ca alys o imp o ing he ac i a ion p ocedu e (i.e. educing ime/ene gy consump ion, o e en ually, imp o ing he ca a- lys s pe o mance o s abili y) may ha e a signi ican impac on he J. Ga cía-Se na e al. Ca alysis Today xxx (xxxx) xxx 3 o e all pe o mance and ime li e o a ca alys , hus imp o ing i s p ope ies as a mo e s able and e icien ma e ial, and hus i s sus ain- abili y in e ms o cos and en i onmen impac [14]. One example is imp o emen s in he design o ca alys s o me hane dehyd o-a oma isa ion (MDA) eac ion, in which a speci ic mixed o me als (Fe, P ) o dope he ac i e phase is able o p omo e a apid o - ma ion o he ac i e si es and, in addi ion, o wi hs and sin e ing/ag- glome a ion, hus, imp o ing he s abili y and op imal pe o mance o he ca alys and also inhibi ing he accumula ion o coke on he ex e nal su ace o he ca alys du ing he eac ion [15,16]. 2.5. S abili y Design o s abili y, o a oid poisoning, deg adabili y and leaching. Despi e ca alys s a e no consumed du ing eac ion, hei s abili y is limi ed and end o deac i a e wi h p olonged eac ion imes. Ca alys deac i a ion leads o a signi ican dec ease in p ocess yield and selec- i i y wi h p oduc ion o undesi able componen s. The e o e, dec easing o a oiding deac i a ion is essen ial o imp o e sus ainabili y in ca al- ysis and hus educing he need o eplace spen ca alys s wi h con- sump ion o new ma e ials, ene gy and wa e . A he same ime, imp o ed s abili y may enhance he e iciency o he chemical p ocess sa ing ope a ion cos and dec easing he p oduc ion o pollu an s and undesi ed by-p oduc s. In o de o design s able ca alys s, i is pa amoun o unde s and hei speci ic deac i a ion easons. The mos common ones a e summa ised below along wi h some s a egies applied o o e come hem. i) Poisoning by componen s in eagen s o eac ion in e media es. A ypical example o poisoning occu s du ing hyd oca bon p o- cessing whe e sulphu is p esen in some eagen molecules (me cap ans, hiophenes…). Sulphu is s ongly chemiso bed o e me allic su ace o ca alys (and may o m s able me al sulphides) and disables i s ca aly ic ac i i y. CO is ano he well- known poison o ca alys s. This is a c i ical issue in uel cells ed wi h hyd ogen p oduced om hyd oca bons. Small p esence o CO in he hyd ogen eed (o e 20 ppm) leads o quick deac- i a ion o P ca alys in he anode o he cell since i is adso bed o e he P su ace o ming s able P -C bonds. Ano he ypical example o poison is coke. I is an undesi able by-p oduc p o- duced du ing hyd oca bon p ocessing a high empe a u es. I does no o m chemical compounds wi h me als o suppo s. Howe e , i g ows o e he ca alys su ace and blocks he access o eagen s o he ca aly ic ac i e si es. ii) Sin e ing, desc ibed as a compac ion and densi ica ion o ac i e me als o suppo s, equen ly occu s when a ca alys is subjec ed o high empe a u es. In suppo ed ca alys s, high empe a u es leads o a nuclea ion o he dispe sed me allic pa icles and hei agg ega ion in he o m o la ge c ys als wi h subsequen loss o ac i e si es exposed o eagen s. The consequence o his p ocess is a dec ease o he ca aly ic ac i i y. Ca aly ic suppo s also su e om his compac ion p ocess and collapse o hei po ous ex u e. The ou come is a educ ion o he su ace a ea o he ca alys , diminishing he ac i e si es exposed o eagen s. Simila compac ion e ec s ake place in bulk ca alys s lowe ing hei ca aly ic ac i i y. iii) Loss o ca alys componen s in he eac ion media. These phe- nomena occu in liquid phase ca alysis (eg. he lixi ia ion o Ca om ca alys s du ing syn hesis o biodiesel) bu also in gas phase eac ions, when me al pa icles o ce ain elemen s ola ise unde high empe a u es (eg. RuO 2 is oxidised and o ms gaseous RuO 3 and RuO 4 molecules). Ano he example unde his sec ion is he dealumina ion o zeoli es used as ca alys s o ca aly ic suppo s when subjec ed o ha sh hyd o he mal condi ions. Di e en s a egies ha e been applied o imp o e he s abili y o ca alys s and o e come o educe hei deac i a ion. Fo example, he addi ion o lan hanides (usually La o Ce oxides) o ca aly ic suppo s p omo e he o ma ion o ca bona e and hyd oxyl in e media es du ing eac ion which con ibu e o he gasi ica ion o coke p oduced om hyd oca bons p ocessing [17]. Sulphu aps a e also used o p e e en ially adso b i and a oid he con amina ion o he ac i e me al si es. The Ellingham diag am o me al sulphides is an in e es ing ool o choose he igh componen s o hese aps since i shows ee ene gy o o ma ion o di e en sulphides a di e en empe a u es. A ecen example is he use o Mn oxides as sulphu aps in emission con ol ca alys s [18]. In o de o a oid sin e ing o alumina suppo s, manu ac u e s ha e enginee ed op imised o mula ions by o ming highly he mally s able alumina es (e.g. LaAlO 3 ) in he su ace o alumina. Despi e he educ ion o he su ace a ea o he no el suppo , he s abili y o i s po ous ex u e unde high empe a u e is g ea ly imp o ed. Zeoli e ca alys s used in luid ca aly ic c acking p ocesses usually su e om dealumina ion by s eam a high empe a u es. A s a egy o add ess his issue is by enginee ing he zeoli es wi h he addi ion o a e- ea h elemen s and phospho us [19]. 2.6. Biomime ic Ca alys s designed by na u e a e e y e ec i e, wo k a ambien condi- ions and a e e y speci ic by using molecula ecogni ion (sel -assembly). John Wa ne , one o he ea ly ounde s o G een Chemis y, illus- a es e y well how he basis o mode n chemis y is based on collision eac ions. The p obabili y o collision is inc eased by inc easing p essu e and empe a u e [20]. A he same ime, he poin s ou ha his model di e s g ea ly om na u e, whe e he e is no single collision eac ion. In na u e, molecules app oach, ecognise, "snuggle" each o he and hen eac a ambien p essu e and empe a u e. Mo eo e , Janine Benyus opened a simple way o design inspi ed by na u e. Biomimic y akes na u e as a model, as a men o and as a measu e. Ca alys s exis in na u e, i is he only way o c ea e e icien and e ec i e eac ions a oom empe a u e and a mosphe ic p essu e. Di ec ly designing an enzyme is s ill a long way o , bu mimicking hem is now possible. The e a e se e al possible op ions o c ea ing biomime ic me al o ganic amewo k (MOF) ca alys s as explained by Chen and Chuan [21]: •Using me als as biomime ic ac i e si es. •Encapsula ion o p e en sel -agg ega ion and inc ease shel li e. •Newly c ea ed suppo o amewo k based on a simila biomime ic s uc u e. •Inco po a ion o biomime ic pa s ia o ganic linke s •Pos -syn hesis modi ica ion The adi ional chemis y o p epa ing imines om aldehydes, ke- ones, amines, ni iles and o he s is well known. Bu o all he possible me hods, e e ence was a ely made o how na u e does i . Speci ically, coppe amine oxidases (CuAOs) a e esponsible o hese p ocesses o con olling he me abolism o amines o di e en ypes. Bioinspi ed by CuAOs, quinone-based ca alys s ha e been de eloped [22]. 2.7. Ci cula by p ocess design o o igin o he esou ce The ca alys should be designed o be ci cula in he suppo , ac i e me al and addi i es. A ca alys based on he ci cula economy can be de eloped based on di e en app oaches, which ypically ake in o accoun he en i e ca alys alue chain, om he o igin and esou ces o he ma e ials he ca alys is made o , o he a e -li e o he ca alys , and key impac / sus ainabili y pa ame e s such as he ca bon oo p in o he manu ac u ing p ocess. Di e en app oaches may be conside ed o quali y a ca alys as sus ainable based on he ci cula i y o a ca alys , as J. Ga cía-Se na e al. Ca alysis Today xxx (xxxx) xxx 4 ou lined below: I. Ci cula by o igin o he aw ma e ials/ esou ces: P esen ly, mos o he ca aly ic ma e ials a e sou ced om ini e geological deposi s. By eco e ing ca alys om was e and eclama ion o ac i e me als om spen ca alys , he dependence on na u al esou ces ha a e unsus ainable will be educed, likewise he quan i y o ma e ials going o land ill. A ci cula economy pe spec i e, conside ing he E-was e managemen along wi h he eco e y o noble me als om spen ca alys s, can be conside ed as a new concep o ca alys c adle- o-c adle p o- cess and, e en ually, a p omising sus ainable sou ce o ca aly ic ma e ials manu ac u ing [23–26]. An example o his eme ging ci cula alue chain is he eco e y o he aluable me als om indus ial and pos -consuming p oduc s such as elec onic was e ma e ials (E-was e). Acco ding o he Global E-was e Moni o 2020 [27], E-was e is he wo ld’s as es g owing was e s eam and he amoun is es ima ed o inc ease o 52.2 million me ic onnes by 2021 and he end could be going up o each he amoun will each 74 million M . in 2030. The inc easing gen- e a ion and accumula ion o E-was e is clea ly poin ing o a c i ical en i onmen al challenge which needs o be add essed in he immedia e u u e. Thus, he design o enewable ca alys made om was e ma e ials o a ca alys based on ecycled ma- e ials is an al e na i e clea ly mo e sus ainable, especially when i is aimed a p ecious me als which a e mo e di icul , expensi e -and en i onmen -cos ly- o ex ac (e.g. Au, P , Pd, Ru, e c.) [28, 29]. In addi ion, he eco e y o aluable mine als om indus- ial e luen s ea men and leaching p ocess in mining exploi- a ions a e po en ial applica ions han can be de elop as po en ial case exploi a ions based o ci cula -by p ocess/design [30,31]. To ha end, se e al s a egies ha e been epo ed o me als e- co e y om E-was e and indus ial s eams, al hough he e is s ill a long way o go o ind en i onmen ally iendly and e icien p o ocols in his ega d [30,32]. In combina ion wi h Sec ion 2.1, when he use o noble me als is equi ed (as subs i u ion is no possible), inding sus ainable ecycling me hods and s a egies will be he key o success. II. Ci cula by he manu ac u ing and pe o mance p ocess design: Ca alys s ha use g een/clean echnologies o hei ab ica- ion in ol e he u ilisa ion o ewe na u al esou ces, educing pollu ion and was e, ecycling and/o eusing ma e ials, and p oducing mode a e emissions in hei p ocesses. All hese inpu s lead he manu ac u ing p ocess o consume less ene gy and e- sou ces making he ab ica ion o he ca alys i sel mo e sus- ainable and cos -compe i i e han o he con en ional p ocesses [28]. The g een echnologies mos equen ly encoun e ed a e he ecycling o was e, was e wa e ea men and enewable ene gy, o ins ance, he applica ion on new hie a chical- i anium diox- ide ca alys s, which include ac i e mic opo ous zeoli es and mesopo ous ma ix o di usion, allows o inno a i e g een applica ions such as he syn hesis o uels om ca aly ic c acking o was e plas ics [33]. III. Ci cula by he end-use o applica ion o he ca alys : A ca alys may be also conside ed sus ainable i i has been designed o special applica ions ocused on clima e change mi iga ion, e.g. h ough he p oduc ion o ca bon-nega i e p oduc s and uels (CO 2 - o- chemicals p ocesses), elimina ion o pollu ion om indus ial/human ac i i y in he wo ld, e c. [34,35]. Addi ionally, he ca alys s o au o- mobile emission con ol a e based on p ecious me als such as pla inum, palladium, and hodium. A p esen , mo e han 15 in e na ional com- panies a e p oducing abou 100 undamen al ypes o solid ca alys s. Ca alys s play an essen ial ole in indus y no only in economic e ms bu also in educing pollu ion o he en i onmen [36]. 2.8. Use o enewable esou ces Ac i e ca alys s wi h enewable ma e ials may help in he ans o ma ion o ou oil-based socie y in o a bio-based socie y. Ac i e ca alys s wi h enewable ma e ials can help ans o m ou pe oleum-based socie y in o a bio-based socie y, o example by p o- ducing chemical building blocks de i ed om CO 2 , such as C1 molecules (me hane, me hanol, o maldehyde) o di e en C2-C4 molecules anging om e hylene/ole ins ma e ials o o he long-chain hyd oca - bons, o e en o e ing an al e na i e o he cu en p oduc ion o p oduc s om c ops o o he bio-based ma e ials (e.g. ag icul u al es- idues such as e penes, a y acids and lipids can be used as bio-based pla o m chemicals o he p epa a ion o biopolyme s). Fo example, ag icul u al esidues such as e penes, a y acids and lipids can be used as bio-based chemicals o he p epa a ion o biopolyme s [37,38]. In addi ion, ac i e ca alys s owa ds biomass and na u al p oduc s con ibu e o he deca bonisa ion o indus y and he economy o boos he ans o ma ion o ou oil-based socie y in o a bio-based socie y. The e a e se e al examples o new ca alys s speci ically designed o he ans o ma ion o biomass in o bio uels and enewable chemicals. These ca alys s will play an impo an ole in in eg a ed bio e ine ies and bio- based indus ies in he u u e [39]. As an example, one o he mos p omising he e ogeneous ca aly ic p ocesses in biomass being s udied is he p oduc ion o u u al. Fu u al is a C5 building block ha can be con e ed in o a la ge numbe o alue-added chemicals and bio- chemicals, as well as p oducing ad anced syn he ic uels [40]. 2.9. Aligned wi h SGDs The p oduc may help in he ad ance o socie y owa ds sus ainabili y. The a ge o he main p oduc should be aligned wi h one o se e al o he SDGs. Humani y aces majo challenges ha a ec billions o li es. In he las 50 yea s he wo ld’s popula ion has doubled om 3.8 billion o 7.8 billion people. The ounda ions o sus ainabili y we e ou lined in he epo Wo ld Commission on En i onmen and De elopmen in 1987 [41]. Fa om ocusing only on he classical de ini ion ha e e s o he i s line o he epo , he e m sus ainabili y is e y deep and di icul o unde s and and o de ine clea ly. I is linked o he wel a e s a e wi h i s needs, aspi a ions and he indi idual in e p e a ion o each o hem [42]. These ideas ha e been ansla ed o e he yea s in o a ious join global ac ions, such as he millennium goals. Howe e , i was no un il 2015 wi h he es ablishmen o he 17 Sus ainable De elopmen Goals (SDGs) ha he e has been a eal ake-o and a global unde s anding, no only by c ea o s, bu also by companies, media and public opinion [43]. So much so ha clea e e ences o he di e en goals can now be ound in p ac ically all p oduc s, p ocesses and o ganisa ions. F om a simplis ic poin o iew, he wel a e s a e, i s needs, a e sa is ied h ough p oduc s (unde s anding p oduc in a global way). The inc ease in popula ion comes wi h an inc ease in he numbe o needs and he e o e an inc ease in he consump ion o p oduc s. The inhe en aspi a ion o imp o e he wel a e s a e o each indi idual also inc eases i . Chemis y and chemical enginee ing a e a he ounda ion o he c ea ion o a ious commodi ies: ood, medicines, cons uc ion, ans- po , communica ions, packaging, clo hing and o he s. Ca alysis and ca alys s ha e no only accele a ed he kine ics o eac ions a he mo- lecula le el, hey ha e se ed o accele a e he de elopmen o he wel a e socie y by gi ing uni e sal access o all hese p oduc s. Ca alysis has helped o educe he consump ion o aw ma e ials and ene gy and o a oid mo e oxic o dange ous p oduc ion ou es, o example. Some imes when we a e in ou labs ying o c ea e a new ca alys o imp o ing one o i s p ocesses we lose pe spec i e, we look oo close by zooming in. We a e e y ocused on educing he empe a u e by 1 ◦C o he p essu e by 1 ba o he amoun o ca alys by 1 mg o make i mo e sus ainable. Bu we ha e no s opped o hink abou wha his eally J. Ga cía-Se na e al. Ca alysis Today xxx (xxxx) xxx 5 means. Zooming ou will help us unde s and why ou ac ions in de eloping a ca alys con ibu e o imp o ed global sus ainabili y. And mo e impo - an ly i will gi e us ex a mo i a ion o con inuous imp o emen . Johnson Ma hey has de eloped his idea in i s GRI epo in which i analyses some o he global needs and explains i s s a egy a he p oduc de elopmen le el (ca alys s) o con ibu e globally [3]. Fo example, hey es ima e ha he demand o hyd ogen will inc ease en old in he coming yea s and p esen a po olio o ca aly ic echnologies o i s gene a ion. They a e also looking a scaling up uel cell p ocesses o elec ici y p oduc ion by hyd ogen con e sion. 2.10. Low impac subp oduc s Ca alys s should be designed o a oid subp oduc s o o minimise hei en i onmen al and economic impac . A oiding he o ma ion o undesi able side p oduc s p e en s he was e o chemicals, minimises he need o pu i ica ion s eps, a ec s he ene gy consump ion o subsequen sepa a ion p ocesses and makes he p ocesses mo e en i onmen ally iendly [13]. Ac ually, ca alys selec- i i y di ec ly de e mines he a omic economy o he ca aly ic p ocess. The e o e, he sma design o he e ogeneous ca alys s should imp o e hei selec i i y by a oiding he o ma ion o subp oduc s and/ o minimising hei en i onmen al and economic impac . Un o una ely, enhancemen o selec i i y is ypically achie ed a he expense o o e all ac i i y [45]. High ca alys selec i i y is achie ed by applying s a egies o coupling, decoupling o con inemen o adso p ion si es and ac i e si es o une he di usion ba ie and ac i- a ion ene gy ba ie in di e en ou es. Fo ins ance, undesi able si es on he su ace o he e ogeneous ca alys s a e o en blocked ia p e- ea men s wi h speci ic chemicals. This is he case o hyd oca bon e o ming ca alys s, which a e exposed o small amoun s o H 2 S be o e in oducing he c ude oil eeds. Sulphu selec i ely blocks he su ace si es o hyd oca bon hyd ogenolysis, a ec ing hose o skele al isom- e iza ion o a much lesse ex en [46]. Ano he example is he hyd o- genolysis o glyce ol o 1,2 – p opanodiol (1,2 – PDO) [47]. Ru/C ca alys s a e poo ly selec i e owa ds he a ge 1,2 – PDO achie ing a 12% selec i i y whe eas he main p oduc ob ained is e hylene glycol. Howe e , when he same ca alys is sul ona ed (Ru-S/C) he selec i i y o 1,2 – PDO g ea ly inc eases o 79%. A simila s a egy has been e- po ed o he selec i e hyd ogena ion o benzene o cyclohexene o e Ru-Zn ca alys s as a syn he ic ou e o ob ain nylon. A c i ical s ep in his eac ion is he undesi ed o ma ion o cyclohexane which is a mo e s able p oduc han cyclohexene. Hyd ophilic modi ica ion o he Ru-based ca alys is he mos e ec i e way o imp o e cyclohexene selec i i y [48]. The s agnan wa e laye o med o e he ca alys suppo is en iched in benzene whe eas cyclohexene ( he i s hyd o- gena ion p oduc ) quickly deso bs om i . This p ocess enables he u he p og ess o his eac ion and a oids addi ional hyd ogena ion o cyclohexene o cyclohexane since he di usion g adien d i es he mig a ion o he o me in o he aqueous phase. 2.11. Open da a and a i icial in elligence Sha ing ca aly ic da a and manu ac u ing echniques oge he wi h a i- icial in elligence (AI) may boos o new sus ainable ca alys s and applica ions. The a ailabili y o ca aly ic open da a om design, cha ac e isa ion, ope a ional a iables (p essu e, empe a u e, low a e, e c.), pe o - mance KPIs (e.g. con e sion, selec i i y, e c.) and kine ics will help in he imp o emen and design o u u e ca alys s and ca aly ic p ocesses. The use o a i icial in elligence elies on he a ailabili y o enough da a and high-quali y da a. A numbe o da abases a e now a ailable ela ed o ma e ial p op- e ies, c ys al s uc u es, ino ganic ma e ials, su ace eac ion ene ge ics and DFT calcula ions, 2D ma e ials, chemical eac ions on ca aly ic su aces and o he s [49]. T aining a p ope ML algo i hm wi h such da a ins an ly (e.g. 788 eac ion da a se ), ac i a ion ene gies can be es i- ma ed wi h 90% accu acy almos [50]. One ecen example can be ound in he web-based ca aly ic pla o m Ca alys Acquisi ion by Da a Science (CADS) p o iding managemen and analysis o da a and p edic ion o p ope ies [51]. 2.12. Ope ando and in-si u acking Measu ing he eal ins an aneous pe o mance o he ca alys a ele an eac ion condi ions will enable a be e op imisa ion o he ca alys s, hei p ocesses, and be e u u e designs. The knowledge o s uc u al cha ac e is ics o he ca alys , e.g. su - ace s uc u e, and he main kine ic pe o mance pa ame e s in e ms o con e sion, eac i i y, selec i i y and yield a e key o a good ca alys design. In si u cha ac e isa ion has been ca ied ou du ing he las 60–70 yea s and p o ides aluable in o ma ion o he ca alys in i s wo king place, bu unde a con olled a mosphe e. Ope ando goes a beyond, measu ing simul aneously he ca alys cha ac e is ics and he p oduc scheme. Unde such app oach he ca alys s uc u e is obse ed unde eal o almos - eal condi ions o p essu e, empe a u e, low, eagen concen a ions, e c. which enables he connec ion be ween s uc u e and pe o mance o a highe le el. Almos any ype o ca alys can be analysed using ope ando, suppo ed o unsuppo ed, me al o me al oxides and o many ypes, such as mesopo ous silica, zeoli es, poly- oxome ala es, bulk mixed oxides, sulphides o e en so ben s in a as numbe o eac ion applica ions [52]. Ope ando is di icul o mas e . Acco ding o he da a ob ained om a Scopus da abase sea ch (i.e. “in si u+ca alysis” s. “ope - ando+ca alysis” o “in si u spec oscopy +ca alysis” s. “ope ando spec oscopy +ca a alysis”) yea a e yea mo e g oups a ound he wo ld a e joining in, wi h chemis y (34%), chemical enginee ing (27%) and ma e ials science (11%) being he a eas ha use i he mos . A he same ime, in si u analysis con inues o g ow and p o ide aluable in- o ma ion. Conside ing scien i ic publica ions, "in si u" is s ill be ween 4 and 9 imes highe in olume han "ope ando" in 2020 depending on whe he he wo d "spec oscopy" is added o he sea ch. The in si u echnique is mo e widely used, as i is unde s andable ha no all g oups in ol ed in ca alys cha ac e isa ion s udy he kine ics and speci ic e- ac ions in such de ail. The cu en man-made clima e change is s ongly ela ed o human ac i i ies and in pa icula o CO 2 emissions. Majo R&D e o s a e being made in CO 2 cap u e in se e al ways. Chemical CO 2 cap u e can be achie ed by non- educing s a egies (ca bona es, u eas, ca bama es, ca boxylic acids, e c.) and by educ i e s a egies (H 2 , CO, me hanol, o mic acid, e c.) [53]. Reduc i e s a egies a e complica ed, as hey equi e la ge amoun s o ene gy and/o mo e d as ic condi ions, so he oom o imp o emen is la ge. As an example, Yang e al. demons a ed he e ec i eness o single-a om he e ogeneous ca alysis in elec o- chemical CO 2 educ ion [54]. They iden i ied he ca aly ic ac i i y o single-Ni-a om, i.e. mono alen Ni(I), o he CO 2 educ ion using ope ando X- ay abso p ion and pho oelec on spec oscopy. Ope ando analysis allows a be e unde s anding o he p inciples o ca alysis and hus he possibili y o be e ca alys design. Cheng e al. ca ied ou a simila esea ch based on he deposi ion o he single-a om-Ni and o he me als on ni ogen-doped ca bon nano ubes [55]. In many cases, he e ms in si u and ope ando a e used in e - changeably, as G ey and Ta ascon poin ed ou [56]. They p esen a comp ehensi e analysis o in si u/ope a ing echniques used in elec- ochemis y o he design and analysis o mo e sus ainable ba e ies. In pa icula , how o imp o e cha ge and discha ge cycles. Reducing he amoun o ac i e me al equi ed o imp o ing he numbe o cycles a e clea examples. J. Ga cía-Se na e al. Ca alysis Today xxx (xxxx) xxx 6 3. Conclusions The wo ld is accele a ing and mo e and mo e p oduc s a e being used e e y day. Chemis y and chemical enginee ing a e a he basis o he c ea ion and p oduc ion o hese p oduc s ha con ibu e o he wel a e socie y. Ce ainly, ca alysis is one o he echnologies ha can d i e he de elopmen and c ea ion o new p oduc s. A he a omic- molecula le el, ca alysis is able o educe he ene gy ba ie and e en elimina e i , making he mi acle possible. We ha e analyzed he bes and mos inno a i e p ac ices in ca alys design conside ing sus ainable chemis y, wi h he basis on he p inci- ples o g een chemis y and g een enginee ing. As a esul o ha we ha e compiled 12 basic p inciples ha may inspi e he imp o emen o c ea ion o new ca alys s conside ing he ac i e me als, he p oduc s c ea ed and enewable esou ces used, scalabili y, s abili y, as - induc ion and ci cula i y. We also ocus on compu e science o possible in silico design and e e y hing ela ed o da a and a i icial in elligence. Impo ance is gi en o biomimic y, ge ing inspi a ion om na u e’s designs and ope ando echniques o un eil he eal ca alys in ac ion. Finally, he pu pose o all his should be based on g and chal- lenges such as he Sus ainable De elopmen Goals. We can ce ainly say ha ca alysis is an exponen ial echnology ( ollowing Pe e Diamandis’ hinking). Ma hema ically, because i is based on A henius’ law, bu p ac ically because i a ec s mo e han a billion people e e y day. CRediT au ho ship con ibu ion s a emen Juan Ga cía-Se na: Concep ualiza ion, Me hodology, Visualiza ion (g aphical abs ac ), W i ing – o iginal d a , W i ing – e iew & edi ing and Supe ision. Raúl Pi˜ ne o-He nanz: W i ing – o iginal d a , W i ing – e iew & edi ing. Desi ´ ee Du ´ an-Ma ín: W i ing – o iginal d a , W i ing – e iew & edi ing. Decla a ion o Compe ing In e es The au ho s decla e ha hey ha e no known compe ing inancial in e es s o pe sonal ela ionships ha could ha e appea ed o in luence he wo k epo ed in his pape . Acknowledgemen s D . Juan Ga cía-Se na hanks he Agencia Es a al de In es igaci´ on and FEDER Funds EU o unding p ojec e e ence PID2019-105975GB- I00 (MICINN/FEDER, EU), and Jun a de Cas illa y Le´ on - Conseje ía de Educaci´ on and FEDER Funds p ojec e e ence CLU-2019-04. Re e ences [1] P.T. Anas as, J.C. Wa ne , G een Chemis y: Theo y and P ac ice, Ox o d Uni e si y P ess, 1998. [2] D.L. T imm, Economic impo ance o ca alys s, in: J. Hagen (Ed.), Ind. Ca al. A P ac . App oach, 2015 h ed., Wiley-VCH, 1980, pp. 31–36, h ps://doi.o g/ 10.1038/122802b0. [3] Johnson Ma hey, Annual Repo and Accoun s - GRI epo (2019). h ps://ma he y.com/-/media/ iles/annual- epo -2019/annual- epo -2019-secu ed.pd . [4] T.P. Umile, Ca alysis o sus ainabili y: Goals, challenges, and impac s, 2015. [5] J.R. Ludwig, C.S. Schindle , Ca alys : sus ainable ca alysis, Chemis y 2 (2017), h ps://doi.o g/10.1016/j.chemp .2017.02.014. [6] K.S. Ego o a, V.P. Ananiko , Toxici y o me al compounds: knowledge and my hs, O ganome allics 36 (2017) 4071–4090, h ps://doi.o g/10.1021/acs. o ganome .7b00605. [7] M. Bys zanowska, P. Pe ko , M. Tobiszewski, Ranking o he e ogeneous ca alys s me als by hei g eenness, ACS Sus ain. Chem. Eng. 7 (2019) 18434–18443, h ps://doi.o g/10.1021/acssuschemeng.9b04230. [8] J. Xu, X.-M. Cao, P. Hu, Pe spec i e on compu a ional eac ion p edic ion using machine lea ning me hods in he e ogeneous ca alysis, Phys. Chem. Chem. Phys. 23 (2021) 11155–11179, h ps://doi.o g/10.1039/d1cp01349a. [9] F. S ud , G and challenges in compu a ional ca alysis, F on . Ca al. 1 (2021) 1–4, h ps://doi.o g/10.3389/ c ls.2021.658965. [10] C. S amp l, Su ace p ocesses and phase ansi ions om ab ini io a omis ic he modynamics and s a is ical mechanics, Ca al. Today 105 (2005) 17–35, h ps://doi.o g/10.1016/j.ca od.2005.04.015. [11] S. Saxena, T.S. Khan, F. Jalid, M. Ram eke, M.A. Haide , In silico high h oughpu sc eening o bime allic and single a om alloys using machine lea ning and ab ini io mic okine ic modelling, J. Ma e . Chem. A 8 (2020) 107–123, h ps://doi.o g/ 10.1039/c9 a07651d. [12] J.T. Mu h, P.G. Dixon, L. Woish, L.J. Gibson, J.A. Lewis, A chi ec ed cellula ce amics wi h ailo ed s i ness ia di ec oam w i ing, P oc. Na l. Acad. Sci. USA 114 (2017) 1832–1837, h ps://doi.o g/10.1073/PNAS.1616769114. [13] R. Zheng, Z. Liu, Y. Wang, Z. Xie, Indus ial ca alysis: s a egies o enhance selec i i y, Chin. J. Ca al. 41 (2020) 1032–1038, h ps://doi.o g/10.1016/S1872- 2067(20)63578-1. [14] S. Zhang, X.S. Li, B. Chen, X. Zhu, C. Shi, A.M. Zhu, CO oxida ion ac i i y a oom empe a u e o e Au/CeO2 ca alys s: disclosu e o induc ion pe iod and humidi y e ec , ACS Ca al. 4 (2014) 3481–3489, h ps://doi.o g/10.1021/cs500614 . [15] Y. Gu, P. Chen, X. Wang, Y. Lyu, W. Liu, X. Liu, Z. Yan, Ac i e si es and induc ion pe iod o Fe/ZSM-5 ca alys in me hane dehyd oa oma iza ion, ACS Ca al. 11 (2021) 6771–6786, h ps://doi.o g/10.1021/acsca al.1c01467. [16] U. Menon, M. Rahman, S.J. Kha ib, A c i ical li e a u e e iew o he ad ances in me hane dehyd oa oma iza ion o e mul i unc ional me al-p omo ed zeoli e ca alys s, Appl. Ca al. A Gen. 608 (2020), 117870, h ps://doi.o g/10.1016/J. APCATA.2020.117870. [17] J.A. Villo ia, M.C. Al a ez-Gal an, S.M. Al-Zah ani, P. Palmisano, S. Specchia, V. Specchia, J.L.G. Fie o, R.M. Na a o, Oxida i e e o ming o diesel uel o e LaCoO3 pe o ski e de i ed ca alys s: in luence o pe o ski e syn hesis me hod on ca alys p ope ies and pe o mance, Appl. Ca al. B En i on. 105 (2011) 276–288, h ps://doi.o g/10.1016/j.apca b.2011.04.010. [18] X. Liu, L. Chen, G. Qi, Enhanced SO2 cap u e pe o mance o MnO2 by doping wi h alkali me al ions o diesel emission con ol, Chem. Eng. Technol. 41 (2018) 1675–1681, h ps://doi.o g/10.1002/cea .201700542. [19] E.T.C. Vog , B.M. Weckhuysen, Fluid ca aly ic c acking: ecen de elopmen s on he g and old lady o zeoli e ca alysis, Chem. Soc. Re . 44 (2015) 7342–7370, h ps://doi.o g/10.1039/c5cs00376h. [20] J. Wa ne , The Mechanisms o Achie e a Ci cula Bioeconomy, 2013. [21] K. Chen, C.De Wu, Designed ab ica ion o biomime ic me al–o ganic amewo ks o ca aly ic applica ions, in: Coo d. Chem. Re . 378, 2019, pp. 445–465, h ps:// doi.o g/10.1016/j.cc .2018.01.016. [22] M. La ge on, Ae obic ca aly ic sys ems inspi ed by coppe amine oxidases: ecen de elopmen s and syn he ic applica ions, O g. Biomol. Chem. 15 (2017) 4722–4730, h ps://doi.o g/10.1039/c7ob00507e. [23] A. Ha , Ci cula economy: closing he ca alys loop wi h me al eclama ion om spen ca alys s, indus ial was e, was e shells and animal bones, Biomass Con e s. Bio e . 1 (2021) 1–16, h ps://doi.o g/10.1007/S13399-021-01942-8. [24] B. De a ajan, R. Sa a anakuma , S. Si alingam, V. Bhu aneswa i, F. Ka imi, L. Rajeshkuma , Ca alys de i ed om was es o bio uel p oduc ion: a c i ical e iew and pa en landscape analysis, Appl. Nanosci. 1 (2021) 1–25, h ps://doi. o g/10.1007/s13204-021-01948-8. [25] B. Alonso-Fa i˜ nas, M. Rod íguez-Gal´ an, C. A enas, F. A oyo To al o, C. Lei a, Sus ainable managemen o spen luid ca aly ic c acking ca alys om a ci cula economy app oach, Was e Manag. 110 (2020) 10–19, h ps://doi.o g/10.1016/J. WASMAN.2020.04.046. [26] S.K. Padama a, A.S. Yasinskiy, P.V. Polyako , E.A. Pa lo , D.Y. Va yukhin, Reco e y o noble me als om spen ca alys s: a e iew, Me all. Ma e . T ans. B 51 (2020) 2413–2435, h ps://doi.o g/10.1007/S11663-020-01913-W, 2020 515. [27] V. Fo i, C.P. Bald´ e, R. Kueh , G. Bel, Su ge in Global E-was e, up 21 pe cen in 5 yea s, Glob. E-Was e Moni . 2020. (2020). 〈h ps://globalewas e.o g/news/su ge-global-was e/〉(accessed Sep embe 27, 2021). [28] D. Rod íguez-Pad ´ on, Z.A. ALO hman, S.M. Osman, R. Luque, Recycling elec onic was e: p ospec s in g een ca alys s design, Cu . Opin. G een Sus ain. Chem. 25 (2020), 100357, h ps://doi.o g/10.1016/J.COGSC.2020.100357. [29] E. Hsu, K. Ba mak, A.C. Wes , A.H.A. Pa k, Ad ancemen s in he ea men and p ocessing o elec onic was e wi h sus ainabili y: a e iew o me al ex ac ion and eco e y echnologies, G een Chem. 21 (2019) 919–936, h ps://doi.o g/10.1039/ c8gc03688h. [30] A.J. Mu ay, J. Zhu, J. Wood, L.E. Macaskie, A no el bio e ine y: bio eco e y o p ecious me als om spen au omo i e ca alys leacha es in o new ca alys s e ec i e in me al educ ion and in he hyd ogena ion o 2-pen yne, Mine . Eng. 113 (2017) 102–108, h ps://doi.o g/10.1016/J.MINENG.2017.08.011. [31] S. Cos is, K.K. Muelle , L. Coude , C.M. Neculi a, N. Reynie , J.F. Blais, Reco e y po en ial o a e ea h elemen s om mining and indus ial esidues: a e iew and cases s udies, J. Geochem. Explo . 221 (2021), 106699, h ps://doi.o g/10.1016/J. GEXPLO.2020.106699. [32] H. Rueda, M. A enas, R. Va gas-Balda, S. Blanco, P. Del as o, P oduc ion o a nickel-based ca alys o u ea elec ooxida ion using spen ba e ies as aw ma e ial: elec ochemical syn hesis and implica ions om a ci cula economy s and-poin , Sus ain. Ma e . Technol. 29 (2021), e00296, h ps://doi.o g/10.1016/ J.SUSMAT.2021.E00296. [33] P.E. Nwankwo , I.O. Onuigbo, C.E. Chukwuneke, M.F. Yahaya, B.O. Agboola, W. J. Jahng, Syn hesis o gasoline ange uels by he ca aly ic c acking o was e plas ics using i anium dioxide and zeoli e, In . J. Ene gy En i on. Eng. 12 (2020) 77–86, h ps://doi.o g/10.1007/S40095-020-00359-9, 2020 121. [34] M. A es a, A. Dibenede o, E. Qua an a, S a e o he a and pe spec i es in ca aly ic p ocesses o CO 2 con e sion in o chemicals and uels: he dis inc i e con ibu ion o chemical ca alysis and bio echnology, J. Ca al. 343 (2016) 2–45, h ps://doi.o g/10.1016/J.JCAT.2016.04.003. J. Ga cía-Se na e al. Ca alysis Today xxx (xxxx) xxx 7 [35] S. Roy, A. Che e o an, S.C. Pe e , The mochemical CO 2 hyd ogena ion o single ca bon p oduc s: scien i ic and echnological challenges, ACS Ene gy Le . 3 (2018) 1938–1966, h ps://doi.o g/10.1021/ACSENERGYLETT.8B00740. [36] H. He, R. Li, Z. Yang, L. Chai, L. Jin, S.I. Alhassan, L. Ren, H. Wang, L. Huang, P epa a ion o MOFs and MOFs de i ed ma e ials and hei ca aly ic applica ion in ai pollu ion: a e iew, Ca al. Today 375 (2021) 10–29, h ps://doi.o g/10.1016/J. CATTOD.2020.02.033. [37] O. Coulembie , P. Deg´ ee, J.L. Hed ick, P. Dubois, F om con olled ing-opening polyme iza ion o biodeg adable alipha ic polyes e : especially poly(β-malic acid) de i a i es, P og. Polym. Sci. 31 (2006) 723–747, h ps://doi.o g/10.1016/J. PROGPOLYMSCI.2006.08.004. [38] C. Cla e , M. Bin Yeamin, M. Regue o, A.M. Masdeu-Bul ´ o, Recen ad ances in he use o ca alys s based on na u al p oduc s o he con e sion o CO 2 in o cyclic ca bona es, G een Chem. 22 (2020) 7665–7706, h ps://doi.o g/10.1039/ D0GC01870H. [39] M.K. Shahid, A. Ba ool, A. Kashi , M.H. Nawaz, M. Aslam, N. Iqbal, Y. Choi, Bio uels and bio e ine ies: de elopmen , applica ion and u u e pe spec i es emphasizing he en i onmen al and economic aspec s, J. En i on. Manag. 297 (2021), 113268, h ps://doi.o g/10.1016/j.jen man.2021.113268. [40] P. Khem hong, C. Yimsukanan, T. Na kkun, A. S i a, T. Wi oon, S. Pongchaiphol, S. Kia phuengpo n, K. Faungnawakij, Ad ances in ca aly ic p oduc ion o alue- added biochemicals and bio uels ia u u al pla o m de i ed lignocellulosic biomass, Biomass Bioene gy 148 (2021), 106033, h ps://doi.o g/10.1016/j. biombioe.2021.106033. [41] Wo ld Commission on En i onmen and De elopmen , Ou Common Fu u e: Repo o he Wo ld Commission, 1987. 〈h ps://sus ainablede elopmen .un. o g/con en /documen s/5987ou -common- u u e.pd 〉. [42] J. Ga cía-Se na, L. P´ e ez-Ba ig´ on, M.J. Coce o, New ends o design owa ds sus ainabili y in chemical enginee ing: g een enginee ing, Chem. Eng. J. 133 (2007) 7–30, h ps://doi.o g/10.1016/j.cej.2007.02.028. [43] Uni ed Na ions, The 17 goals, (2015). 〈h ps://sdgs.un.o g/goals〉(accessed Sep embe 26, 2021). [45] Z. Weng, F. Zae a, Inc ease in ac i i y and selec i i y in ca alysis ia su ace modi ica ion wi h sel -assembled monolaye s, J. Phys. Chem. C 118 (2014) 3672–3679, h ps://doi.o g/10.1021/jp412364d. [46] Z. Pa´ al, M. Muhle , K. Ma usek, Sul ided P ca alys s, J. Ca al. 175 (1998) 245–251, h ps://doi.o g/10.1006/jca .1998.1995. [47] C. Mon assie , J.C. M´ en´ ezo, L.C. Hoang, C. Renaud, J. Ba bie , Aqueous polyol con e sions on u henium and on sul u -modi ied u henium, J. Mol. Ca al. 70 (1991) 99–110, h ps://doi.o g/10.1016/0304-5102(91)85008-P. [48] H. Sun, W. Guo, X. Zhou, Z. Chen, Z. Liu, S. Liu, P og ess in Ru-based amo phous alloy ca alys s o selec i e hyd ogena ion o benzene o cyclohexene, Cuihua Xuebao/Chin. J. Ca al. 32 (2011) 1–16, h ps://doi.o g/10.1016/s1872-2067(10) 60154-4. [49] P. Schlexe Lamou eux, K.T. Win he , J.A. Ga ido To es, V. S eibel, M. Zhao, M. Bajdich, F. Abild-Pede sen, T. Bligaa d, Machine lea ning o compu a ional he e ogeneous ca alysis, ChemCa Chem 11 (2019) 3581–3601, h ps://doi.o g/ 10.1002/cc c.201900595. [50] W. Yang, T.T. Fidelis, W.-H. Sun, Machine lea ning in ca alysis, om p oposal o p ac icing, ACS Omega 5 (2020) 83–88, h ps://doi.o g/10.1021/ acsomega.9b03673. [51] J. Fujima, Y. Tanaka, I. Miyaza o, L. Takahashi, K. Takahashi, Ca alys acquisi ion by da a science (CADS): a web-based ca alys in o ma ics pla o m o disco e ing ca alys s, Reac . Chem. Eng. 5 (2020) 903–911, h ps://doi.o g/10.1039/ d0 e00098a. [52] A. Chak aba i, M.E. Fo d, D. G ego y, R. Hu, C.J. Ke u akis, S. Lwin, Y. Tang, Z. Yang, M. Zhu, M.A. Ba˜ na es, I.E. Wachs, A decade+o ope ando spec oscopy s udies, Ca al. Today 283 (2017) 27–53, h ps://doi.o g/10.1016/j. ca od.2016.12.012. [53] A.J. Ma ín, G.O. La az´ abal, J. P´ e ez-Ramí ez, Towa ds sus ainable uels and chemicals h ough he elec ochemical educ ion o CO 2 : lessons om wa e elec olysis, G een Chem. 17 (2015) 5114–5130, h ps://doi.o g/10.1039/ C5GC01893E. [54] H. Bin Yang, S.F. Hung, S. Liu, K. Yuan, S. Miao, L. Zhang, X. Huang, H.Y. Wang, W. Cai, R. Chen, J. Gao, X. Yang, W. Chen, Y. Huang, H.M. Chen, C.M. Li, T. Zhang, B. Liu, A omically dispe sed Ni(i) as he ac i e si e o elec ochemical CO 2 educ ion, Na . Ene gy 3 (2018) 140–147, h ps://doi.o g/10.1038/s41560-017- 0078-8. [55] Y. Cheng, S. Zhao, B. Johannessen, J.P. Vede , M. Saunde s, M.R. Rowles, M. Cheng, C. Liu, M.F. Chisholm, R. De Ma co, H.M. Cheng, S.Z. Yang, S.P. Jiang, A omically dispe sed ansi ion me als on ca bon nano ubes wi h ul ahigh loading o selec i e elec ochemical ca bon dioxide educ ion, Ad . Ma e . 30 (2018) 1–7, h ps://doi.o g/10.1002/adma.201706287. [56] C.P. G ey, J.M. Ta ascon, Sus ainabili y and in si u moni o ing in ba e y de elopmen , Na . Ma e . 16 (2016) 45–56, h ps://doi.o g/10.1038/nma 4777. J. Ga cía-Se na e al.